EP0520582A1 - Sprühgetrocknete Waschmittelzusammensetzungen auf Zeolithbasis und Verfahren zur deren Herstellung - Google Patents
Sprühgetrocknete Waschmittelzusammensetzungen auf Zeolithbasis und Verfahren zur deren Herstellung Download PDFInfo
- Publication number
- EP0520582A1 EP0520582A1 EP92201881A EP92201881A EP0520582A1 EP 0520582 A1 EP0520582 A1 EP 0520582A1 EP 92201881 A EP92201881 A EP 92201881A EP 92201881 A EP92201881 A EP 92201881A EP 0520582 A1 EP0520582 A1 EP 0520582A1
- Authority
- EP
- European Patent Office
- Prior art keywords
- spray
- detergent
- weight
- composition
- zeolite
- 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
- 239000003599 detergent Substances 0.000 title claims abstract description 117
- 239000000203 mixture Substances 0.000 title claims abstract description 99
- 239000010457 zeolite Substances 0.000 title claims abstract description 54
- HNPSIPDUKPIQMN-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Al]O[Al]=O HNPSIPDUKPIQMN-UHFFFAOYSA-N 0.000 title claims abstract description 50
- 229910021536 Zeolite Inorganic materials 0.000 title claims abstract description 45
- 238000004519 manufacturing process Methods 0.000 title description 10
- 239000002002 slurry Substances 0.000 claims abstract description 57
- 239000002245 particle Substances 0.000 claims abstract description 51
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 30
- 150000001875 compounds Chemical class 0.000 claims abstract description 27
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 26
- 238000000034 method Methods 0.000 claims abstract description 26
- 239000011324 bead Substances 0.000 claims abstract description 25
- 125000000129 anionic group Chemical group 0.000 claims abstract description 22
- 239000004115 Sodium Silicate Substances 0.000 claims abstract description 17
- NTHWMYGWWRZVTN-UHFFFAOYSA-N sodium silicate Chemical compound [Na+].[Na+].[O-][Si]([O-])=O NTHWMYGWWRZVTN-UHFFFAOYSA-N 0.000 claims abstract description 17
- 229910052911 sodium silicate Inorganic materials 0.000 claims abstract description 17
- 238000005728 strengthening Methods 0.000 claims abstract description 15
- 238000001694 spray drying Methods 0.000 claims abstract description 14
- 239000007787 solid Substances 0.000 claims abstract description 12
- 239000004744 fabric Substances 0.000 claims abstract description 11
- 125000002091 cationic group Chemical group 0.000 claims abstract description 8
- 239000000440 bentonite Substances 0.000 claims abstract description 6
- SVPXDRXYRYOSEX-UHFFFAOYSA-N bentoquatam Chemical compound O.O=[Si]=O.O=[Al]O[Al]=O SVPXDRXYRYOSEX-UHFFFAOYSA-N 0.000 claims abstract description 6
- 229940080314 sodium bentonite Drugs 0.000 claims abstract description 3
- 229910000280 sodium bentonite Inorganic materials 0.000 claims abstract description 3
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 claims description 21
- 239000001509 sodium citrate Substances 0.000 claims description 14
- NLJMYIDDQXHKNR-UHFFFAOYSA-K sodium citrate Chemical group O.O.[Na+].[Na+].[Na+].[O-]C(=O)CC(O)(CC([O-])=O)C([O-])=O NLJMYIDDQXHKNR-UHFFFAOYSA-K 0.000 claims description 14
- 150000003839 salts Chemical class 0.000 claims description 9
- 229910019142 PO4 Inorganic materials 0.000 claims description 8
- 229920001495 poly(sodium acrylate) polymer Polymers 0.000 claims description 6
- NNMHYFLPFNGQFZ-UHFFFAOYSA-M sodium polyacrylate Chemical group [Na+].[O-]C(=O)C=C NNMHYFLPFNGQFZ-UHFFFAOYSA-M 0.000 claims description 6
- 239000010452 phosphate Substances 0.000 claims description 5
- 238000003860 storage Methods 0.000 claims description 5
- MGFYIUFZLHCRTH-UHFFFAOYSA-N nitrilotriacetic acid Chemical class OC(=O)CN(CC(O)=O)CC(O)=O MGFYIUFZLHCRTH-UHFFFAOYSA-N 0.000 claims description 4
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 claims description 4
- 229920000058 polyacrylate Polymers 0.000 claims description 4
- 238000005299 abrasion Methods 0.000 claims description 3
- 239000004337 magnesium citrate Substances 0.000 claims description 3
- 229960005336 magnesium citrate Drugs 0.000 claims description 3
- 235000002538 magnesium citrate Nutrition 0.000 claims description 3
- PLSARIKBYIPYPF-UHFFFAOYSA-H trimagnesium dicitrate Chemical compound [Mg+2].[Mg+2].[Mg+2].[O-]C(=O)CC(O)(CC([O-])=O)C([O-])=O.[O-]C(=O)CC(O)(CC([O-])=O)C([O-])=O PLSARIKBYIPYPF-UHFFFAOYSA-H 0.000 claims description 3
- -1 bleaches Substances 0.000 description 26
- 125000004432 carbon atom Chemical group C* 0.000 description 21
- IAYPIBMASNFSPL-UHFFFAOYSA-N Ethylene oxide Chemical compound C1CO1 IAYPIBMASNFSPL-UHFFFAOYSA-N 0.000 description 19
- 238000007792 addition Methods 0.000 description 14
- 238000002156 mixing Methods 0.000 description 13
- 239000004094 surface-active agent Substances 0.000 description 12
- 239000000463 material Substances 0.000 description 11
- 239000000047 product Substances 0.000 description 11
- 229910052783 alkali metal Inorganic materials 0.000 description 10
- 239000007921 spray Substances 0.000 description 9
- 125000000217 alkyl group Chemical group 0.000 description 8
- 150000003871 sulfonates Chemical class 0.000 description 8
- 238000005406 washing Methods 0.000 description 8
- 102000004190 Enzymes Human genes 0.000 description 7
- 108090000790 Enzymes Proteins 0.000 description 7
- 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 7
- 150000002191 fatty alcohols Chemical class 0.000 description 7
- 229910052708 sodium Inorganic materials 0.000 description 7
- 239000011734 sodium Substances 0.000 description 7
- RZVAJINKPMORJF-UHFFFAOYSA-N Acetaminophen Chemical compound CC(=O)NC1=CC=C(O)C=C1 RZVAJINKPMORJF-UHFFFAOYSA-N 0.000 description 6
- BPQQTUXANYXVAA-UHFFFAOYSA-N Orthosilicate Chemical compound [O-][Si]([O-])([O-])[O-] BPQQTUXANYXVAA-UHFFFAOYSA-N 0.000 description 6
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 description 6
- 239000002671 adjuvant Substances 0.000 description 6
- 150000001340 alkali metals Chemical class 0.000 description 6
- 229920001577 copolymer Polymers 0.000 description 6
- 239000004615 ingredient Substances 0.000 description 6
- 239000002304 perfume Substances 0.000 description 6
- 235000021317 phosphate Nutrition 0.000 description 6
- 239000000843 powder Substances 0.000 description 6
- 150000004996 alkyl benzenes Chemical class 0.000 description 5
- 239000002736 nonionic surfactant Substances 0.000 description 5
- 229920000642 polymer Polymers 0.000 description 5
- CDBYLPFSWZWCQE-UHFFFAOYSA-L sodium carbonate Substances [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 5
- 239000003760 tallow Substances 0.000 description 5
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 description 4
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 description 4
- PMZURENOXWZQFD-UHFFFAOYSA-L Sodium Sulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=O PMZURENOXWZQFD-UHFFFAOYSA-L 0.000 description 4
- UIIMBOGNXHQVGW-UHFFFAOYSA-M Sodium bicarbonate Chemical compound [Na+].OC([O-])=O UIIMBOGNXHQVGW-UHFFFAOYSA-M 0.000 description 4
- 229910000323 aluminium silicate Inorganic materials 0.000 description 4
- 150000001768 cations Chemical class 0.000 description 4
- 239000008187 granular material Substances 0.000 description 4
- 239000012188 paraffin wax Substances 0.000 description 4
- 229910052700 potassium Inorganic materials 0.000 description 4
- 239000011591 potassium Substances 0.000 description 4
- 229910052938 sodium sulfate Inorganic materials 0.000 description 4
- 235000011152 sodium sulphate Nutrition 0.000 description 4
