EP1279725A2 - Method of production of bleach activator granulate - Google Patents
Method of production of bleach activator granulate Download PDFInfo
- Publication number
- EP1279725A2 EP1279725A2 EP02016000A EP02016000A EP1279725A2 EP 1279725 A2 EP1279725 A2 EP 1279725A2 EP 02016000 A EP02016000 A EP 02016000A EP 02016000 A EP02016000 A EP 02016000A EP 1279725 A2 EP1279725 A2 EP 1279725A2
- Authority
- EP
- European Patent Office
- Prior art keywords
- rounder
- extrudates
- weight
- bleach activator
- sec
- 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.)
- Withdrawn
Links
- 238000000034 method Methods 0.000 title claims abstract description 29
- 239000012190 activator Substances 0.000 title claims abstract description 16
- 239000007844 bleaching agent Substances 0.000 title claims abstract description 15
- 239000008187 granular material Substances 0.000 title claims description 30
- 238000004519 manufacturing process Methods 0.000 title description 8
- 239000000203 mixture Substances 0.000 claims abstract description 14
- 229920001515 polyalkylene glycol Polymers 0.000 claims abstract description 7
- 125000000129 anionic group Chemical group 0.000 claims abstract description 4
- 238000002360 preparation method Methods 0.000 claims abstract description 3
- 229920001223 polyethylene glycol Polymers 0.000 claims description 16
- FBUKVWPVBMHYJY-UHFFFAOYSA-N nonanoic acid Chemical compound CCCCCCCCC(O)=O FBUKVWPVBMHYJY-UHFFFAOYSA-N 0.000 claims description 14
- 235000014113 dietary fatty acids Nutrition 0.000 claims description 7
- 229930195729 fatty acid Natural products 0.000 claims description 7
- 239000000194 fatty acid Substances 0.000 claims description 7
- 239000003945 anionic surfactant Substances 0.000 claims description 6
- 150000004665 fatty acids Chemical class 0.000 claims description 6
- 239000002736 nonionic surfactant Substances 0.000 claims description 5
- 239000007789 gas Substances 0.000 claims description 4
- 239000002202 Polyethylene glycol Substances 0.000 claims description 3
- 239000003795 chemical substances by application Substances 0.000 claims description 3
- 238000001816 cooling Methods 0.000 claims description 3
- 229940057838 polyethylene glycol 4000 Drugs 0.000 claims description 3
- 150000008055 alkyl aryl sulfonates Chemical class 0.000 claims 1
- 239000000112 cooling gas Substances 0.000 claims 1
- 239000002245 particle Substances 0.000 abstract description 24
- 238000009826 distribution Methods 0.000 abstract description 9
- 239000004094 surface-active agent Substances 0.000 abstract description 2
- 238000005469 granulation Methods 0.000 abstract 1
- 230000003179 granulation Effects 0.000 abstract 1
- -1 alkali metal salts Chemical class 0.000 description 11
- 239000003599 detergent Substances 0.000 description 8
- 238000000465 moulding Methods 0.000 description 7
- 238000005299 abrasion Methods 0.000 description 6
- 239000000428 dust Substances 0.000 description 6
- BGRWYDHXPHLNKA-UHFFFAOYSA-N Tetraacetylethylenediamine Chemical compound CC(=O)N(C(C)=O)CCN(C(C)=O)C(C)=O BGRWYDHXPHLNKA-UHFFFAOYSA-N 0.000 description 5
- 239000000654 additive Substances 0.000 description 5
- RTZKZFJDLAIYFH-UHFFFAOYSA-N ether Substances CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 5
- 239000004014 plasticizer Substances 0.000 description 5
- 159000000000 sodium salts Chemical class 0.000 description 5
- 239000012530 fluid Substances 0.000 description 4
- 238000009472 formulation Methods 0.000 description 4
- 230000002093 peripheral effect Effects 0.000 description 4
- 238000003860 storage Methods 0.000 description 4
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 description 3
- 229920001030 Polyethylene Glycol 4000 Polymers 0.000 description 3
- 125000000217 alkyl group Chemical group 0.000 description 3
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 description 3
- 239000012459 cleaning agent Substances 0.000 description 3
- 150000001875 compounds Chemical class 0.000 description 3
- 229920001451 polypropylene glycol Polymers 0.000 description 3
- 150000003839 salts Chemical class 0.000 description 3
- 239000002904 solvent Substances 0.000 description 3
- 150000003467 sulfuric acid derivatives Chemical class 0.000 description 3
- VNEUMNOZRFLRPI-UHFFFAOYSA-N 4-nonanoyloxybenzenesulfonic acid Chemical compound CCCCCCCCC(=O)OC1=CC=C(S(O)(=O)=O)C=C1 VNEUMNOZRFLRPI-UHFFFAOYSA-N 0.000 description 2
- AEMRFAOFKBGASW-UHFFFAOYSA-N Glycolic acid Chemical compound OCC(O)=O AEMRFAOFKBGASW-UHFFFAOYSA-N 0.000 description 2
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 2
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 2
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 2
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Chemical compound NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 description 2
- 239000001083 [(2R,3R,4S,5R)-1,2,4,5-tetraacetyloxy-6-oxohexan-3-yl] acetate Substances 0.000 description 2
- 239000004480 active ingredient Substances 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 238000004140 cleaning Methods 0.000 description 2
- 239000000470 constituent Substances 0.000 description 2
- 230000003247 decreasing effect Effects 0.000 description 2
- 150000002148 esters Chemical class 0.000 description 2
- 150000002191 fatty alcohols Chemical class 0.000 description 2
- 230000002349 favourable effect Effects 0.000 description 2
- IPCSVZSSVZVIGE-UHFFFAOYSA-N hexadecanoic acid Chemical compound CCCCCCCCCCCCCCCC(O)=O IPCSVZSSVZVIGE-UHFFFAOYSA-N 0.000 description 2
- JVTAAEKCZFNVCJ-UHFFFAOYSA-N lactic acid Chemical compound CC(O)C(O)=O JVTAAEKCZFNVCJ-UHFFFAOYSA-N 0.000 description 2
- 239000007788 liquid Substances 0.000 description 2
- 239000000314 lubricant Substances 0.000 description 2
- 229910052751 metal Inorganic materials 0.000 description 2
- 239000002184 metal Substances 0.000 description 2
- MGFYIUFZLHCRTH-UHFFFAOYSA-N nitrilotriacetic acid Chemical compound OC(=O)CN(CC(O)=O)CC(O)=O MGFYIUFZLHCRTH-UHFFFAOYSA-N 0.000 description 2
- 229920000151 polyglycol Polymers 0.000 description 2
- 239000010695 polyglycol Substances 0.000 description 2
- 239000000843 powder Substances 0.000 description 2
- 238000007493 shaping process Methods 0.000 description 2
- RPACBEVZENYWOL-XFULWGLBSA-M sodium;(2r)-2-[6-(4-chlorophenoxy)hexyl]oxirane-2-carboxylate Chemical compound [Na+].C=1C=C(Cl)C=CC=1OCCCCCC[C@]1(C(=O)[O-])CO1 RPACBEVZENYWOL-XFULWGLBSA-M 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 238000005406 washing Methods 0.000 description 2
- 239000004711 α-olefin Substances 0.000 description 2
- WRIDQFICGBMAFQ-UHFFFAOYSA-N (E)-8-Octadecenoic acid Natural products CCCCCCCCCC=CCCCCCCC(O)=O WRIDQFICGBMAFQ-UHFFFAOYSA-N 0.000 description 1
- VBDFPNJHQVMOPA-UHFFFAOYSA-N 2-acetyloxybenzenesulfonic acid Chemical compound CC(=O)OC1=CC=CC=C1S(O)(=O)=O VBDFPNJHQVMOPA-UHFFFAOYSA-N 0.000 description 1
- LQJBNNIYVWPHFW-UHFFFAOYSA-N 20:1omega9c fatty acid Natural products CCCCCCCCCCC=CCCCCCCCC(O)=O LQJBNNIYVWPHFW-UHFFFAOYSA-N 0.000 description 1
- YTWUZAQZEVOPGG-UHFFFAOYSA-N 3-acetyl-1-phenylimidazolidine-2,4-dione Chemical compound O=C1N(C(=O)C)C(=O)CN1C1=CC=CC=C1 YTWUZAQZEVOPGG-UHFFFAOYSA-N 0.000 description 1
- QSBYPNXLFMSGKH-UHFFFAOYSA-N 9-Heptadecensaeure Natural products CCCCCCCC=CCCCCCCCC(O)=O QSBYPNXLFMSGKH-UHFFFAOYSA-N 0.000 description 1
- VCXQWGFEOMPTEC-UHFFFAOYSA-N CC(CCCCC(=O)OC=1C=CC=C(C=1)S(=O)(=O)O)(C)C Chemical compound CC(CCCCC(=O)OC=1C=CC=C(C=1)S(=O)(=O)O)(C)C VCXQWGFEOMPTEC-UHFFFAOYSA-N 0.000 description 1
- 235000013162 Cocos nucifera Nutrition 0.000 description 1
- 244000060011 Cocos nucifera Species 0.000 description 1
- FBPFZTCFMRRESA-FSIIMWSLSA-N D-Glucitol Natural products OC[C@H](O)[C@H](O)[C@@H](O)[C@H](O)CO FBPFZTCFMRRESA-FSIIMWSLSA-N 0.000 description 1
- 102000004190 Enzymes Human genes 0.000 description 1
- 108090000790 Enzymes Proteins 0.000 description 1
- AEMRFAOFKBGASW-UHFFFAOYSA-M Glycolate Chemical compound OCC([O-])=O AEMRFAOFKBGASW-UHFFFAOYSA-M 0.000 description 1
- 241001272567 Hominoidea Species 0.000 description 1
- 101500021084 Locusta migratoria 5 kDa peptide Proteins 0.000 description 1