- KVCGISUBCHHTDD-UHFFFAOYSA-M sodium;4-methylbenzenesulfonate Chemical compound [Na+].CC1=CC=C(S([O-])(=O)=O)C=C1 KVCGISUBCHHTDD-UHFFFAOYSA-M 0.000 description 4
- 239000000126 substance Substances 0.000 description 4
- 238000010998 test method Methods 0.000 description 4
- 239000012190 activator Substances 0.000 description 3
- 229910052784 alkaline earth metal Inorganic materials 0.000 description 3
- 239000003945 anionic surfactant Substances 0.000 description 3
- 239000002585 base Substances 0.000 description 3
- 229940092782 bentonite Drugs 0.000 description 3
- 229910000278 bentonite Inorganic materials 0.000 description 3
- 239000007859 condensation product Substances 0.000 description 3
- 238000001035 drying Methods 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 239000000945 filler Chemical class 0.000 description 3
- 150000003013 phosphoric acid derivatives Chemical class 0.000 description 3
- 239000000344 soap Substances 0.000 description 3
- 229910000029 sodium carbonate Inorganic materials 0.000 description 3
- QLAJNZSPVITUCQ-UHFFFAOYSA-N 1,3,2-dioxathietane 2,2-dioxide Chemical compound O=S1(=O)OCO1 QLAJNZSPVITUCQ-UHFFFAOYSA-N 0.000 description 2
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 description 2
- NIXOWILDQLNWCW-UHFFFAOYSA-N 2-Propenoic acid Natural products OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 2
- CPELXLSAUQHCOX-UHFFFAOYSA-M Bromide Chemical compound [Br-] CPELXLSAUQHCOX-UHFFFAOYSA-M 0.000 description 2
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 description 2
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 description 2
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 2
- CSNNHWWHGAXBCP-UHFFFAOYSA-L Magnesium sulfate Chemical compound [Mg+2].[O-][S+2]([O-])([O-])[O-] CSNNHWWHGAXBCP-UHFFFAOYSA-L 0.000 description 2
- 239000006057 Non-nutritive feed additive Substances 0.000 description 2
- 229920000388 Polyphosphate Polymers 0.000 description 2
- 230000002411 adverse Effects 0.000 description 2
- 150000001298 alcohols Chemical class 0.000 description 2
- 125000001931 aliphatic group Chemical group 0.000 description 2
- 229910000318 alkali metal phosphate Inorganic materials 0.000 description 2
- 150000001336 alkenes Chemical class 0.000 description 2
- 150000003863 ammonium salts Chemical class 0.000 description 2
- 150000001450 anions Chemical class 0.000 description 2
- 229910052791 calcium Inorganic materials 0.000 description 2
- 239000011575 calcium Substances 0.000 description 2
- 230000000052 comparative effect Effects 0.000 description 2
- 230000008021 deposition Effects 0.000 description 2
- 235000014113 dietary fatty acids Nutrition 0.000 description 2
- 238000004851 dishwashing Methods 0.000 description 2
- 239000000194 fatty acid Substances 0.000 description 2
- 229930195729 fatty acid Natural products 0.000 description 2
- 150000004665 fatty acids Chemical class 0.000 description 2
- 239000006260 foam Substances 0.000 description 2
- 238000013467 fragmentation Methods 0.000 description 2
- 238000006062 fragmentation reaction Methods 0.000 description 2
- 239000007789 gas Substances 0.000 description 2
- 238000010438 heat treatment Methods 0.000 description 2
- 230000036571 hydration Effects 0.000 description 2
- 238000006703 hydration reaction Methods 0.000 description 2
- XMBWDFGMSWQBCA-UHFFFAOYSA-N hydrogen iodide Chemical compound I XMBWDFGMSWQBCA-UHFFFAOYSA-N 0.000 description 2
- 125000001165 hydrophobic group Chemical group 0.000 description 2
- 230000003993 interaction Effects 0.000 description 2
- 238000004900 laundering Methods 0.000 description 2
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 description 2
- 239000000049 pigment Substances 0.000 description 2
- 229920000728 polyester Polymers 0.000 description 2
- 229920000139 polyethylene terephthalate Polymers 0.000 description 2
- 239000001205 polyphosphate Substances 0.000 description 2
- 235000011176 polyphosphates Nutrition 0.000 description 2
- 150000003856 quaternary ammonium compounds Chemical class 0.000 description 2
- 230000003763 resistance to breakage Effects 0.000 description 2
- 229910000030 sodium bicarbonate Inorganic materials 0.000 description 2
- 235000017557 sodium bicarbonate Nutrition 0.000 description 2
- 235000019832 sodium triphosphate Nutrition 0.000 description 2
- 230000003381 solubilizing effect Effects 0.000 description 2
- 239000000243 solution Substances 0.000 description 2
- KDYFGRWQOYBRFD-UHFFFAOYSA-N succinic acid Chemical compound OC(=O)CCC(O)=O KDYFGRWQOYBRFD-UHFFFAOYSA-N 0.000 description 2
- BDHFUVZGWQCTTF-UHFFFAOYSA-M sulfonate Chemical compound [O-]S(=O)=O BDHFUVZGWQCTTF-UHFFFAOYSA-M 0.000 description 2
- 150000008053 sultones Chemical class 0.000 description 2
- 101100277337 Arabidopsis thaliana DDM1 gene Proteins 0.000 description 1
- BVKZGUZCCUSVTD-UHFFFAOYSA-M Bicarbonate Chemical compound OC([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-M 0.000 description 1
- BHPQYMZQTOCNFJ-UHFFFAOYSA-N Calcium cation Chemical compound [Ca+2] BHPQYMZQTOCNFJ-UHFFFAOYSA-N 0.000 description 1
- 235000013162 Cocos nucifera Nutrition 0.000 description 1
- 244000060011 Cocos nucifera Species 0.000 description 1
- 229920000742 Cotton Polymers 0.000 description 1
- 241000280258 Dyschoriste linearis Species 0.000 description 1
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 1
- CERQOIWHTDAKMF-UHFFFAOYSA-M Methacrylate Chemical compound CC(=C)C([O-])=O CERQOIWHTDAKMF-UHFFFAOYSA-M 0.000 description 1
- IGFHQQFPSIBGKE-UHFFFAOYSA-N Nonylphenol Natural products CCCCCCCCCC1=CC=C(O)C=C1 IGFHQQFPSIBGKE-UHFFFAOYSA-N 0.000 description 1
- 239000004677 Nylon Substances 0.000 description 1
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 1
- 229920003171 Poly (ethylene oxide) Polymers 0.000 description 1
- GOOHAUXETOMSMM-UHFFFAOYSA-N Propylene oxide Chemical compound CC1CO1 GOOHAUXETOMSMM-UHFFFAOYSA-N 0.000 description 1
- BWDQZRPVSDRKEH-UHFFFAOYSA-M S(=O)(=O)(OC)[O-].C(CCCCCCCCCCCCCCCCC)[N+](C)(C)CCCCCCCCCCCCCCCCCC.[Cl-].C[NH2+]C Chemical compound S(=O)(=O)(OC)[O-].C(CCCCCCCCCCCCCCCCC)[N+](C)(C)CCCCCCCCCCCCCCCCCC.[Cl-].C[NH2+]C BWDQZRPVSDRKEH-UHFFFAOYSA-M 0.000 description 1
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 1
- PJANXHGTPQOBST-VAWYXSNFSA-N Stilbene Natural products C=1C=CC=CC=1/C=C/C1=CC=CC=C1 PJANXHGTPQOBST-VAWYXSNFSA-N 0.000 description 1
- LSNNMFCWUKXFEE-UHFFFAOYSA-N Sulfurous acid Chemical class OS(O)=O LSNNMFCWUKXFEE-UHFFFAOYSA-N 0.000 description 1
- GSEJCLTVZPLZKY-UHFFFAOYSA-N Triethanolamine Chemical class OCCN(CCO)CCO GSEJCLTVZPLZKY-UHFFFAOYSA-N 0.000 description 1
- YKTSYUJCYHOUJP-UHFFFAOYSA-N [O--].[Al+3].[Al+3].[O-][Si]([O-])([O-])[O-] Chemical compound [O--].[Al+3].[Al+3].[O-][Si]([O-])([O-])[O-] YKTSYUJCYHOUJP-UHFFFAOYSA-N 0.000 description 1
- 238000013019 agitation Methods 0.000 description 1
- 230000005791 algae growth Effects 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- 229910000288 alkali metal carbonate Inorganic materials 0.000 description 1
- 150000008041 alkali metal carbonates Chemical class 0.000 description 1
- 150000001342 alkaline earth metals Chemical class 0.000 description 1
- 125000003282 alkyl amino group Chemical group 0.000 description 1
- 150000008051 alkyl sulfates Chemical class 0.000 description 1
- 150000001412 amines Chemical class 0.000 description 1
- 230000003625 amylolytic effect Effects 0.000 description 1
- 239000012736 aqueous medium Substances 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 229940077388 benzenesulfonate Drugs 0.000 description 1
- 238000004061 bleaching Methods 0.000 description 1
- 239000007844 bleaching agent Substances 0.000 description 1