- ZQPPMHVWECSIRJ-UHFFFAOYSA-N Oleic acid Natural products CCCCCCCCC=CCCCCCCCC(O)=O ZQPPMHVWECSIRJ-UHFFFAOYSA-N 0.000 description 1
- 239000005642 Oleic acid Substances 0.000 description 1
- 229910019142 PO4 Inorganic materials 0.000 description 1
- 235000021314 Palmitic acid Nutrition 0.000 description 1
- SCKXCAADGDQQCS-UHFFFAOYSA-N Performic acid Chemical compound OOC=O SCKXCAADGDQQCS-UHFFFAOYSA-N 0.000 description 1
- 239000004721 Polyphenylene oxide Substances 0.000 description 1
- OFOBLEOULBTSOW-UHFFFAOYSA-N Propanedioic acid Natural products OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 0.000 description 1
- 235000021355 Stearic acid Nutrition 0.000 description 1
- KDYFGRWQOYBRFD-UHFFFAOYSA-N Succinic acid Natural products OC(=O)CCC(O)=O KDYFGRWQOYBRFD-UHFFFAOYSA-N 0.000 description 1
- ZJCCRDAZUWHFQH-UHFFFAOYSA-N Trimethylolpropane Chemical compound CCC(CO)(CO)CO ZJCCRDAZUWHFQH-UHFFFAOYSA-N 0.000 description 1
- 229910021536 Zeolite Inorganic materials 0.000 description 1
- UAOKXEHOENRFMP-ZJIFWQFVSA-N [(2r,3r,4s,5r)-2,3,4,5-tetraacetyloxy-6-oxohexyl] acetate Chemical compound CC(=O)OC[C@@H](OC(C)=O)[C@@H](OC(C)=O)[C@H](OC(C)=O)[C@@H](OC(C)=O)C=O UAOKXEHOENRFMP-ZJIFWQFVSA-N 0.000 description 1
- ZYPMNZKYVVSXOJ-YNEHKIRRSA-N [(2r,3s,4r)-2,3,4-triacetyloxy-5-oxopentyl] acetate Chemical compound CC(=O)OC[C@@H](OC(C)=O)[C@H](OC(C)=O)[C@@H](OC(C)=O)C=O ZYPMNZKYVVSXOJ-YNEHKIRRSA-N 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 230000000996 additive effect Effects 0.000 description 1
- 229910052783 alkali metal Inorganic materials 0.000 description 1
- 125000002877 alkyl aryl group Chemical group 0.000 description 1
- 150000005215 alkyl ethers Chemical class 0.000 description 1
- 150000008051 alkyl sulfates Chemical class 0.000 description 1
- 150000001412 amines Chemical class 0.000 description 1
- 150000001414 amino alcohols Chemical class 0.000 description 1
- 150000003863 ammonium salts Chemical class 0.000 description 1
- JXLHNMVSKXFWAO-UHFFFAOYSA-N azane;7-fluoro-2,1,3-benzoxadiazole-4-sulfonic acid Chemical compound N.OS(=O)(=O)C1=CC=C(F)C2=NON=C12 JXLHNMVSKXFWAO-UHFFFAOYSA-N 0.000 description 1
- 238000004061 bleaching Methods 0.000 description 1
- KDYFGRWQOYBRFD-NUQCWPJISA-N butanedioic acid Chemical compound O[14C](=O)CC[14C](O)=O KDYFGRWQOYBRFD-NUQCWPJISA-N 0.000 description 1
- 239000004202 carbamide Substances 0.000 description 1
- 125000004432 carbon atom Chemical group C* 0.000 description 1
- 150000007942 carboxylates Chemical class 0.000 description 1
- 150000001735 carboxylic acids Chemical class 0.000 description 1
- 239000003054 catalyst Substances 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 229910017052 cobalt Inorganic materials 0.000 description 1
- 239000010941 cobalt Substances 0.000 description 1
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 description 1
- 239000008139 complexing agent Substances 0.000 description 1
- 238000007906 compression Methods 0.000 description 1
- 230000006835 compression Effects 0.000 description 1
- 238000005520 cutting process Methods 0.000 description 1
- 230000007423 decrease Effects 0.000 description 1
- 239000000645 desinfectant Substances 0.000 description 1
- 150000004844 dioxiranes Chemical class 0.000 description 1
- HNPSIPDUKPIQMN-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Al]O[Al]=O HNPSIPDUKPIQMN-UHFFFAOYSA-N 0.000 description 1
- 238000004851 dishwashing Methods 0.000 description 1
- VFNGKCDDZUSWLR-UHFFFAOYSA-N disulfuric acid Chemical class OS(=O)(=O)OS(O)(=O)=O VFNGKCDDZUSWLR-UHFFFAOYSA-N 0.000 description 1
- 150000002170 ethers Chemical class 0.000 description 1
- 238000001125 extrusion Methods 0.000 description 1
- 150000002193 fatty amides Chemical class 0.000 description 1
- 150000002334 glycols Chemical class 0.000 description 1
- 230000001771 impaired effect Effects 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- SUMDYPCJJOFFON-UHFFFAOYSA-N isethionic acid Chemical class OCCS(O)(=O)=O SUMDYPCJJOFFON-UHFFFAOYSA-N 0.000 description 1
- QXJSBBXBKPUZAA-UHFFFAOYSA-N isooleic acid Natural products CCCCCCCC=CCCCCCCCCC(O)=O QXJSBBXBKPUZAA-UHFFFAOYSA-N 0.000 description 1
- 150000002576 ketones Chemical class 0.000 description 1
- 239000004310 lactic acid Substances 0.000 description 1
- 235000014655 lactic acid Nutrition 0.000 description 1
- VZCYOOQTPOCHFL-UPHRSURJSA-N maleic acid Chemical compound OC(=O)\C=C/C(O)=O VZCYOOQTPOCHFL-UPHRSURJSA-N 0.000 description 1
- 239000011976 maleic acid Substances 0.000 description 1
- WPBNNNQJVZRUHP-UHFFFAOYSA-L manganese(2+);methyl n-[[2-(methoxycarbonylcarbamothioylamino)phenyl]carbamothioyl]carbamate;n-[2-(sulfidocarbothioylamino)ethyl]carbamodithioate Chemical compound [Mn+2].[S-]C(=S)NCCNC([S-])=S.COC(=O)NC(=S)NC1=CC=CC=C1NC(=S)NC(=O)OC WPBNNNQJVZRUHP-UHFFFAOYSA-L 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 239000000155 melt Substances 0.000 description 1
- 150000004682 monohydrates Chemical class 0.000 description 1
- WQEPLUUGTLDZJY-UHFFFAOYSA-N n-Pentadecanoic acid Natural products CCCCCCCCCCCCCCC(O)=O WQEPLUUGTLDZJY-UHFFFAOYSA-N 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
- ZQPPMHVWECSIRJ-KTKRTIGZSA-N oleic acid Chemical compound CCCCCCCC\C=C/CCCCCCCC(O)=O ZQPPMHVWECSIRJ-KTKRTIGZSA-N 0.000 description 1
- 150000004843 oxaziridines Chemical class 0.000 description 1
- 238000005453 pelletization Methods 0.000 description 1
- 239000002304 perfume Substances 0.000 description 1
- 150000004965 peroxy acids Chemical class 0.000 description 1
- 235000021317 phosphate Nutrition 0.000 description 1
- 229920003023 plastic Polymers 0.000 description 1
- 239000004033 plastic Substances 0.000 description 1
- 229920000570 polyether Polymers 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 229920002451 polyvinyl alcohol Polymers 0.000 description 1
- 235000019422 polyvinyl alcohol Nutrition 0.000 description 1
- 229920000036 polyvinylpyrrolidone Polymers 0.000 description 1
- 235000013855 polyvinylpyrrolidone Nutrition 0.000 description 1
- 239000012048 reactive intermediate Substances 0.000 description 1
- 230000009257 reactivity Effects 0.000 description 1
- WBHHMMIMDMUBKC-XLNAKTSKSA-N ricinelaidic acid Chemical compound CCCCCC[C@@H](O)C\C=C\CCCCCCCC(O)=O WBHHMMIMDMUBKC-XLNAKTSKSA-N 0.000 description 1
- 229960003656 ricinoleic acid Drugs 0.000 description 1
- FEUQNCSVHBHROZ-UHFFFAOYSA-N ricinoleic acid Natural products CCCCCCC(O[Si](C)(C)C)CC=CCCCCCCCC(=O)OC FEUQNCSVHBHROZ-UHFFFAOYSA-N 0.000 description 1
- 238000005204 segregation Methods 0.000 description 1
- 239000000377 silicon dioxide Substances 0.000 description 1
- PHIMXFJEDZOCMI-UHFFFAOYSA-M sodium;2-hexanoyloxy-3,4,5-trimethylbenzenesulfonate Chemical compound [Na+].CCCCCC(=O)OC1=C(C)C(C)=C(C)C=C1S([O-])(=O)=O PHIMXFJEDZOCMI-UHFFFAOYSA-M 0.000 description 1
- OVONNAXAHAIEDF-UHFFFAOYSA-M sodium;4-benzoyloxybenzenesulfonate Chemical compound [Na+].C1=CC(S(=O)(=O)[O-])=CC=C1OC(=O)C1=CC=CC=C1 OVONNAXAHAIEDF-UHFFFAOYSA-M 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 239000000600 sorbitol Substances 0.000 description 1
- 239000008117 stearic acid Substances 0.000 description 1
- 239000010902 straw Substances 0.000 description 1
- 150000003871 sulfonates Chemical class 0.000 description 1
- 150000004685 tetrahydrates Chemical class 0.000 description 1
- VZCYOOQTPOCHFL-UHFFFAOYSA-N trans-butenedioic acid Natural products OC(=O)C=CC(O)=O VZCYOOQTPOCHFL-UHFFFAOYSA-N 0.000 description 1
- 229910052723 transition metal Inorganic materials 0.000 description 1
- 150000003624 transition metals Chemical class 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
- 239000010457 zeolite Substances 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
- C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
- C11D11/00—Special methods for preparing compositions containing mixtures of detergents
- C11D11/0082—Special methods for preparing compositions containing mixtures of detergents one or more of the detergent ingredients being in a liquefied state, e.g. slurry, paste or melt, and the process resulting in solid detergent particles such as granules, powders or beads
-
- C—CHEMISTRY; METALLURGY
- C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