- 229910021538 borax Inorganic materials 0.000 description 1
- 229910000019 calcium carbonate Inorganic materials 0.000 description 1
- 229910001424 calcium ion Inorganic materials 0.000 description 1
- 239000000378 calcium silicate Substances 0.000 description 1
- 229910052918 calcium silicate Inorganic materials 0.000 description 1
- OYACROKNLOSFPA-UHFFFAOYSA-N calcium;dioxido(oxo)silane Chemical compound [Ca+2].[O-][Si]([O-])=O OYACROKNLOSFPA-UHFFFAOYSA-N 0.000 description 1
- 150000007942 carboxylates Chemical class 0.000 description 1
- 239000003093 cationic surfactant Substances 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 101150113676 chr1 gene Proteins 0.000 description 1
- 239000004927 clay Substances 0.000 description 1
- 238000004140 cleaning Methods 0.000 description 1
- 235000019864 coconut oil Nutrition 0.000 description 1
- 239000003240 coconut oil Substances 0.000 description 1
- 239000003086 colorant Substances 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- ZBCBWPMODOFKDW-UHFFFAOYSA-N diethanolamine Chemical class OCCNCCO ZBCBWPMODOFKDW-UHFFFAOYSA-N 0.000 description 1
- 239000003085 diluting agent Substances 0.000 description 1
- 125000000118 dimethyl group Chemical group [H]C([H])([H])* 0.000 description 1
- IQDGSYLLQPDQDV-UHFFFAOYSA-N dimethylazanium;chloride Chemical compound Cl.CNC IQDGSYLLQPDQDV-UHFFFAOYSA-N 0.000 description 1
- PGZPBNJYTNQMAX-UHFFFAOYSA-N dimethylazanium;methyl sulfate Chemical compound C[NH2+]C.COS([O-])(=O)=O PGZPBNJYTNQMAX-UHFFFAOYSA-N 0.000 description 1
- REZZEXDLIUJMMS-UHFFFAOYSA-M dimethyldioctadecylammonium chloride Chemical compound [Cl-].CCCCCCCCCCCCCCCCCC[N+](C)(C)CCCCCCCCCCCCCCCCCC REZZEXDLIUJMMS-UHFFFAOYSA-M 0.000 description 1
- 230000003467 diminishing effect Effects 0.000 description 1
- 238000006073 displacement reaction Methods 0.000 description 1
- 239000004664 distearyldimethylammonium chloride (DHTDMAC) Substances 0.000 description 1
- 239000000975 dye Substances 0.000 description 1
- 230000002708 enhancing effect Effects 0.000 description 1
- 125000001301 ethoxy group Chemical group [H]C([H])([H])C([H])([H])O* 0.000 description 1
- 238000001704 evaporation Methods 0.000 description 1
- 230000007717 exclusion Effects 0.000 description 1
- 239000012530 fluid Substances 0.000 description 1
- 239000004088 foaming agent Substances 0.000 description 1
- 238000001879 gelation Methods 0.000 description 1
- 150000004820 halides Chemical class 0.000 description 1
- 229920001519 homopolymer Polymers 0.000 description 1
- BHEPBYXIRTUNPN-UHFFFAOYSA-N hydridophosphorus(.) (triplet) Chemical compound [PH] BHEPBYXIRTUNPN-UHFFFAOYSA-N 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- MTNDZQHUAFNZQY-UHFFFAOYSA-N imidazoline Chemical compound C1CN=CN1 MTNDZQHUAFNZQY-UHFFFAOYSA-N 0.000 description 1
- 239000003112 inhibitor Substances 0.000 description 1
- 238000005342 ion exchange Methods 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 229910052744 lithium Inorganic materials 0.000 description 1
- 238000011068 loading method Methods 0.000 description 1
- 150000002680 magnesium Chemical class 0.000 description 1
- 229910052943 magnesium sulfate Inorganic materials 0.000 description 1
- 235000019341 magnesium sulphate Nutrition 0.000 description 1
- FPYJFEHAWHCUMM-UHFFFAOYSA-N maleic anhydride Chemical compound O=C1OC(=O)C=C1 FPYJFEHAWHCUMM-UHFFFAOYSA-N 0.000 description 1
- 239000011159 matrix material Substances 0.000 description 1
- 239000002609 medium Substances 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- SKDZEPBJPGSFHS-UHFFFAOYSA-N n,n-bis(2-hydroxyethyl)tetradecanamide Chemical compound CCCCCCCCCCCCCC(=O)N(CCO)CCO SKDZEPBJPGSFHS-UHFFFAOYSA-N 0.000 description 1
- SNQQPOLDUKLAAF-UHFFFAOYSA-N nonylphenol Chemical compound CCCCCCCCCC1=CC=CC=C1O SNQQPOLDUKLAAF-UHFFFAOYSA-N 0.000 description 1
- 230000000050 nutritive effect Effects 0.000 description 1
- 229920001778 nylon Polymers 0.000 description 1
- 239000011368 organic material Substances 0.000 description 1
- 239000011236 particulate material Substances 0.000 description 1
- 229920005646 polycarboxylate Polymers 0.000 description 1
- 239000005020 polyethylene terephthalate Substances 0.000 description 1
- 229920001296 polysiloxane Polymers 0.000 description 1
- 239000011148 porous material Substances 0.000 description 1
- BITYAPCSNKJESK-UHFFFAOYSA-N potassiosodium Chemical compound [Na].[K] BITYAPCSNKJESK-UHFFFAOYSA-N 0.000 description 1
- 159000000001 potassium salts Chemical class 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 230000002035 prolonged effect Effects 0.000 description 1
- 230000001737 promoting effect Effects 0.000 description 1
- 230000002797 proteolythic effect Effects 0.000 description 1
- 238000005086 pumping Methods 0.000 description 1
- 230000001105 regulatory effect Effects 0.000 description 1
- 239000011347 resin Chemical class 0.000 description 1
- 229920005989 resin Chemical class 0.000 description 1
- 239000003352 sequestering agent Substances 0.000 description 1
- 239000010865 sewage Substances 0.000 description 1
- 229960001922 sodium perborate Drugs 0.000 description 1
- 239000004328 sodium tetraborate Substances 0.000 description 1
- 235000010339 sodium tetraborate Nutrition 0.000 description 1
- 229940048842 sodium xylenesulfonate Drugs 0.000 description 1
- QUCDWLYKDRVKMI-UHFFFAOYSA-M sodium;3,4-dimethylbenzenesulfonate Chemical compound [Na+].CC1=CC=C(S([O-])(=O)=O)C=C1C QUCDWLYKDRVKMI-UHFFFAOYSA-M 0.000 description 1
- YKLJGMBLPUQQOI-UHFFFAOYSA-M sodium;oxidooxy(oxo)borane Chemical compound [Na+].[O-]OB=O YKLJGMBLPUQQOI-UHFFFAOYSA-M 0.000 description 1
- 239000002689 soil Substances 0.000 description 1
- 241000894007 species Species 0.000 description 1
- 238000005507 spraying Methods 0.000 description 1
- 239000003381 stabilizer Substances 0.000 description 1
- PJANXHGTPQOBST-UHFFFAOYSA-N stilbene Chemical compound C=1C=CC=CC=1C=CC1=CC=CC=C1 PJANXHGTPQOBST-UHFFFAOYSA-N 0.000 description 1
- 235000021286 stilbenes Nutrition 0.000 description 1
- 239000001384 succinic acid Substances 0.000 description 1
- 125000001273 sulfonato group Chemical group [O-]S(*)(=O)=O 0.000 description 1
- 230000001755 vocal effect Effects 0.000 description 1
- 239000003643 water by type Substances 0.000 description 1
- 239000004711 α-olefin Substances 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
- C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
- C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
- C11D3/16—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
- C11D11/00—Special methods for preparing compositions containing mixtures of detergents
- C11D11/02—Preparation in the form of powder by spray drying
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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
- C11D3/128—Aluminium silicates, e.g. zeolites
-
- 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
Definitions
- the present invention relates to a process for manufacturing a free-flowing spray-dried particulate detergent composition containing a zeolite builder and at least one surface active detergent compound, which composition is characterized by improved particle strength and integrity concomitant with reduced residue deposition properties. More particularly, this invention relates to a process for producing a spray-dried detergent composition characterized by the absence of sodium silicate in the aqueous crutcher slurry and the presence of a bead strengthening agent to provide particles having desired properties of enhanced mechanical strength.
- the invention also relates to particulate detergent compositions produced by the aforementioned process of manufacture which have improved washing properties by virtue of providing little, if any, residue on washed fabrics as well as having excellent mechanical strength and resistance to breakage so as to allow such compositions to be extensively stored, handled and transported without causing undo abrasion or fragmentation of the particles.
- Zeolites natural as well as synthetic, are known to be effective calcium sequestrants and are commonly used to replace phosphates, such as sodium tripolyphosphate, as detergent builders in commercial low-P or zero-P detergent compositions. But the presence of zeolite has heretofore often created a problem with regard to water-insoluble residue being deposited on laundry washed with such zeolite-containing compositions. This is generally attributed to its interaction with sodium silicate, a common ingredient in spray-dried particulate compositions, to form an insoluble zeolite-silicate agglomerate which becomes entrapped in the washed fabrics and forms an unsightly "residue" on the laundered clothing, seriously detracting from the washing performance.
- sodium silicate a common ingredient in spray-dried particulate compositions
- Sodium silicate is generally considered a critical ingredient in particulate detergent compositions. It is reported to serve many functions: first, as a corrosion inhibitor to provide protection for metal parts of the washing machine which come into contact with aqueous solutions of the washing composition; second, to increase the alkalinity of the aqueous washing solution; and most important, particularly in a spray-dried composition, it serves to provide stability and integrity to the detergent particles or beads formed during the spray-drying operation.
- Spray-dried detergent compositions containing a zeolite builder and sodium citrate are well known in the detergent art.
- U.S. Patent 3,801,511 to Lemoff discloses a spray-dried detergent composition in which an anti-caking agent such as sodium citrate is added to the aqueous slurry prior to spray-drying so as to provide crisp, free-flowing granules of said detergent composition.
- Sodium silicate is a preferred component of the detergent composition.
- U.S. 4,303,556 to Llenado describes a spray-dried detergent composition containing an aluminosilicate ion exchange material, sodium silicate and optionally an auxiliary builder which may be citric acid. Anionic surfactants are added to the aqueous slurry which is spray dried.
- U.S. 4,861,503 to Hollingsworth discloses a low-phosphate spray-dried detergent composition prepared from a crutcher slurry containing one or more anionic or nonionic detergent active compounds; from 0 to 10% of sodium silicate; a non-phosphate builder; from 0.5 to 2.5% of a salt of succinic acid; and 0.5 to 10% of a polymeric polycarboxylate. The compositions described in the Examples contain 4 or 5% sodium silicate.
- U.S. Patent 5,024,778 to Grecsek describes zeolite-containing spray dried base beads for detergent compositions which contain 5 to 60% of zeolite, 0 to 5% of water soluble silicate, 2 to 40% of bentonite and about 5 to 60% of polyphosphate.
- the presence of bentonite is intended to prevent the interaction of zeolite and silicate to form an objectionable aggregate which deposits on washed fabrics.
- the patent also discloses using citric acid and magnesium sulfate as anti-gelling processing aids to be added to the crutcher mix when the crutcher includes silicate in combination with carbonate and/or bicarbonate because of the tendency of such combination to solidify or cause gelation in the crutcher.
- U.S. Patent 4,231,887 to Denney discloses zeolite agglomerates for detergent compositions in a matrix of sodium citrate and ethoxylated linear alcohol.
- the sodium citrate is referred to as a "crisping agent" which imparts crispness to the agglomerates while permitting them to disintegrate upon contact with water.
- a zeolite-containing detergent composition which also contains sodium citrate.
- the working Examples 1-6 at page 26 of the publication describe spray dried compositions containing a minimum of 10%, by weight, of anionic and/or nonionic detergent compounds.
- sodium citrate and zeolite are present in the finished composition in the absence of sodium silicate.
- the surfactant detergent compounds are all added to the crutcher slurry; none being post-added or applied subsequent to spray drying to the spray-dried particles.
- U.S. Patent 4,988,454 to Eertink et al describes a process for preparing a low or zero-phosphorous detergent powder containing zeolite, sodium silicate, surfactant and polyacrylate.
- the process of manufacture restricts the amount of silicate in the crutcher slurry to no more than 2%, by weight, of the silicate in the final powder, and compensates for such restricted amount of silicate by post-dosing sodium silicate with the spray-dried powder as well as incorporating a polymer or copolymer of acrylic acid as a "structuring agent".
- the present invention provides a process for producing a free-flowing spray-dried particulate detergent composition having a density of from about 0.3 to about 1.0 g/cc and containing a zeolite and one or more anionic, nonionic and/or cationic surface active detergent compounds, said detergent composition having improved particle mechanical strength and integrity to allow extensive storage and handling of the composition with only minimum breakage and abrasion of the particles concomitant with high solubility characteristics such that the amount of visible residue deposited on fabrics laundered with such detergent composition is significantly minimized comprising the steps of:
- the present invention further provides a spray-dried particulate detergent composition containing (a) at least 5%, by weight, of a zeolite; (b) an effective amount of a bead strengthening agent as herein defined; (c) from about 0 to 50%, by weight, of a supplementary detergent builder other than (a) and (b); and (d) one or more anionic nonionic or cationic surfactant active detergent compounds in an amount sufficient to obtain the desired properties of detergency or softening for the particulate detergent composition, said detergent composition by prepared by the process of the invention defined herein.
- the detergent powders of the invention preferably have a phosphorous content of less than about 2.5%, by weight, preferably below about 1%, by weight, and most preferably are zero-P compositions.
- the present invention is predicated on the discovery that, in contradistinction to the practice of the prior art, the exclusion of sodium silicate from the aqueous crutcher slurry in preparing zeolite-containing spray-dried particles, the inclusion of a bead strengthening agent as herein described and the restriction on the amount of surfactant in the crutcher slurry are three important process parameters which when practiced in combination provide a particulate detergent composition having excellent mechanical strength and integrity as well as superior washing characteristics such that fabrics laundered therewith are substantially free of the characteristic residue observed on fabrics laundered with most commercially available zeolite-containing spray-dried laundry compositions. Further, unlike the disclosure of U.S. Patent 5,024,778, the avoidance of residue is effected in the absence of bentonite.
- the restriction on surfactant compounds in the crutcher slurry is required because the presence of anionic or nonionic surface active detergent compounds in the crutcher in significant amounts adversely affects the mechanical strength and integrity of the spray-dried particles leaving the tower (commonly referred to as "tower particles") as well as diminishing the absorptivity of such particles for oversprayed surfactant in a subsequent processing step.
- Tower particles commonly referred to as "tower particles”
- anionic and nonionic surfactants have the effect of expanding the particles formed during spray-drying such that depending on the amount present, fragmented and dusty particles are formed substantially lacking mechanical strength.
- the level of anionic and nonionic surface active compounds in the crutcher slurry is maintained below about 3%, by weight, preferably below about 1%, by weight, and most preferably is substantially free of anionic and nonionic surfactant compounds, the above percentages being based on the solids content of the slurry, in the absence of water.