- C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
- C11D1/00—Detergent compositions based essentially on surface-active compounds; Use of these compounds as a detergent
- C11D1/02—Anionic compounds
- C11D1/12—Sulfonic acids or sulfuric acid esters; Salts thereof
- C11D1/22—Sulfonic acids or sulfuric acid esters; Salts thereof derived from aromatic compounds
-
- C—CHEMISTRY; METALLURGY
- C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
- C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
- 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
-
- C—CHEMISTRY; METALLURGY
- C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
- C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
- C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
- C11D3/39—Organic or inorganic per-compounds
- C11D3/3902—Organic or inorganic per-compounds combined with specific additives
- C11D3/3905—Bleach activators or bleach catalysts
- C11D3/3907—Organic compounds
-
- C—CHEMISTRY; METALLURGY
- C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
- C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
- C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
- C11D3/39—Organic or inorganic per-compounds
- C11D3/3902—Organic or inorganic per-compounds combined with specific additives
- C11D3/3905—Bleach activators or bleach catalysts
- C11D3/3935—Bleach activators or bleach catalysts granulated, coated or protected
-
- C—CHEMISTRY; METALLURGY
- C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
- C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
- C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
- C11D3/39—Organic or inorganic per-compounds
- C11D3/3902—Organic or inorganic per-compounds combined with specific additives
- C11D3/3905—Bleach activators or bleach catalysts
- C11D3/3907—Organic compounds
- C11D3/3915—Sulfur-containing compounds
-
- C—CHEMISTRY; METALLURGY
- C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
- C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
- C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
- C11D3/39—Organic or inorganic per-compounds
- C11D3/3902—Organic or inorganic per-compounds combined with specific additives
- C11D3/3905—Bleach activators or bleach catalysts
- C11D3/3907—Organic compounds
- C11D3/3917—Nitrogen-containing compounds
Definitions
- the present invention relates to a process for the production of cylindrical to spherical extrudates which contain bleach activators, with defined particle sizes and narrow particle size distribution, which show low abrasion behavior and good flow behavior.
- EP 486 592 describes the production of extruded moldings, in which a solid and free-flowing premix is extruded using a plasticizer and / or lubricant when using relatively high pressures between about 25 and 200 bar.
- the strand has such a consistency that it can be cut directly to predetermined granule dimensions after exiting the hole shape by means of a cutting device.
- aqueous anionic surfactant pastes, aqueous polymer solutions and / or nonionic surfactants which are liquid at room temperature are mentioned as plasticizers and / or lubricants.
- the extruded moldings that can be produced in this way generally have a size of up to 2 cm, preferably up to 0.8 cm, the length-diameter ratio advantageously being between 1: 1 and 3: 1.
- bleach activators are advantageously packaged in the form of cylindrical extrudates in order to ensure compatibility with other detergent constituents and adequate storage stability. It is assumed that the highly reactive bleach activator is predominantly embedded in the interior of the cylindrical granulate and that the surface consists mainly of binding materials and plasticizers.
- the particle diameter should between 0.2 mm and 2 mm, preferably between 0.5 mm and 0.8 mm, the particle length in the range from 0.5 mm to 3.5 mm, ideally between 0.9 mm and 2.5 mm.
- the object of the invention was to produce cylindrical to spherical extrudates containing bleach activators for use in detergents or cleaning agents, which have a very narrow particle size distribution and at the same time have a low tendency to abrasion, low dust formation, favorable flow behavior and good dissolving behavior show during the washing and cleaning process.
- the invention relates to a process for the preparation of bleach activator granules, characterized in that a mixture of bleach activator, anionic or nonionic surfactant and polyalkylene glycol at temperatures from 40 to 120 ° C, preferably 60 to 80 ° C and a pressure of 5 to Extruded 30 bar and the extrudates obtained at a temperature of 40 to 120 ° C, preferably 60 to 80 ° C granulated on a rounder.
- bleach activators are, for example, N, N, N ', N'-tetraacetylethylenediamine (TAED), glucose pentaacetate (GPA), xylose tetraacetate (TAX), sodium 4-benzoyloxybenzenesulfonate (SBOBS), sodium trimethylhexanoyloxybenzenesulfonate (TetraCletyl) glycolate (STetraBluetylglycolate) (STETHacetylglycolate) (STHACSulfyl), tetra (tetraacetylglycolate) Tetraacetylcyanoic acid (TACA), di-N-acetyldimethylglyoxime (ADMG), 1-phenyl-3-acetylhydantoin (PAH), nonanoylcaprolactamphenylsulfonate ester (APES), nitrilotriacetate (NTA), preferably the sodium salt of nonan
- Preferred anionic surfactants are alkali metal salts, ammonium salts, amine salts and salts of amino alcohols of the following compounds: alkyl sulfates, alkyl ether sulfates, alkyl amide sulfates and ether sulfates, alkylaryl polyether sulfates, monoglyceride sulfates, alkyl sulfonate sulfates, alkyl amide sulfonates, alkyl aryl sulfonate sulfates, ⁇ -olefin sulfonates, ⁇ -olefin sulfates Alkylpolyglycerin carboxylates, alkyl phosphates, alkyl ether, alkyl sarcosinates, Alkylpolypeptidate, Alkylamidopolypeptidate, isethionates, taurates, alkyl polyglycol ether or fatty acids such as
- alkyl radical of all these compounds normally contains 8-32, preferably 8-22, carbon atoms.
- Linear straight-chain alkylbenzenesulfonates are particularly preferred, in particular with a C 8 -C 20 -, particularly preferably with a C 11-13 -alkyl group.
- Preferred nonionic surfactants are polyethoxylated, polypropoxylated or polyglycerolated ethers of fatty alcohols, polyethoxylated, polypropoxylated and polyglycerolized fatty acid esters, polyethoxylated esters of fatty acids and of sorbitol, polyethoxylated or polyglycerolated fatty amides.
- Polyalkylene glycols are polyethylene glycols, 1,2-polypropylene glycols and modified polyethylene glycols and polypropylene glycols.
- the modified polyalkylene glycols include in particular sulfates and / or disulfates of polyethylene glycols or polypropylene glycols with a relative molecular weight between 600 and 12000 and in particular between 1000 and 4000.
- Another group consists of mono- and / or disuccinates of the polyalkylene glycols, which in turn have relative molecular weights between 600 and 6000, preferably between 1000 and 4000.
- ethoxylated derivatives such as trimethylolpropane with 5 to 30 EO are also included.
- the preferably used polyethylene glycols can have a linear or branched structure, in particular linear polyethylene glycols are preferred.
- the particularly preferred polyethylene glycols include those with relative molecular weights between 2000 and 12000, advantageously around 4000, polyethylene glycols with relative molecular weights below 3500 and above 5000 especially in combination with polyethylene glycols with a relative molecular weight around 4000 can be used and such combinations advantageously to more than 50% by weight, based on the total amount of the polyethylene glycols, have polyethylene glycols with a relative molecular weight between 3500 and 5000.
- the modified polyethylene glycols also include polyethylene glycols which are end group-capped on one or more sides, the end groups preferably being C 1 -C 12 -alkyl chains, preferably C 1 -C 6 , which may be linear or branched.
- Polyethylene glycol derivatives capped at one end may also correspond to the formula Cx (EO) y (PO) z, where Cx can be an alkyl chain with a C chain length of 1 to 20, y 50 to 500 and z 0 to 20.