- Another significant feature of the process of the invention is that it is capable of providing spray-dried particulate compositions over a range of densities up to about 1.0 g/cc. This is particularly important for the manufacture of so-called concentrated and superconcentrated laundry detergent powders which require high density products capable of providing effective laundering at recommended dosages of "1/4 cup” or "1/2 cup” corresponding to about 35-45 grams or about 60-70 grams of product per wash, respectively, under U.S. washing conditions.
- the density of the particles leaving the spray tower can be as high as 0.8 g/cc. Further increases in density are effected during the post-addition of the surfactant detergent compounds as well as upon addition of optional post-added ingredients such as bleaches, activators, supplementary builders, clay, perfume and the like.
- the density of tower particles are conveniently regulated in accordance with the invention by the addition to the crutcher slurry of an organic "density modifying agent" which lowers the density of the spray-dried particle by creating, in effect, an expanded particle or bead during spray drying.
- the amount of such modifying agent added to the crutcher slurry will generally be from about .01% to 5% depending on the desired density of the tower particles.
- Preferred density modifying agents for use herein include organic materials such as sodium toluene sulfonate and homopolymers and copolymers of acrylic acid such as with maleic anhydride or methacrylate in a range of molecular weight from 2000 to 200,000, sodium polyacrylate being particularly preferred for this purpose in a molecular weight range of 40,000 to 60,000.
- Other useful density modifying agents include sodium xylene sulfonate.
- the bead strengthening agent is generally added to the slurry in an amount of from about 1 to about 50%, preferably at least about 3%, such as, from about 3 to 30%, and most preferably from about 5 to 20%, by weight, based on the solids content of the slurry in the absence of water.
- An alkali or alkaline earth metal salt of citric acid is preferred for this purpose, most preferably sodium citrate or magnesium citrate.
- an aqueous crutcher slurry is formed containing a mixture of water with many or most of the ingredients desired in the final detergent composition.
- the solids content of the slurry is generally from about 40% to about 70%, preferably 50% to 65% thereof the balance being water.
- the crutcher slurry is then atomized by pumping it through a nozzle at a pressure of about 500 psi into a spray-drying tower, the typical dimensions of a commercial tower being about 35-100 feet in height and about 12-30 feet in diameter.
- air is introduced at a temperature of from about 300-1000°F which contacts the atomized slurry to provide a hot drying gas for the droplets of the slurry thereby evaporating most of the water.
- the resulting particles or beads are collected at the bottom of the tower, the moisture and heated air existing at the top.
- Heat or water-sensitive ingredients such as perfume, bleach, activator and enzyme are conventionally post-added to the tower particles in a subsequent mixing or blending operation.
- the crutcher slurry is preferably made by sequentially adding the various components thereof in the manner which will result in the most miscible, readily pumpable and non-setting slurry for spray drying.
- the order of addition of the various components may be varied, depending on the circumstances. Normally it is preferable for all or almost all of the water to be added to the crutcher first, preferably at about the processing temperature, after which the processing aids, such as density modifying agents, e.g. sodium polyacrylate and sodium toluene sulfonate, and other minor components, including pigments and fluorescent brighteners are added, followed by a supplementary builder, if present, such as sodium bicarbonate or carbonate and the bead strengthening agent, e.g. sodium citrate.
- density modifying agents e.g. sodium polyacrylate and sodium toluene sulfonate
- other minor components including pigments and fluorescent brighteners
- the zeolite and any filler salts are added to the crutcher mix.
- each component will be mixed in thoroughly before addition of the next component but methods of addition may be varied, depending on the circumstances, so as to allow co-additions when such are feasible.
- component additions may be in two or more parts to effect good mixing, e.g. during zeolite addition. Different components may sometimes be pre-mixed before addition to speed the mixing process. Normally, mixing speed and power will be increased as the materials are added. For example, low speeds may be used until after admixing in of the supplementary builder and the bead strengthening agent, after which the speed may be increased during and after addition of the zeolite to provide a homogeneous slurry mix.
- the temperature of the aqueous medium in the crutcher will usually be about room temperature or elevated, normally being in the 20 to 70°C range, and preferably from about 25 to 40°C. Heating the crutcher medium may promote solution of the water soluble salts of the mix and thereby increase miscibility, but the heating operation, when effected in the crutcher, can slow production rates. Temperatures higher than 70°C are usually avoided because of the possibility of decomposition of one or more crutcher mix components, e.g., sodium bicarbonate.
- crutcher mixing times to obtain thoroughly mixed homogeneous slurries can vary widely, from as little as five minutes in small crutchers and for slurries of higher moisture contents, to as much as two hours, in some cases, although 30 minutes is a preferable upper limit.
- the uniform crutcher slurry is thereafter transferred in the usual manner to a spray drying tower, which is located near the crutcher.
- the slurry is normally dropped from the bottom of the crutcher to a positive displacement pump, which forces it at high pressure through spray nozzles into the spray tower (countercurrent or concurrent), wherein the droplets of the slurry fall through a hot drying gas to form absorptive particles or beads.
- the product After drying, the product is screened to desired size, e.g., 10 to 100 mesh, U.S. Sieve Series, and is ready for application of a nonionic and/or anionic detergent overspray in a mixing drum onto the tumbling particles, the particles or beads being either in warm or cooled (to room temperature) condition.
- the nonionic detergent will usually be at an elevated temperature to assure that it will be liquid; yet, upon cooling to room temperature, desirably it will be a solid, often resembling a waxy solid. This characteristic will not adversely affect the flowability of the final composition because the nonionic detergent normally penetrates to below the bead surface.
- Zeolite A-type aluminosilicate builder usually hydrated, with about 15 to 25% of water of hydration is used advantageously as the zeolite of the present invention.
- Hydrated zeolites X and Y may be useful too, as may be naturally occurring zeolites that can act as detergent builders.
- zeolite 4A a type of zeolite molecule wherein the pore size is about 4 Angstroms, is often preferred. This type of zeolite is well known in the art and methods for its manufacture are described in the art such as in U.S. Patent 3,114,603.
- the zeolite builders are generally of the formula wherein x is 1, y is from 0.8 to 1.2, preferably about 1, z is from 1.5 to 3.5, preferably 2 to 3 or about 2, and w is from 0 to 9, preferably 2.5 to 6.
- the crystalline types of zeolite which may be employed herein include those described in "Zeolite Molecular Series" by Donald Breck, published in 1974 by John Wiley & Sons, typical commercially available zeolites being listed in Table 9.6 at pages 747-749 of the text, such Table being incorporated herein by reference.
- the zeolite builder should be a univalent cation exchanging zeolite, i.e., it should be an aluminosilicate of a univalent cation such as sodium, potassium, lithium (when practicable) or other alkali metal, or ammonium.
- a zeolite having an alkali metal cation, especially sodium, is most preferred, as is indicated in the formula shown above.
- the zeolites employed may be characterized as having a high exchange capacity for calcium ion, which is normally from about 200 to 400 or more milligram equivalents of calcium carbonate hardness per gram of the aluminosilicate, preferably 250 to 350 mg. eg./g., on an anhydrous zeolite basis.
- the hydrated zeolites normally have a moisture or water of hydration content in the range of 5 to 30%, preferably about 15 to 25% and more preferably 17 to 22%, e.g., about 20%.
- the zeolites, as charged to a crutcher slurry from which beads or particles are spray-dried, should be in finely divided state, with the ultimate particle diameters being up to 20 microns, preferably 0.01 to 8 microns mean particle size, e.g., 3 to 7 microns, if crystalline, and 0.01 to 0.1 micron, e.g., 0.01 to 0.05 micron, if amorphous.
- the zeolite particles are of sizes within the range of No. 100 to 400 sieve, preferably No. 140 to 325 sieve, as charged to the crutcher.
- the weight percent of zeolite in the crutcher slurry is at least about 5% for purposes of the invention, preferably from about 5 to 50%, and most preferably from about 10 to 40%, by weight, based on the solids content of the slurry.
- a nonionic detergent is conveniently added to the tower beads to form a detergent composition by post-spraying onto surfaces of the particles in a blender or mixing drum.
- various nonionic detergents of satisfactory physical characteristics may be utilized, including condensation products of ethylene oxide and propylene oxide with each other and with hydroxy-containing bases, such as nonyl phenol and Oxo-type alcohols, it is highly preferred that the nonionic detergent be a condensation product of ethylene oxide and higher fatty alcohol.