- Low molecular weight polyvinylpyrrolidones and derivatives thereof with relative molecular weights of up to a maximum of 30,000 are also suitable. Relative molecular weight ranges between 3,000 and 30,000 are preferred here.
- Polyvinyl alcohols are preferably used in combination with polyethylene glycols.
- one or more components can also be added which are liquid at room temperature or are present as a melt under the processing conditions, for example linear or branched fatty acids, in particular nonanoic acid or ethoxylated fatty acids 2 to 100 EO.
- the mixture of all components described above can additionally contain small amounts of a solvent, preferably less than 15% by weight, preferably less than 10% by weight, particularly preferably less than 7% by weight.
- the preferred solvent is water.
- additives are substances that influence the pH during storage and use. These include organic carboxylic acids or their salts, such as citric acid in anhydrous or hydrated form, glycolic acid, succinic acid, maleic acid or lactic acid.
- additives are possible which influence the bleaching capacity, such as complexing agents and transition metal complexes, for example metal complexes containing iron, cobalt or manganese, as described in EP-A-0 458 397 and EP-A-0 458 398.
- Particularly advantageous embodiments of the invention contain the sodium salt of nonanoyloxyphenylsulphonate (NOBS) as bleach activator, linear straight-chain alkylbenzenesulfonates as solubilizers, in particular with a C 8 -C 20 -, particularly preferably with a C11-13-alkyl group (LAS), as well as nonanoic acid and polyethylene glycol ( PEG) 4000 as a consistency agent and plasticizer, the proportion of NOBS being 70% by weight to 90% by weight, preferably 80% by weight to 87% by weight, particularly preferably 81% by weight to 85% by weight %, of LAS 2% by weight to 10% by weight, preferably 3% by weight to 5% by weight, particularly preferably 3.7% by weight to 4.5% by weight, of nonanoic acid 0 , 1% by weight to 6% by weight, preferably 1% by weight to 4% by weight, particularly preferably 2.5% by weight to 3.5% by weight, of PEG 4000 1% by weight. % to 15% by
- Bleach activator for example nonanoyloxyphenylsulphonate (NOBS) and anionic or nonionic surfactant, for example alkylbenzenesulfonate (LAS), are advantageously mixed in powder form, plasticizers, for example nonanoic acid and PEG 4000, are introduced at 50 to 70 ° C., preferably 60 to 65 ° C., and at a temperature in the range from 60 to 70 ° C and a pressure of 14 bar to 22 bar extruded.
- NOBS nonanoyloxyphenylsulphonate
- LAS alkylbenzenesulfonate
- the mixture is fed continuously to a 1-shaft extruder, 2-shaft extruder or 2-screw extruder with co-rotating or counter-rotating screw guidance, the housing and the extruder pelletizing head of which are heated to the predetermined extrusion temperature can.
- the mixture Under the shear action of the extruder screws, the mixture is compressed under pressure, plasticized, extruded in the form of strands through the perforated die plate in the extruder head, optionally powdered with fine-grained anti-caking agent, for example TiO2, silica, zeolite, self-dust, roughly Chopped straw pieces and transferred to a rounder tempered to 40 to 120 ° C., preferably 60 to 80 ° C., in particular 60 to 65 ° C.
- fine-grained anti-caking agent for example TiO2, silica, zeolite, self-dust, roughly Chopped straw pieces and transferred to a rounder tempered to 40 to 120 ° C., preferably 60 to 80 ° C., in particular 60 to 65 ° C.
- the subsequent rounding process gives cylindrical to spherical granules with defined particle sizes and a very narrow particle size distribution, the particle diameter between 0.2 mm and 2 mm, preferably between 0.5 mm and 0.8 mm, the particle length in the range of 0.5 mm to 3.5 mm, ideally between 0.9 mm and 2.5 mm.
- the extrudates are placed directly on the rounder or, if necessary, roughly comminuted.
- the shaping process according to the invention is carried out continuously in cascade operation, but batch-wise work is also possible.
- the size and shape of the particles can be influenced and brought about in the rounding process by means of several parameters.
- the shaping process is determined by the filling quantity, the temperature of the mixture, the residence time of the mixture in the rounder, by the speed of rotation of the rounding wheel, and by the plastic deformability of the mixture.
- the residence time of the mixture in the rounder depends not only on the plasticity but also on the filling quantity and is preferably 10 seconds to 120 seconds, particularly preferably 20 seconds to 60 seconds, and the peripheral speed is 10 m / sec. up to 30 m / sec., preferably 12 m / sec. up to 20 m / sec.
- the temperature in the rounder is controlled by air or gas flow (N2), preferably via the splitting device.
- the temperature of the air or gas streams is 50 to 120 ° C., preferably 60 to 90 ° C., so that, depending on the design of the rounder, the desired working temperature can be maintained in the rounder.
- the cylindrically shaped and rounded particles are cooled in a downstream apparatus, preferably in a fluid bed cooler, to temperatures below 40 ° C. in a cold air or gas stream in order to avoid the granules from sticking together.
- the granules obtained in this way are characterized by favorable flow behavior, low dust content and high abrasion resistance.
- the bulk density is in the range from 300 g / l to 2000 g / l, preferably in the range from 400 g / l to 1500 g / l and particularly preferably in the range from 500 to 800 g / l.
- the granules obtained according to the invention are directly suitable for use in detergents and cleaning agents. If necessary, they can be provided with a coating envelope.
- additives are substances which react in the wash liquor with the peroxycarboxylic acid released from the activator to form reactive intermediates, such as dioxiranes or oxaziridines, and can thus increase the reactivity.
- Corresponding compounds are ketones and sulfonimines corresponding to US-A-3 822 114 and EP-A-O 446 982.
- the amount of the additive depends in particular on its type.
- acidifying additives and organic catalysts for increasing the performance of the peracid are used in amounts of 0 to 20% by weight, in particular in amounts of 1 to 10% by weight, based on the total weight. added, however, metal complexes in concentrations in the ppm range.
- the granules obtained are characterized by very good abrasion resistance and storage stability in powder detergent, cleaning and disinfectant formulations. They are ideal for use in heavy-duty detergents, stain salts, machine dishwashing detergents, powdered all-purpose cleaners and denture cleaners.
- the granules according to the invention are mostly used in combination with a hydrogen peroxide source.
- a hydrogen peroxide source examples for this are Perborate monohydrate, perborate tetrahydrate, percarbonates and hydrogen peroxide adducts with urea or amine oxides.
- the formulation can have further detergent constituents, such as organic and inorganic builders and co-builders, surfactants, enzymes, brighteners and perfume.
- Example 1 Production of a NOBS granulate, active ingredient content: 84.4% by weight Granule diameter d 0.7 mm Granule length I 1.4 mm 844 g of the sodium salt of nonanoyloxybenzenesulphonate (NOBS), 50 g of linear C 11-13 -alkylbenzenesulfonate, Na salt, 31 g of nonanoic acid and 75 g of polyethylene glycol 4000 are added to the ploughshare mixer (manufacturer Lödige) at room temperature at a speed of 120 per minute and switched on Cutter head mixed homogeneously over a period of 150 seconds, heated to 65 to 71 ° C, transferred to a single-shaft dome extruder (manufacturer Fitzpatrick) with a hole diameter of 0.7 mm in the punch die and at an extruder screw speed of 45 per minute, a throughput of 287 g / min.
- NOBS nonanoyloxybenzenesulphonate
- Example 2 Production of a NOBS granulate, active ingredient content: 85.8% by weight Granule diameter d 0.7 mm Granule length I 1.4 mm 858 g of the sodium salt of nonanoyloxybenzenesulphonate (NOBS), 42 g of linear C 11-13 -alkylbenzenesulfonate, Na salt, 29 g of nonanoic acid and 71 g of polyethylene glycol 4000 are mixed in the ploughshare mixer (manufacturer Lödige) at room temperature at a speed of 120 per minute and switched on Cutter head mixed homogeneously over a period of 150 seconds, heated to 62 to 65 ° C, transferred to a single-shaft dome extruder (manufacturer Fitzpatrick) with a hole diameter of 0.7 mm in the punch die and at an extruder screw speed of 45 per minute, a throughput of 199 g / min.
- Example 3 Production of a TAED granulate, Granule diameter d 0.7 mm Granule length I 1.4 mm 675 g of tetraacetylethylene diamine (TAED) and 100.9 g of fatty alcohol polyglycol ether C 16 -C 18 were in a ploughshare mixer (manufacturer Lödige) at room temperature at a speed of 120 per minute and the cutter head switched on in one Homogeneously mixed for a period of 150 seconds, heated to 65-68 ° C, transferred to a single-shaft dome extruder (manufacturer Fitzpatrick) with a hole diameter of 0.7 mm in the perforated die and at an extruder screw speed of 45 per minute, a throughput of 199 g / min, extruded.
- TAED tetraacetylethylene diamine
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Abstract
Description
Die vorliegende Erfindung betrifft ein Verfahren zur Herstellung von zylinderförmigen bis kugelförmige Extrudaten, die Bleichaktivatoren enthalten, mit definierten Partikelgrößen und enger Partikelgrößenverteilung, die ein geringes Abriebverhalten und ein gutes Fließverhalten zeigen.The present invention relates to a process for the production of cylindrical to spherical extrudates which contain bleach activators, with defined particle sizes and narrow particle size distribution, which show low abrasion behavior and good flow behavior.
Aus zahlreichen Patentschriften sind Verfahren zur Herstellung extrudierter Waschund Reinigungsmittel bekannt. In EP 486 592 wird die Herstellung von extrudierten Formkörpern beschrieben, wobei ein festes und rieselfähiges Vorgemisch unter Einsatz eines Plastifizier- und/ oder Gleitmittels bei Anwendung relativ hoher Drucke zwischen etwa 25 und 200 bar strangförmig verpresst wird. Der Strang weist eine derartige Konsistenz auf, dass er nach Austritt aus der Lochform mittels einer Schneidevorrichtung direkt auf vorbestimmte Granulatdimension geschnitten werden kann. Als Plastifizier- und/ oder Gleitmittel werden insbesondere wässrige Aniontensidpasten, wässrige Polymerlösungen und/oder bei Raumtemperatur flüssige nichtionische Tenside genannt. Die so herstellbaren extrudierten Formkörper weisen im allgemeinen eine Größe bis 2 cm, vorzugsweise bis 0,8 cm auf, wobei das Länge-Durchmesser-Verhältnis vorteilhafterweise zwischen 1 : 1 und 3:1 liegt.Methods for the production of extruded washing and cleaning agents are known from numerous patents. EP 486 592 describes the production of extruded moldings, in which a solid and free-flowing premix is extruded using a plasticizer and / or lubricant when using relatively high pressures between about 25 and 200 bar. The strand has such a consistency that it can be cut directly to predetermined granule dimensions after exiting the hole shape by means of a cutting device. In particular, aqueous anionic surfactant pastes, aqueous polymer solutions and / or nonionic surfactants which are liquid at room temperature are mentioned as plasticizers and / or lubricants. The extruded moldings that can be produced in this way generally have a size of up to 2 cm, preferably up to 0.8 cm, the length-diameter ratio advantageously being between 1: 1 and 3: 1.
Wie in WO 99/27061 beschrieben, werden Bleichaktivatoren vorteilhaft in Form zylinderförmiger Extrudate konfektioniert, um die Kompatibilität mit anderen Waschmittelbestandteilen und eine ausreichende Lagerstabilität zu gewährleisten. Man geht davon aus, dass der hochreaktive Bleichaktivator vorwiegend im Inneren des zylinderförmigen Granulates eingebettet ist und die Oberfläche überwiegend aus Bindematerialien und Plastifiziermittel besteht.
Um ein Entmischen der unterschiedlichen Partikel in der Waschmittelformulierung während Transport und Lagerung zu vermeiden, sollte der Partikeldurchmesser zwischen 0,2 mm und 2 mm, bevorzugt zwischen 0,5 mm und 0,8 mm, die Teilchenlänge im Bereich von 0,5 mm bis 3,5 mm, idealerweise zwischen 0,9 mm und 2,5 mm liegen.
Alle bisher beschriebenen Verfahren zur Herstellung von Extrudaten liefern entweder Formkörper mit einer relativ breiten Partikelgrößenverteilung und/oder einem vergleichsweise hohen Staubanteil. Die Partikel weisen an den Schnittstellen scharfe Ecken und Kanten auf, die einen hohen Abrieb mit Staubbildung und ein ungünstiges Fließverhalten verursachen. Erfolgt die Herstellung der Extrudate unter hohen Verdichtungskräften wird das Löseverhalten der Partikel wesentlich beeinträchtigt.As described in WO 99/27061, bleach activators are advantageously packaged in the form of cylindrical extrudates in order to ensure compatibility with other detergent constituents and adequate storage stability. It is assumed that the highly reactive bleach activator is predominantly embedded in the interior of the cylindrical granulate and that the surface consists mainly of binding materials and plasticizers.
In order to avoid segregation of the different particles in the detergent formulation during transport and storage, the particle diameter should between 0.2 mm and 2 mm, preferably between 0.5 mm and 0.8 mm, the particle length in the range from 0.5 mm to 3.5 mm, ideally between 0.9 mm and 2.5 mm.
All of the previously described processes for the production of extrudates either provide moldings with a relatively broad particle size distribution and / or a comparatively high dust content. The particles have sharp corners and edges at the interfaces, which cause high abrasion with dust formation and an unfavorable flow behavior. If the extrudates are produced under high compression forces, the dissolving behavior of the particles is significantly impaired.
Die Aufgabe der Erfindung bestand nun darin, zylinderförmige bis kugelförmige Extrudate mit einem Gehalt an Bleichaktivatoren für den Einsatz in Wasch- oder Reinigungsmittel herzustellen, welche eine sehr enge Partikelgrößenverteilung aufweisen und zugleich eine geringe Abriebtendenz, geringe Staubbildung, ein günstiges Fließverhalten, sowie ein gutes Löseverhalten während des Wasch- und Reinigungsvorganges zeigen.The object of the invention was to produce cylindrical to spherical extrudates containing bleach activators for use in detergents or cleaning agents, which have a very narrow particle size distribution and at the same time have a low tendency to abrasion, low dust formation, favorable flow behavior and good dissolving behavior show during the washing and cleaning process.
Gegenstand der Erfindung ist ein Verfahren zur Herstellung von Bleichaktivator-Granulaten, dadurch gekennzeichnet, dass man ein Gemisch aus Bleichaktivator, anionischem oder nichtionischem Tensid und Polyalkylenglykol bei Temperaturen von 40 bis 120°C, vorzugsweise 60 bis 80°C und einem Druck von 5 bis 30 bar extrudiert und die erhaltenen Extrudate bei einer Temperatur von 40 bis 120°C, vorzugsweise 60 bis 80°C auf einem Rondierer granuliert.The invention relates to a process for the preparation of bleach activator granules, characterized in that a mixture of bleach activator, anionic or nonionic surfactant and polyalkylene glycol at temperatures from 40 to 120 ° C, preferably 60 to 80 ° C and a pressure of 5 to Extruded 30 bar and the extrudates obtained at a temperature of 40 to 120 ° C, preferably 60 to 80 ° C granulated on a rounder.
Als Bleichaktivatoren kommen beispielsweise in Frage N,N,N',N'-Tetraacetylethylendiamin (TAED), Glucosepentaacetat (GPA), Xylosetetraacetat (TAX), Natrium-4-benzoyloxybenzolsulfonat (SBOBS), Natriumtrimethylhexanoyloxybenzolsulfonat (STHOBS), Tetraacetylglycoluril (TAGU), Tetraacetylcyansäure (TACA), Di-N-acetyldimethylglyoxim (ADMG), 1-Phenyl-3-acetylhydantoin (PAH), Nonanoylcaprolactamphenylsulfonatester (APES), Nitrilotriacetat (NTA), bevorzugt das Natriumsalz von Nonanoyloxybenzolsulphonat (NOBS), das Natriumsalz von 3,5,5-Trimethylhexanoyloxyphenylsulfonat (iso-NOBS) oder das Natriumsalz von Acetoxyphenylsulfonat (ABS).Possible bleach activators are, for example, N, N, N ', N'-tetraacetylethylenediamine (TAED), glucose pentaacetate (GPA), xylose tetraacetate (TAX), sodium 4-benzoyloxybenzenesulfonate (SBOBS), sodium trimethylhexanoyloxybenzenesulfonate (TetraCletyl) glycolate (STetraBluetylglycolate) (STETHacetylglycolate) (STHACSulfyl), tetra (tetraacetylglycolate) Tetraacetylcyanoic acid (TACA), di-N-acetyldimethylglyoxime (ADMG), 1-phenyl-3-acetylhydantoin (PAH), nonanoylcaprolactamphenylsulfonate ester (APES), nitrilotriacetate (NTA), preferably the sodium salt of nonanoyloxybenzobenzene sulphonate, 3,5-n-benzol sulfonate , 5-Trimethylhexanoyloxyphenylsulfonat (iso-NOBS) or the sodium salt of Acetoxyphenyl sulfonate (ABS).