- the higher fatty alcohol will normally be linear and of 10 to 20 carbon atoms, preferably 12 to 16 carbon atoms, and sometimes most preferably of 12 to 15 or 12 to 14 carbon atoms. Because such fatty alcohols are normally available commercially only as mixtures, the number of carbon atoms given are necessarily averages.
- the ethylene oxide (EtO) contents of the nonionic detergents will normally be in the range of 1 to 15 moles of EtO per mole of higher fatty alcohol, although as much as 20 moles of EtO may be present.
- EtO content will be 3 to 10 moles and more preferably it will be 6 to 7 moles, e.g., 6.5 or 7 moles per mole of higher fatty alcohol (and per mole of nonionic detergent).
- the polyethoxylate limits given are also limits on the averages of the numbers of EtO groups present in the condensation product.
- Both broad ranges ethoxylates and narrow range ethoxylate may be employed, with the difference between them being in the "spread" of number of ethoxylate groups present, which average within the ranges given.
- NRE's which average 5 to 10 EtO groups per mole in the nonionic detergent will have at least 70% of the EtO content in polyethoxy groups of 4 to 12 moles of EtO and will preferably have over 85% of the EtO content in such range.
- BRE nonionic detergents have a broader range of ethoxy contents than NRE's, often with a spread from 1 to 15 moles of EtO when the EtO chain is in the 5 to 10 EtO range (average).
- BRE nonionic detergents examples include those sold by Shell Chemical Company under the trademark Neodol®, including Neodol 25-7, Neodol 23-6.5 and Neodol 25-3. Supplies of NRE nonionic detergents have been obtained from Shell Development Company, which identifies such materials as 23-7P and 23-7Z, and from Hoechst, which identifies such preferred products as Tergitol® having one of the following designations: 24-L-60N, 24-L-45N, 24-L-75N and 26-L-60N.
- Nonionic detergent compounds include the alkylpolyglycoside and alkylpolysaccharide surfactants, which are well known in the art.
- anionic surface active agents useful in the present invention are those surface active compounds which contain an organic hydrophobic group containing from about 8 to 26 carbon atoms and preferably from about 10 to 18 carbon atoms in their molecular structure and at least one water-solubilizing group selected from the group of sulfonate, sulfate, carboxylate, phosphorate and phosphate so as to form a water-soluble detergent.
- Suitable anionic detergents include soaps, such as, the water-soluble salts (e.g., the sodium potassium, ammonium and alkanol-ammonium salts) of higher fatty acids or resin salts containing from about 8 to 20 carbon atoms and preferably 10 to 18 carbon atoms. Particularly useful are the sodium and potassium salts of the fatty acid mixtures derived from coconut oil and tallow, for example, sodium coconut soap and potassium tallow soap.
- the water-soluble salts e.g., the sodium potassium, ammonium and alkanol-ammonium salts
- the sodium and potassium salts of the fatty acid mixtures derived from coconut oil and tallow for example, sodium coconut soap and potassium tallow soap.
- the anionic class of detergents also includes the water-soluble sulfated and sulfonated detergents having an aliphatic, preferably an alkyl radical containing from about 8 to 26, and preferably from about 12 to 22 carbon atoms.
- the sulfonated anionic detergents are the higher alkyl aromatic sulfonates such as the higher alkyl benzene sulfonates containing from about 10 to 16 carbon atoms in the higher alkyl group in a straight or branched chain, such as, for example, the sodium, potassium and ammonium salts of higher alkyl benzene sulfonates, higher alkyl toluene sulfonates and higher alkyl phenol sulfonates.
- Suitable anionic detergents are the olefin sulfonates including long chain alkene sulfonates, long chain hydroxyalkane sulfonates or mixtures of alkene sulfonates and hydroxyalkane sulfonates and hydroxyalkane sulfonates.
- sulfate or sulfonate detergents are paraffin sulfonates containing from about 10 to 20 carbon atoms, and preferably from about 15 to 20 carbon atoms.
- the primary paraffin sulfonates are made by reacting long chain alpha olefins and bisulfites. Paraffin sulfonates having the sulfonate group distributed along the paraffin chain are shown in U.S. Nos. 2,503,280; 2,507,088; 3,260,741; 3,372,188 and German Patent No. 735,096.
- Suitable anionic detergents are sulfated ethoxylated higher fatty alcohols of the formula RO(C2H4O) m SO3M, wherein R is a fatty alkyl of from 10 to 18 carbon atoms, m is from 2 to 6 (preferably having a value from about 1/5 to 1/2 the number of carbon atoms in R) and M is a solubilizing salt-forming cation, such as an alkali metal, ammonium, lower alkylamino or lower alkanolamino, or a higher alkyl benzene sulfonate wherein the higher alkyl is of 10 to 15 carbon atoms.
- R is a fatty alkyl of from 10 to 18 carbon atoms
- m is from 2 to 6 (preferably having a value from about 1/5 to 1/2 the number of carbon atoms in R)
- M is a solubilizing salt-forming cation, such as an alkali metal, ammonium, lower alkylamino or
- the proportion of ethylene oxide in the polyethoxylated higher alkanol sulfate is preferably 2 to 5 moles of ethylene oxide groups per mole of anionic detergent, with three moles being most preferred, especially when the higher alkanol is of 11 to 15 carbon atoms.
- a preferred polyethoxylated alcohol sulfate detergent is marketed by Shell Chemical Company as Neodol 25-3S.
- the most highly preferred water-soluble anionic detergent compounds are the ammonium and substituted ammonium (such as mono, di and triethanolamine), alkali metal (such as, sodium and potassium) and alkaline earth metal (such as, calcium and magnesium) salts of the higher alkyl benzene sulfonates, olefine sulfonates and higher alkyl sulfates.
- alkali metal such as, sodium and potassium
- alkaline earth metal such as, calcium and magnesium
- the most preferred are the sodium linear alkyl benzene sulfonates (LABS), and especially those wherein the alkyl group is a straight chain alkyl radical of 12 or 13 carbon atoms.
- Cationic surface active compounds may also be employed. They comprise surface active detergent compounds which contain an organic hydrophobic group which forms part of a cation when the compound is dissolved in water, and an anionic group. Typical cationic detergents are amine and quaternary ammonium compounds.
- the quaternary ammonium compounds useful herein are known materials and are of the high-softening type. Included are the N1N-di-(higher) C14-C24, N1N-di(lower) C1-C4 alkyl quaternary ammonium salts with water solubilizing anions such as halide, e.g. chloride, bromide and iodide; sulfate, methosulfate and the like and the heterocyclic imides such as imidazolinium.
- the aliphatic quaternary ammonium salts may be structurally defined as follows: wherein R and R1 represent alkyl of 14 to 24 and preferably 14 to 22 carbon atoms; R2 and R3 represent lower alkyl of 1 to 4 and preferably 1 to 3 carbon atoms, X represents an anion capable of imparting water solubility or dispersibility including the aforementioned chloride, bromide, iodide, sulfate and methosulfate.
- Particularly preferred species of aliphatic quats include: distearyl dimethylammonium chloride di-hydrogenated tallow dimethyl ammonium chloride di tallow dimethyl ammonium chloride distearyl dimethyl ammonium methyl sulfate di-hydrogenated tallow dimethyl ammonium methyl sulfate.
- a builder supplementary to the zeolite and the defined bead strengthening agents may be added to the crutcher slurry, if desired.
- Any suitable water soluble or water insoluble builder, either inorganic or organic, may be used for this purpose providing that it is useful as a builder for the particular nonionic detergent or mixture of detergents that may be employed.
- Such builders are well known to those of skill in the detergent art and include: alkali metal phosphates, such as alkali metal polyphosphates including alkali metal tripolyphosphates with the caveat that such alkali metal phosphates are preferably used only in the restricted amounts herein stipulated for a low-P product; alkali metal carbonates; alkali metal bicarbonates; alkali metal polyacrylates, e.g. sodium polyacrylate; alkali metal borates, e.g., borax and alkali metal gluconates.
- alkali metal phosphates such as alkali metal polyphosphates including alkali metal tripolyphosphates with the caveat that such alkali metal phosphates are preferably used only in the restricted amounts herein stipulated for a low-P product
- alkali metal carbonates alkali metal bicarbonates
- alkali metal polyacrylates e.g. sodium polyacrylate
- alkali metal borates e.g., bo
- Suitable fillers may be present in the detergent compositions to improve the properties and in some cases, to act as diluents or fillers.