Bevorzugte anionische Tenside sind Alkalisalze, Ammoniumsalze, Aminsalze und Salze von Aminoalkoholen von folgenden Verbindungen: Alkylsulfate, Alkylethersulfate, Alkylamid-sulfate und -ethersulfate, Alkylarylpolyethersulfate, Monoglyceridsulfate, Alkylsulfonate, Alkylamidsulfonate, Alkylarylsulfonate, α-Olefinsulfonate, Alkylsulfosuccinate, Alkyläthersulfosuccinate, Alkylamidsulfosuccinate, Alkylsulfoacetate, Alkylpolyglycerin-carboxylate, Alkylphosphate, Alkyletherphosphaten, Alkylsarcosinate, Alkylpolypeptidate, Alkylamidopolypeptidate, Alkylisethionate, Alkyltaurate, Alkylpolyglykolethercarbonsäuren oder Fettsäuren, wie Oleinsäure, Ricinoleinsäure, Palmitinsäure, Stearinsäure, Kopraölsäuresalz oder hydrierte Kopraölsäuresalze. Der Alkylrest all dieser Verbindungen enthält normalerweise 8 - 32, vorzugsweise 8 - 22 C-Atome. Besonders bevorzugt sind lineare geradkettige Alkylbenzolsulfonate, insbesondere mit einer C8-C20-, besonders bevorzugt mit einer C11-13-Alkylgruppe.Preferred anionic surfactants are alkali metal salts, ammonium salts, amine salts and salts of amino alcohols of the following compounds: alkyl sulfates, alkyl ether sulfates, alkyl amide sulfates and ether sulfates, alkylaryl polyether sulfates, monoglyceride sulfates, alkyl sulfonate sulfates, alkyl amide sulfonates, alkyl aryl sulfonate sulfates, α-olefin sulfonates, α-olefin sulfates Alkylpolyglycerin carboxylates, alkyl phosphates, alkyl ether, alkyl sarcosinates, Alkylpolypeptidate, Alkylamidopolypeptidate, isethionates, taurates, alkyl polyglycol ether or fatty acids such as oleic acid, ricinoleic acid, palmitic acid, stearic acid, Kopraölsäuresalz or hydrogenated copra. The alkyl radical of all these compounds normally contains 8-32, preferably 8-22, carbon atoms. Linear straight-chain alkylbenzenesulfonates are particularly preferred, in particular with a C 8 -C 20 -, particularly preferably with a C 11-13 -alkyl group.
Als nichtionische Tenside werden polyethoxylierte, polypropoxylierte oder polyglycerinierte Ether von Fettalkoholen, polyethoxylierte, polypropoxylierte und polyglycerinierte Fettsäureester, polyethoxylierte Ester von Fettsäuren und von Sorbit, polyethoxilierte oder polyglycerinierte Fettamide bevorzugt.Preferred nonionic surfactants are polyethoxylated, polypropoxylated or polyglycerolated ethers of fatty alcohols, polyethoxylated, polypropoxylated and polyglycerolized fatty acid esters, polyethoxylated esters of fatty acids and of sorbitol, polyethoxylated or polyglycerolated fatty amides.
Als Polyalkylenglykole kommen Polyethylenglykole, 1,2-Polypropylenglykole sowie modifizierte Polyethylenglykole und Polypropylenglykole in Betracht. Zu den modifizierten Polyalkylenglykolen zählen insbesondere Sulfate und/oder Disulfate von Polyethylenglykolen oder Polypropylenglykolen mit einer relativen Molekülmasse zwischen 600 und 12000 und insbesondere zwischen 1000 und 4000. Eine weitere Gruppe besteht aus Mono- und/oder Disuccinaten der Polyalkylenglykole, welche wiederum relative Molekülmassen zwischen 600 und 6000, vorzugsweise zwischen 1000 und 4000 aufweisen. Ferner werden auch ethoxylierte Derivate wie Trimethylolpropan mit 5 bis 30 EO umfasst.
Die vorzugsweise eingesetzten Polyethylenglykole können eine lineare oder verzweigte Struktur aufweisen, wobei insbesondere lineare Polyethylenglykole bevorzugt sind. Zu den insbesondere bevorzugten Polyethylenglykolen gehören solche mit relativen Molekülmassen zwischen 2000 und 12000, vorteilhafterweise um 4000, wobei Polyethylenglykole mit relativen Molekülmassen unterhalb 3500 und oberhalb 5000 insbesondere in Kombination mit Polyethylenglykolen mit einer relativen Molekülmasse um 4000 eingesetzt werden können und derartige Kombinationen vorteilhafterweise zu mehr als 50 Gew.-%, bezogen auf die gesamte Menge der Polyethylenglykole, Polyethylenglykole mit einer relativen Molekülmasse zwischen 3500 und 5000 aufweisen.
Zu den modifizierten Polyethylenglykolen gehören auch ein- oder mehrseitig endgruppenverschlossene Polyethylenglykole, wobei die Endgruppen vorzugsweise C1-C12-Alkylketten, bevorzugt C1-C6, die linear oder verzweigt sein können, darstellen. Einseitig endgruppenverschlossene Polyethylenglykolderivate können auch der Formel Cx(EO)y(PO)z entsprechen, wobei Cx eine Alkylkette mit einer C-Kettenlänge von 1 bis 20, y 50 bis 500 und z 0 bis 20 sein können.
Ebenso geeignet sind niedermolekulare Polyvinylpyrrolidone und Derivate von diesen mit relativen Molekülmassen bis maximal 30 000. Bevorzugt sind hierbei relative Molekülmassenbereiche zwischen 3000 und 30 000. Polyvinylalkohole werden vorzugsweise in Kombination mit Polyethylenglykolen eingesetzt.Polyalkylene glycols are polyethylene glycols, 1,2-polypropylene glycols and modified polyethylene glycols and polypropylene glycols. The modified polyalkylene glycols include in particular sulfates and / or disulfates of polyethylene glycols or polypropylene glycols with a relative molecular weight between 600 and 12000 and in particular between 1000 and 4000. Another group consists of mono- and / or disuccinates of the polyalkylene glycols, which in turn have relative molecular weights between 600 and 6000, preferably between 1000 and 4000. Furthermore, ethoxylated derivatives such as trimethylolpropane with 5 to 30 EO are also included.
The preferably used polyethylene glycols can have a linear or branched structure, in particular linear polyethylene glycols are preferred. The particularly preferred polyethylene glycols include those with relative molecular weights between 2000 and 12000, advantageously around 4000, polyethylene glycols with relative molecular weights below 3500 and above 5000 especially in combination with polyethylene glycols with a relative molecular weight around 4000 can be used and such combinations advantageously to more than 50% by weight, based on the total amount of the polyethylene glycols, have polyethylene glycols with a relative molecular weight between 3500 and 5000.
The modified polyethylene glycols also include polyethylene glycols which are end group-capped on one or more sides, the end groups preferably being C 1 -C 12 -alkyl chains, preferably C 1 -C 6 , which may be linear or branched. Polyethylene glycol derivatives capped at one end may also correspond to the formula Cx (EO) y (PO) z, where Cx can be an alkyl chain with a C chain length of 1 to 20, y 50 to 500 and z 0 to 20.
Low molecular weight polyvinylpyrrolidones and derivatives thereof with relative molecular weights of up to a maximum of 30,000 are also suitable. Relative molecular weight ranges between 3,000 and 30,000 are preferred here. Polyvinyl alcohols are preferably used in combination with polyethylene glycols.
Zur Verbesserung der Plastifizier- und Gleiteigenschaften, aber auch der Abriebfestigkeit der Bleichaktivator-Granulate können zusätzlich eine oder auch mehrere Komponenten zugesetzt, die bei Raumtemperatur flüssig sind oder unter den Verarbeitungsbedingungen als Schmelze vorliegen, beispielsweise lineare oder verzweigte Fettsäuren, insbesondere Nonansäure oder ethoxylierte Fettsäuren mit 2 bis 100 EO.To improve the plasticizing and sliding properties, but also the abrasion resistance of the bleach activator granules, one or more components can also be added which are liquid at room temperature or are present as a melt under the processing conditions, for example linear or branched fatty acids, in particular nonanoic acid or ethoxylated fatty acids 2 to 100 EO.
Die oben beschriebene Mischung aller Komponenten kann zusätzlich geringe Mengen eines Lösungsmittels enthalten, bevorzugt weniger als 15 Gew.-%, bevorzugt weniger als 10 Gew.-%, besonders bevorzugt weniger als 7 Gew.-%. Bevorzugtes Lösungsmittel ist Wasser.The mixture of all components described above can additionally contain small amounts of a solvent, preferably less than 15% by weight, preferably less than 10% by weight, particularly preferably less than 7% by weight. The preferred solvent is water.
Weitere geeignete Zusätze sind Stoffe, die den pH-Wert während Lagerung und Anwendung beeinflussen. Dazu zählen organische Carbonsäuren oder deren Salze, wie Zitronensäure in wasserfreier oder hydratisierter Form, Glykolsäure, Bernsteinsäure, Maleinsäure oder Milchsäure. Daneben sind Zusätze möglich, die das Bleichvermögen beeinflussen, wie Komplexbildner und Übergangsmetallkomplexe, z.B. Eisen-, Cobalt- bzw. Mangan-haltige Metallkomplexe wie in EP-A-0 458 397und EP-A-0 458 398 beschriebene.Other suitable additives are substances that influence the pH during storage and use. These include organic carboxylic acids or their salts, such as citric acid in anhydrous or hydrated form, glycolic acid, succinic acid, maleic acid or lactic acid. In addition, additives are possible which influence the bleaching capacity, such as complexing agents and transition metal complexes, for example metal complexes containing iron, cobalt or manganese, as described in EP-A-0 458 397 and EP-A-0 458 398.
Besonders vorteilhafte Ausführungsformen der Erfindung enthalten als Bleichaktivator das Natriumsalz von Nonanoyloxyphenylsulphonat (NOBS), als Lösungsvermittler lineare geradkettige Alkylbenzolsulfonate, insbesondere mit einer C8-C20-, besonders bevorzugt mit einer C11-13-Alkylgruppe (LAS), sowie Nonansäure und Polyethylenglykol (PEG) 4000 als Konsistenzgeber und Plastifiziermittel, wobei der Anteil an NOBS 70 Gew.-% bis 90 Gew.-%, bevorzugt 80 Gew.-% bis 87 Gew.-%, besonders bevorzugt 81 Gew.-% bis 85 Gew.-%, an LAS 2 Gew.-% bis 10 Gew.-%, bevorzugt 3 Gew.-% bis 5 Gew.-%, besonders bevorzugt 3,7 Gew.-% bis 4,5 Gew.-%, an Nonansäure 0,1 Gew.-% bis 6 Gew.-%, bevorzugt 1 Gew.-% bis 4 Gew.-%, besonders bevorzugt 2,5 Gew.-% bis 3,5 Gew.-%, an PEG 4000 1 Gew.-% bis 15 Gew.-%, bevorzugt 5 Gew.-% bis 10 Gew.-%, besonders bevorzugt 7 Gew.-% bis 8 Gew.-% beträgt.Particularly advantageous embodiments of the invention contain the sodium salt of nonanoyloxyphenylsulphonate (NOBS) as bleach activator, linear straight-chain alkylbenzenesulfonates as solubilizers, in particular with a C 8 -C 20 -, particularly preferably with a C11-13-alkyl group (LAS), as well as nonanoic acid and polyethylene glycol ( PEG) 4000 as a consistency agent and plasticizer, the proportion of NOBS being 70% by weight to 90% by weight, preferably 80% by weight to 87% by weight, particularly preferably 81% by weight to 85% by weight %, of LAS 2% by weight to 10% by weight, preferably 3% by weight to 5% by weight, particularly preferably 3.7% by weight to 4.5% by weight, of nonanoic acid 0 , 1% by weight to 6% by weight, preferably 1% by weight to 4% by weight, particularly preferably 2.5% by weight to 3.5% by weight, of PEG 4000 1% by weight. % to 15% by weight, preferably 5% to 10% by weight, particularly preferably 7% to 8% by weight.
Vorteilhafterweise werden Bleichaktivator, beispielsweise Nonanoyloxyphenylsulphonat (NOBS) und anionischer oder nichtionischer Tensid, beispielsweise Alkylbenzolsulfonat (LAS) pulverförmig vermischt, Plastifiziermittel, beispielsweise Nonansäure und PEG 4000 bei 50 bis 70°C, bevorzugt 60 bis 65°C eingetragen und bei einer Temperatur im Bereich von 60 bis 70°C und einem Druck von 14 bar bis 22 bar strangförmig verpresst. In einer bevorzugten Ausführungsform der Erfindung wird dabei das Gemisch kontinuierlich einem 1-Wellen-Extruder, 2-Wellen-Extruder bzw. 2-Schnecken-Extruder mit gleichlaufender oder gegenlaufender Schneckenführung zugeführt, dessen Gehäuse und dessen Extruder-Granulierkopf auf die vorbestimmte Extrudiertemperatur aufgeheizt sein können. Unter der Schereinwirkung der Extruderschnecken wird das Gemisch unter Druck verdichtet, plastifiziert, in Form von Strängen durch die Lochdüsenplatte im Extruderkopf extrudiert, gegebenenfalls mit feinkörnigem Antibackmittel, beispielsweise TiO2, Kieselsäure, Zeolith, Eigenstaub abgepudert, in grobe Straw-Stücke zerkleinert und auf einen auf 40 bis 120°C, bevorzugt 60 bis 80°C, insbesondere 60 bis 65°C temperierten Rondierer überführt.Bleach activator, for example nonanoyloxyphenylsulphonate (NOBS) and anionic or nonionic surfactant, for example alkylbenzenesulfonate (LAS), are advantageously mixed in powder form, plasticizers, for example nonanoic acid and PEG 4000, are introduced at 50 to 70 ° C., preferably 60 to 65 ° C., and at a temperature in the range from 60 to 70 ° C and a pressure of 14 bar to 22 bar extruded. In a preferred embodiment of the invention, the mixture is fed continuously to a 1-shaft extruder, 2-shaft extruder or 2-screw extruder with co-rotating or counter-rotating screw guidance, the housing and the extruder pelletizing head of which are heated to the predetermined extrusion temperature can. Under the shear action of the extruder screws, the mixture is compressed under pressure, plasticized, extruded in the form of strands through the perforated die plate in the extruder head, optionally powdered with fine-grained anti-caking agent, for example TiO2, silica, zeolite, self-dust, roughly Chopped straw pieces and transferred to a rounder tempered to 40 to 120 ° C., preferably 60 to 80 ° C., in particular 60 to 65 ° C.
Durch das anschließende Rondierverfahren werden zylinderförmige bis kugelförmige Granulate mit definierten Partikelgrößen und sehr enger Partikelgrößenverteilung erhalten, wobei der Partikeldurchmesser zwischen 0,2 mm und 2 mm, bevorzugt zwischen 0,5 mm und 0,8 mm, die Teilchenlänge im Bereich von 0,5 mm bis 3,5 mm, idealerweise zwischen 0,9 mm und 2,5 mm liegt. Die Extrudate werden direkt auf den Rondierer gegeben oder gegebenenfalls grob vorzerkleinert. In einer bevorzugten Ausführungsform wird der erfindungsgemäße Formungsprozess kontinuierlich im Kaskadenbetrieb durchgeführt, doch ist auch ein absatzweises Arbeiten möglich.
Größe und Form der Partikel können im Rondierverfahren durch mehrere Parameter beeinflusst und herbeigeführt werden. Der Formungsprozess wird bestimmt durch die Füllmenge, die Temperatur der Mischung, die Verweilzeit der Mischung im Rondierer, durch die Drehgeschwindigkeit der Rondierscheibe, sowie durch die plastische Verformbarkeit der Mischung.
Mit abnehmender Füllmenge im Rondierer werden kürzere Zylindergranulate und eine engere Verteilung der Partikelgrößen erhalten. Mit abnehmender Temperatur und damit geringer werdender Plastizität werden längere Granulate erhalten, bei weiterer Abkühlung nimmt der Staubanteil stark zu.
Die Verweilzeit der Mischung im Rondierer hängt neben der Plastizität von der Füllmenge ab und beträgt bevorzugt 10 sec. bis 120 sec., besonders bevorzugt 20 sec. bis 60 sec., die Umfangsgeschwindigkeit 10 m/sec. bis 30 m/sec., bevorzugt 12 m/sec. bis 20 m/sec.The subsequent rounding process gives cylindrical to spherical granules with defined particle sizes and a very narrow particle size distribution, the particle diameter between 0.2 mm and 2 mm, preferably between 0.5 mm and 0.8 mm, the particle length in the range of 0.5 mm to 3.5 mm, ideally between 0.9 mm and 2.5 mm. The extrudates are placed directly on the rounder or, if necessary, roughly comminuted. In a preferred embodiment, the shaping process according to the invention is carried out continuously in cascade operation, but batch-wise work is also possible.
The size and shape of the particles can be influenced and brought about in the rounding process by means of several parameters. The shaping process is determined by the filling quantity, the temperature of the mixture, the residence time of the mixture in the rounder, by the speed of rotation of the rounding wheel, and by the plastic deformability of the mixture.
As the filling quantity in the rounder decreases, shorter cylinder granules and a narrower distribution of particle sizes are obtained. With decreasing temperature and thus decreasing plasticity, longer granules are obtained, with further cooling the dust content increases significantly.
The residence time of the mixture in the rounder depends not only on the plasticity but also on the filling quantity and is preferably 10 seconds to 120 seconds, particularly preferably 20 seconds to 60 seconds, and the peripheral speed is 10 m / sec. up to 30 m / sec., preferably 12 m / sec. up to 20 m / sec.
In einer besonderen Ausführungsform wird die Temperatur im Rondierer durch Luftoder Gasstromzufuhr (N2), bevorzugt über die Spaltvorrichtung, gesteuert. Die Temperatur der Luft- bzw. Gasströme beträgt 50 bis 120°C, bevorzugt 60 bis 90°C, so dass je nach Ausführung des Rondierers die gewünschte Arbeitstemperatur im Rondierer aufrecht erhalten werden kann.In a particular embodiment, the temperature in the rounder is controlled by air or gas flow (N2), preferably via the splitting device. The temperature of the air or gas streams is 50 to 120 ° C., preferably 60 to 90 ° C., so that, depending on the design of the rounder, the desired working temperature can be maintained in the rounder.
Nach dem Formungsprozess werden die zylindrisch geformten und abgerundeten Partikel in einem nachgeschalteten Apparat, vorzugsweise in einem Fließbettkühler im kalten Luft- oder Gasstrom auf Temperaturen unterhalb 40°C abgekühlt, um ein Verkleben der Granulate zu vermeiden.After the molding process, the cylindrically shaped and rounded particles are cooled in a downstream apparatus, preferably in a fluid bed cooler, to temperatures below 40 ° C. in a cold air or gas stream in order to avoid the granules from sticking together.
Die so erhaltenen Granulate zeichnen sich durch ein günstiges Fließverhalten, geringen Staubanteil, hoher Abriebfestigkeit aus.
Das Schüttgewicht liegt im Bereich 300 g/l bis 2000 g/l, bevorzugt im Bereich 400 g/l bis 1500 g/l und besonders bevorzugt im Bereich von 500 - 800 g/l.The granules obtained in this way are characterized by favorable flow behavior, low dust content and high abrasion resistance.