- suitable fillers the most preferred is sodium sulfate.
- suitable adjuvants are enzymes, which may be present to promote cleaning of hard to remove stains from laundry or hard surfaces.
- enzymes the most useful in laundering operations are the proteolytic and amylolytic enzymes.
- foaming agents such as lauric myristic diethanolamide, when foam is desired, and anti-foams, when desired, such as dimethyl silicone fluids.
- bleaches such as sodium perborate, which may be accompanied by suitable activator(s) to promote bleaching actions in warm or cold water.
- Flow promoting agents such as hydrated synthetic calcium silicate, which is sold under the trademark Microcel® C, may be employed in relatively small proportions.
- Other adjuvants that are usually present in detergent compositions include fluorescent brighteners, such as the stilbene brighteners; perfumes; and colorants, including dyes and water dispersible pigments.
- compositions according to the invention there may be mentioned the copolymers of polyethylene terephthalate and polyoxyethylene terephthalate (PET-POET copolymers), which are known to be effective as soil release promoters.
- PET-POET copolymers polyoxyethylene terephthalate
- the PET-POET copolymers employed will usually be of molecular weights in the range of 15,000 to 50,000, preferably 19,000 to 43,000, e.g., about 30,000 or 40,000, according to molecular weight determinations performed on samples of materials of such types. Such molecular weights are weight average molecular weights.
- the polyoxyethylene will usually be of a molecular weight in the range of about 1,000 to 10,000 and the molar ratio of polyethylene terephthalates to polyoxyethylene terephthalate units will be within the range of 2:1 to 6:1.
- the proportion of ethylene oxide to phthalic moiety in the polymer will normally be at least 10:1 and often will be 20:1 or more.
- the polymer may be considered as being essentially a modified ethylene oxide polymer with the phthalic moiety being only a minor component thereof, whether calculated on a molar or weight basis.
- a preferred PET-POET copolymer is obtained from Alkaril Chemical Company as Alkaril SRP-2-F, which also contains 5% of polyacrylate stabilizer.
- a spray-dried detergent powder in accordance with the invention having the ingredients shown below was prepared as follows, all percentages referring to the crutcher slurry are based on the solids content of the slurry in the absence of water.
- COMPONENT WEIGHT PERCENT Nonionic surfactant Naodol® 25-7 sold by Shell Chemical Company
- Adjuvants (brightener, perfume, enzyme, etc.) Balance
- An aqueous crutcher slurry is prepared by adding to water at 38°C, 3% sodium polyacrylate and 0.1% sodium toluene sulfonate while mixing with a turbine blade mixer at a low speed (10-50 rpm). After about 1 minute of agitation, there is added to the slurry a brightener, 23% sodium carbonate and 5% sodium citrate while mixing at a high speed (100 rpm) for 1-2 minutes. Zeolite at a weight percent of 35.5 is then added in 4 equal parts to the slurry to insure proper mixing, followed by 9% sodium sulfate. The mixer speed during the latter additions is at 200 rpm. All of the aforementioned percentages being based on the solids content of the slurry, in the absence of water.
- the finished batch temperature of the crutcher is about 55°C and the solids content is 62%.
- the slurry is dropped into a large hold tank prior to being pumped to a spray tower for spray drying. Typical spray pressures for this product are 500 pounds per square inch.
- Inlet air temperatures are about 400-450°C with outlet air temperatures about 95-105°C.
- the tower particles exiting the spray tower are transported to a rotary mixing drum where the nonionic surfactant heated to about 50°C is oversprayed onto the tumbling particles.
- Adjuvants such as perfume, or enzyme are also added, if desired, to the mixing drum.
- the finished particulate detergent composition may be used as a laundry composition or as a dishwashing detergent composition for automatic dishwashing machines.
- compositions of four commercial spray-dried No-P, zeolite-containing laundry detergent products sold in the United States are shown in Table I below and designated A-D.
- the presence or absence of adjuvants such as perfume, brightener and enzymes is not noted in the Table.
- Composition E is a spray-dried composition prepared in accordance with the present invention.
- the detergent compositions of Table I were each tested for mechanical strength by an empirical "Frangibility Test” (described below) which determines the frangibility (or resistance to breakage) of granular materials. Each of the compositions was also tested to determine the amount of residue (or insolubles) deposited on fabrics laundered with such composition; the test method used to rate each detergent composition being referred to as the "Residue Test” described below.
- the test method consists of placing 100 grams of 0% through 100 mesh granular material on a 100 mesh U.S. Std. sieve screen, adding three rubber balls, and shaking for two 15 minute periods. The amount of material that passes through the 100 mesh screen is weighed after 30 minutes. This figure is defined as the 100 mesh frangibility number.
- the apparatus used consists of the following:
- the apparatus used in the test method was a General Electric top-loading washing machine.
- the fabrics laundered consisted of a 3 lb. load of the following darkly colored mens garments (e.g., black, navy blue, brown or dark green): 63/35% polyester/cotton permanent press dress shirt; 100% nylon knit sport shirt; 100% polyester doubleknit or gabardine pants; and denim pants.
- darkly colored mens garments e.g., black, navy blue, brown or dark green
- a wash load as described above was laundered in the General Electric machine under cold wash water conditions (10°C) at a water level of 17 gallons containing 200 ppm water hardness. The wash cycle was five minutes.
- the wet garments were line-dried indoors and then evaluated for residue by a three member panel which checked for the following: specks, particles (large specks), streaks, smudges and polka-dots (a smudge circle).
- Each dry garment was inspected for residue, and a numerical rating assigned for each garment according to the description below.
- composition E in accordance with the invention, had superior mechanical strength as reflected in a Frangibility number below 10, and virtually no residue deposited on laundered fabrics.
- a detergent composition containing sodium citrate, surfactant and zeolite in the absence of sodium silicate similar to that described in EP 1853 published May 1979 at page 26 thereof (Example 4) is prepared by the process described in such Example for purposes of comparing its measured Frangibility relative to Composition E of the present invention described in Example 2.
- the comparative composition is designated "F” and described in Table 3 below.
Landscapes
- Chemical & Material Sciences (AREA)
- Oil, Petroleum & Natural Gas (AREA)
- Life Sciences & Earth Sciences (AREA)
- Engineering & Computer Science (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Wood Science & Technology (AREA)
- Organic Chemistry (AREA)
- Emergency Medicine (AREA)
- Health & Medical Sciences (AREA)
- Inorganic Chemistry (AREA)
- Detergent Compositions (AREA)
- Silicates, Zeolites, And Molecular Sieves (AREA)
- Glanulating (AREA)
Applications Claiming Priority (2)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
US72314691A | 1991-06-28 | 1991-06-28 | |
US723146 | 1991-06-28 |
Publications (2)
Publication Number | Publication Date |
---|---|
EP0520582A1 true EP0520582A1 (de) | 1992-12-30 |
EP0520582B1 EP0520582B1 (de) | 1998-02-04 |
Family
ID=24905058
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
EP92201881A Revoked EP0520582B1 (de) | 1991-06-28 | 1992-06-24 | Verfahren zur Herstellung von sprühgetrockneten Waschmittelzusammensetzungen auf Zeolithbasis |
Country Status (11)
Country | Link |
---|---|
EP (1) | EP0520582B1 (de) |
JP (1) | JPH05247497A (de) |
AT (1) | ATE163041T1 (de) |
AU (1) | AU653408B2 (de) |
CA (1) | CA2072506A1 (de) |
DE (1) | DE69224330D1 (de) |
EG (1) | EG20047A (de) |
MX (1) | MX9202828A (de) |
NO (1) | NO922543L (de) |
NZ (1) | NZ243130A (de) |
ZA (1) | ZA924406B (de) |
Cited By (10)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
EP0763594A1 (de) * | 1995-09-18 | 1997-03-19 | The Procter & Gamble Company | Verfahren zur Herstellung von körnigen Reinigungsmitteln |
GB2315768A (en) * | 1996-08-01 | 1998-02-11 | Procter & Gamble | Detergent compositions |
US5962397A (en) * | 1995-07-10 | 1999-10-05 | The Procter & Gamble Company | Process for making granular detergent component |
EP0969082A1 (de) † | 1997-12-10 | 2000-01-05 | Kao Corporation | Waschmittelteilchen |
WO2000077158A1 (fr) * | 1999-06-14 | 2000-12-21 | Kao Corporation | Base granulaire et detergent particulaire |
EP1215277A1 (de) * | 2000-12-18 | 2002-06-19 | Kao Corporation | Trägerpartikel sowie Waschmittelteilchen |
KR100456508B1 (ko) * | 1996-12-28 | 2005-02-02 | 주식회사 엘지생활건강 | 흡수체를이용한분말세제조성물및그의제조방법 |
WO2009115380A1 (de) * | 2008-03-19 | 2009-09-24 | Henkel Ag & Co. Kgaa | Sprühgetrocknete wasch- oder reinigungsmittelprodukte |
EP3301153A1 (de) * | 2016-10-03 | 2018-04-04 | The Procter & Gamble Company | Verfahren zur herstellung von sprühgetrockneten waschmittelpartikeln |
EP3546556A1 (de) * | 2018-03-28 | 2019-10-02 | The Procter & Gamble Company | Verfahren zur herstellung von sprühgetrocknetem waschmittelpartikel |
Families Citing this family (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JP3359591B2 (ja) * | 1999-05-10 | 2002-12-24 | 花王株式会社 | 界面活性剤担持用顆粒群の製法 |
Citations (5)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
EP0001853A1 (de) * | 1977-11-07 | 1979-05-16 | THE PROCTER & GAMBLE COMPANY | Reinigungsmittelmischungen mit verbesserter Bleichwirkung |
EP0191187A2 (de) * | 1985-02-09 | 1986-08-20 | Degussa Aktiengesellschaft | Waschmittelbuilder |
EP0313144A2 (de) * | 1987-10-23 | 1989-04-26 | Unilever N.V. | Phosphatfreie Reinigungs- und Bleichmittel |
EP0319053A2 (de) * | 1987-12-02 | 1989-06-07 | Unilever N.V. | Phosphatfreie Bleichmittel |
EP0344629A1 (de) * | 1988-06-03 | 1989-12-06 | Henkel Kommanditgesellschaft auf Aktien | Körniges Adsorptionsmittel mit verbessertem Einspülverhalten |
Family Cites Families (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US5024778A (en) * | 1981-02-26 | 1991-06-18 | Colgate-Palmolive Company | Spray dried base beads for detergent compositions containing zeolite, bentonite and polyphosphate |
-
1992
- 1992-06-12 MX MX9202828A patent/MX9202828A/es not_active IP Right Cessation
- 1992-06-12 NZ NZ243130A patent/NZ243130A/en unknown
- 1992-06-16 ZA ZA924406A patent/ZA924406B/xx unknown
- 1992-06-18 AU AU18464/92A patent/AU653408B2/en not_active Ceased
- 1992-06-24 EP EP92201881A patent/EP0520582B1/de not_active Revoked
- 1992-06-24 AT AT92201881T patent/ATE163041T1/de not_active IP Right Cessation
- 1992-06-24 DE DE69224330T patent/DE69224330D1/de not_active Expired - Lifetime
- 1992-06-26 NO NO92922543A patent/NO922543L/no unknown
- 1992-06-26 CA CA002072506A patent/CA2072506A1/en not_active Abandoned
- 1992-06-29 EG EG6034292A patent/EG20047A/xx active
- 1992-06-29 JP JP4171241A patent/JPH05247497A/ja active Pending
Patent Citations (5)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
EP0001853A1 (de) * | 1977-11-07 | 1979-05-16 | THE PROCTER & GAMBLE COMPANY | Reinigungsmittelmischungen mit verbesserter Bleichwirkung |
EP0191187A2 (de) * | 1985-02-09 | 1986-08-20 | Degussa Aktiengesellschaft | Waschmittelbuilder |
EP0313144A2 (de) * | 1987-10-23 | 1989-04-26 | Unilever N.V. | Phosphatfreie Reinigungs- und Bleichmittel |
EP0319053A2 (de) * | 1987-12-02 | 1989-06-07 | Unilever N.V. | Phosphatfreie Bleichmittel |
EP0344629A1 (de) * | 1988-06-03 | 1989-12-06 | Henkel Kommanditgesellschaft auf Aktien | Körniges Adsorptionsmittel mit verbessertem Einspülverhalten |
Cited By (21)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US5962397A (en) * | 1995-07-10 | 1999-10-05 | The Procter & Gamble Company | Process for making granular detergent component |
EP0763594A1 (de) * | 1995-09-18 | 1997-03-19 | The Procter & Gamble Company | Verfahren zur Herstellung von körnigen Reinigungsmitteln |
GB2315768A (en) * | 1996-08-01 | 1998-02-11 | Procter & Gamble | Detergent compositions |
KR100456508B1 (ko) * | 1996-12-28 | 2005-02-02 | 주식회사 엘지생활건강 | 흡수체를이용한분말세제조성물및그의제조방법 |
EP0969082B2 (de) † | 1997-12-10 | 2013-10-16 | Kao Corporation | Waschmittelteilchen |
EP0969082A1 (de) † | 1997-12-10 | 2000-01-05 | Kao Corporation | Waschmittelteilchen |
WO2000077158A1 (fr) * | 1999-06-14 | 2000-12-21 | Kao Corporation | Base granulaire et detergent particulaire |
EP1215277A1 (de) * | 2000-12-18 | 2002-06-19 | Kao Corporation | Trägerpartikel sowie Waschmittelteilchen |
US6894019B2 (en) | 2000-12-18 | 2005-05-17 | Kao Corporation | Base particles and detergent particles |
EP2787064A3 (de) * | 2008-03-19 | 2014-10-15 | Henkel AG&Co. KGAA | Sprühgetrocknete Wasch- oder Reinigungsmittel |
WO2009115380A1 (de) * | 2008-03-19 | 2009-09-24 | Henkel Ag & Co. Kgaa | Sprühgetrocknete wasch- oder reinigungsmittelprodukte |
EP3301153A1 (de) * | 2016-10-03 | 2018-04-04 | The Procter & Gamble Company | Verfahren zur herstellung von sprühgetrockneten waschmittelpartikeln |
WO2018067494A1 (en) * | 2016-10-03 | 2018-04-12 | The Procter & Gamble Company | Low ph laundry detergent composition |
CN109790489A (zh) * | 2016-10-03 | 2019-05-21 | 宝洁公司 | 低pH衣物洗涤剂组合物 |
US10676703B2 (en) * | 2016-10-03 | 2020-06-09 | The Procter & Gamble Company | Process for preparing a spray-dried laundry detergent particle |
CN109790489B (zh) * | 2016-10-03 | 2021-06-01 | 宝洁公司 | 低pH衣物洗涤剂组合物 |
EP3546556A1 (de) * | 2018-03-28 | 2019-10-02 | The Procter & Gamble Company | Verfahren zur herstellung von sprühgetrocknetem waschmittelpartikel |
WO2019191172A1 (en) * | 2018-03-28 | 2019-10-03 | The Procter & Gamble Company | Process for preparing a spray-dried laundry detergent particle |
CN111742040A (zh) * | 2018-03-28 | 2020-10-02 | 宝洁公司 | 用于制备喷雾干燥的衣物洗涤剂颗粒的方法 |
CN111742040B (zh) * | 2018-03-28 | 2021-10-29 | 宝洁公司 | 用于制备喷雾干燥的衣物洗涤剂颗粒的方法 |
US11505768B2 (en) | 2018-03-28 | 2022-11-22 | The Procter & Gamble Company | Process for preparing a spray-dried laundry detergent particle |
Also Published As
Publication number | Publication date |
---|---|
DE69224330D1 (de) | 1998-03-12 |
NZ243130A (en) | 1994-02-25 |
EG20047A (en) | 1997-03-27 |
MX9202828A (es) | 1992-12-01 |
NO922543L (no) | 1992-12-29 |
AU653408B2 (en) | 1994-09-29 |
JPH05247497A (ja) | 1993-09-24 |
EP0520582B1 (de) | 1998-02-04 |
ZA924406B (en) | 1993-12-17 |
NO922543D0 (no) | 1992-06-26 |
ATE163041T1 (de) | 1998-02-15 |
AU1846492A (en) | 1993-01-07 |
CA2072506A1 (en) | 1992-12-29 |
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