The bulk density is in the range from 300 g / l to 2000 g / l, preferably in the range from 400 g / l to 1500 g / l and particularly preferably in the range from 500 to 800 g / l.
Die erfindungsgemäßen erhaltenen Granulate sind direkt zum Einsatz in Waschund Reinigungsmitteln geeignet. Sie können gegebenenfalls mit einer Coatinghülle versehen werden.The granules obtained according to the invention are directly suitable for use in detergents and cleaning agents. If necessary, they can be provided with a coating envelope.
Weitere mögliche Zusätze sind Stoffe, die in der Waschlauge mit der aus dem Aktivator freigesetzten Peroxicarbonsäure unter Bildung reaktiver Zwischenstufen, wie Dioxiranen oder Oxaziridinen, reagieren und auf diese Weise die Reaktivität erhöhen können. Entsprechende Verbindungen sind Ketone und Sulfonimine entsprechend US-A-3 822 114 und EP-A-O 446 982.Other possible additives are substances which react in the wash liquor with the peroxycarboxylic acid released from the activator to form reactive intermediates, such as dioxiranes or oxaziridines, and can thus increase the reactivity. Corresponding compounds are ketones and sulfonimines corresponding to US-A-3 822 114 and EP-A-O 446 982.
Die Menge des Zusatzstoffes richtet sich insbesondere nach seiner Art. So werden acidifizierende Zusätze und organische Katalysatoren zur Leistungssteigerung der Persäure in Mengen von 0 bis 20 Gew.-%, insbesondere in Mengen von 1 bis 10 Gew.-%, bezogen auf das Gesamtgewicht, zugesetzt, Metallkomplexe hingegen in Konzentrationen im ppm Bereich.
Die erhaltenen Granulate zeichnen sich durch eine sehr gute Abriebfestigkeit und Lagerstabilität in pulverförmigen Wasch-, Reinigungs- und Desinfektionsmittelformulierungen aus. Sie sind ideal zum Einsatz in Vollwaschmitteln, Fleckensalzen, Maschinengeschirrspülmitteln, pulverförmigen Allzweckreinigern und Gebissreinigern.The amount of the additive depends in particular on its type. For example, acidifying additives and organic catalysts for increasing the performance of the peracid are used in amounts of 0 to 20% by weight, in particular in amounts of 1 to 10% by weight, based on the total weight. added, however, metal complexes in concentrations in the ppm range.
The granules obtained are characterized by very good abrasion resistance and storage stability in powder detergent, cleaning and disinfectant formulations. They are ideal for use in heavy-duty detergents, stain salts, machine dishwashing detergents, powdered all-purpose cleaners and denture cleaners.
In diesen Formulierungen werden die erfindungsgemäßen Granulate meist in Kombination mit einer Wasserstoffperoxydquelle eingesetzt. Beispiele hierfür sind Perborat-Monohydrat, Perborat-Tetrahydrat, Percarbonate sowie Wasserstoffperoxid-Addukte an Harnstoff oder Aminoxiden. Daneben kann die Formulierung dem Stand der Technik entsprechend weitere Waschmittelbestandteile aufweisen, wie organische und anorganische Builder und Co-Builder, Tenside, Enzyme, Aufheller und Parfüm.In these formulations, the granules according to the invention are mostly used in combination with a hydrogen peroxide source. examples for this are Perborate monohydrate, perborate tetrahydrate, percarbonates and hydrogen peroxide adducts with urea or amine oxides. In addition, according to the state of the art, the formulation can have further detergent constituents, such as organic and inorganic builders and co-builders, surfactants, enzymes, brighteners and perfume.
Nachfolgende Beispiele sollen die Erfindung näher erläutern ohne sie darauf einzuschränken.The following examples are intended to explain the invention in more detail without restricting it.
Beispiel 1: Herstellung eines NOBS-Granulates, Wirkstoffanteil: 84,4 Gew.-%
Beispiel 2: Herstellung eines NOBS-Granulates, Wirkstoffanteil: 85,8 Gew.-%
Beispiel 3: Herstellung eines TAED-Granulates,
Claims (15)
Applications Claiming Priority (2)
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DE10136805A DE10136805A1 (en) | 2001-07-25 | 2001-07-25 | Process for the production of bleach activator granules |
DE10136805 | 2001-07-25 |
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EP1279725A2 true EP1279725A2 (en) | 2003-01-29 |
EP1279725A3 EP1279725A3 (en) | 2003-09-03 |
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EP02016000A Withdrawn EP1279725A3 (en) | 2001-07-25 | 2002-07-18 | Method of production of bleach activator granulate |
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US (1) | US7122511B2 (en) |
EP (1) | EP1279725A3 (en) |
JP (1) | JP4219632B2 (en) |
DE (1) | DE10136805A1 (en) |
Cited By (3)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
EP1500644A1 (en) * | 2003-07-25 | 2005-01-26 | Clariant GmbH | Process for the preparation of granulated acyloxybenzenesulfonates or acyloxybenzenecarboxylic acids and their salts |
EP1870447A1 (en) * | 2006-06-24 | 2007-12-26 | Cognis IP Management GmbH | Solid tensides in granular form |
WO2017102473A1 (en) * | 2015-12-18 | 2017-06-22 | Henkel Ag & Co. Kgaa | Particulate agent for increasing the bleaching effect |
Families Citing this family (3)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
DE10134364A1 (en) * | 2001-07-14 | 2003-01-23 | Clariant Gmbh | Process for the production of bleach activator granules |
DE102006040103A1 (en) * | 2006-08-28 | 2008-03-06 | Henkel Kgaa | Melt granules for detergents and cleaners |
US20140243252A1 (en) * | 2013-02-28 | 2014-08-28 | Futurefuel Chemical Company | Laundry detergent formulation |
Citations (3)
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WO1992002608A1 (en) * | 1990-08-03 | 1992-02-20 | Henkel Kommanditgesellschaft Auf Aktien | Granular bleach activators |
DE4143016A1 (en) * | 1991-12-24 | 1993-07-01 | Henkel Kgaa | BLEACH ACTIVATORS IN GRANULATE FORM (II) |
EP1275709A1 (en) * | 2001-07-14 | 2003-01-15 | Clariant GmbH | Process for the production of bleach activator granules |
Family Cites Families (7)
Publication number | Priority date | Publication date | Assignee | Title |
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GB1368400A (en) | 1971-08-05 | 1974-09-25 | Procter & Gamble | Bleaching process and compositions therefor |
EP0006655B1 (en) * | 1978-06-26 | 1982-10-13 | THE PROCTER & GAMBLE COMPANY | Particulate detergent additive product |
KR927003783A (en) | 1989-08-09 | 1992-12-18 | 게오르그 차이트 | Manufacturing method of compressed granules for detergent |
US5047163A (en) | 1990-03-16 | 1991-09-10 | Lever Brothers Company, Division Of Conopco, Inc. | Activation of bleach precursors with sulfonimines |
EP0458398B1 (en) | 1990-05-21 | 1997-03-26 | Unilever N.V. | Bleach activation |
US6200944B1 (en) * | 1996-06-28 | 2001-03-13 | The Procter & Gamble Company | Bleach precursor compositions |
CA2311378C (en) | 1997-11-20 | 2004-04-20 | The Procter & Gamble Company | Detergent composition containing optimally sized bleach activator particles |
-
2001
- 2001-07-25 DE DE10136805A patent/DE10136805A1/en not_active Withdrawn
-
2002
- 2002-07-18 EP EP02016000A patent/EP1279725A3/en not_active Withdrawn
- 2002-07-23 JP JP2002213778A patent/JP4219632B2/en not_active Expired - Fee Related
- 2002-07-23 US US10/201,459 patent/US7122511B2/en not_active Expired - Fee Related
Patent Citations (3)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
WO1992002608A1 (en) * | 1990-08-03 | 1992-02-20 | Henkel Kommanditgesellschaft Auf Aktien | Granular bleach activators |
DE4143016A1 (en) * | 1991-12-24 | 1993-07-01 | Henkel Kgaa | BLEACH ACTIVATORS IN GRANULATE FORM (II) |
EP1275709A1 (en) * | 2001-07-14 | 2003-01-15 | Clariant GmbH | Process for the production of bleach activator granules |
Cited By (3)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
EP1500644A1 (en) * | 2003-07-25 | 2005-01-26 | Clariant GmbH | Process for the preparation of granulated acyloxybenzenesulfonates or acyloxybenzenecarboxylic acids and their salts |
EP1870447A1 (en) * | 2006-06-24 | 2007-12-26 | Cognis IP Management GmbH | Solid tensides in granular form |
WO2017102473A1 (en) * | 2015-12-18 | 2017-06-22 | Henkel Ag & Co. Kgaa | Particulate agent for increasing the bleaching effect |
Also Published As
Publication number | Publication date |
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JP4219632B2 (en) | 2009-02-04 |
US20030045445A1 (en) | 2003-03-06 |
US7122511B2 (en) | 2006-10-17 |
EP1279725A3 (en) | 2003-09-03 |
JP2003138299A (en) | 2003-05-14 |
DE10136805A1 (en) | 2003-02-13 |
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