WO1995005449A1 - Procede de preparation de compositions detergentes - Google Patents
Procede de preparation de compositions detergentes Download PDFInfo
- Publication number
- WO1995005449A1 WO1995005449A1 PCT/US1994/009325 US9409325W WO9505449A1 WO 1995005449 A1 WO1995005449 A1 WO 1995005449A1 US 9409325 W US9409325 W US 9409325W WO 9505449 A1 WO9505449 A1 WO 9505449A1
- Authority
- WO
- WIPO (PCT)
- Prior art keywords
- weight
- powder
- hydrophobic silica
- process according
- polymer
- Prior art date
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- 238000000034 method Methods 0.000 title claims abstract description 61
- 239000000203 mixture Substances 0.000 title claims abstract description 58
- 230000008569 process Effects 0.000 title claims abstract description 50
- 239000003599 detergent Substances 0.000 title claims abstract description 39
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims abstract description 114
- 239000000843 powder Substances 0.000 claims abstract description 86
- 239000004094 surface-active agent Substances 0.000 claims abstract description 53
- 239000000377 silicon dioxide Substances 0.000 claims abstract description 51
- 230000002209 hydrophobic effect Effects 0.000 claims abstract description 47
- 229920000642 polymer Polymers 0.000 claims abstract description 42
- 238000002156 mixing Methods 0.000 claims abstract description 32
- 238000005469 granulation Methods 0.000 claims abstract description 23
- 230000003179 granulation Effects 0.000 claims abstract description 23
- 239000008187 granular material Substances 0.000 claims abstract description 20
- 239000007788 liquid Substances 0.000 claims abstract description 18
- 239000003945 anionic surfactant Substances 0.000 claims abstract description 17
- 239000006185 dispersion Substances 0.000 claims abstract description 16
- 239000002736 nonionic surfactant Substances 0.000 claims abstract description 14
- 125000000129 anionic group Chemical group 0.000 claims abstract description 8
- HNPSIPDUKPIQMN-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Al]O[Al]=O HNPSIPDUKPIQMN-UHFFFAOYSA-N 0.000 claims description 29
- 239000012530 fluid Substances 0.000 claims description 22
- 229920001577 copolymer Polymers 0.000 claims description 13
- 239000010457 zeolite Substances 0.000 claims description 12
- 229910021536 Zeolite Inorganic materials 0.000 claims description 11
- 238000001694 spray drying Methods 0.000 claims description 11
- VZCYOOQTPOCHFL-UHFFFAOYSA-N trans-butenedioic acid Natural products OC(=O)C=CC(O)=O VZCYOOQTPOCHFL-UHFFFAOYSA-N 0.000 claims description 10
- OFOBLEOULBTSOW-UHFFFAOYSA-N Propanedioic acid Natural products OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 0.000 claims description 9
- VZCYOOQTPOCHFL-UPHRSURJSA-N maleic acid Chemical compound OC(=O)\C=C/C(O)=O VZCYOOQTPOCHFL-UPHRSURJSA-N 0.000 claims description 9
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 claims description 8
- NIXOWILDQLNWCW-UHFFFAOYSA-N 2-Propenoic acid Natural products OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 claims description 8
- 229920000036 polyvinylpyrrolidone Polymers 0.000 claims description 7
- 235000013855 polyvinylpyrrolidone Nutrition 0.000 claims description 7
- 239000001267 polyvinylpyrrolidone Substances 0.000 claims description 5
- 229920002472 Starch Polymers 0.000 claims description 4
- 239000001768 carboxy methyl cellulose Substances 0.000 claims description 4
- 239000011248 coating agent Substances 0.000 claims description 4
- 239000011976 maleic acid Substances 0.000 claims description 4
- 108010064470 polyaspartate Proteins 0.000 claims description 4
- 239000008107 starch Substances 0.000 claims description 4
- 235000019698 starch Nutrition 0.000 claims description 4
- 229920002134 Carboxymethyl cellulose Polymers 0.000 claims description 3
- 235000010948 carboxy methyl cellulose Nutrition 0.000 claims description 3
- 239000008112 carboxymethyl-cellulose Substances 0.000 claims description 3
- 229920002554 vinyl polymer Polymers 0.000 claims description 3
- 235000011837 pasties Nutrition 0.000 claims 1
- 125000004432 carbon atom Chemical group C* 0.000 description 39
- 125000000217 alkyl group Chemical group 0.000 description 36
- 239000011734 sodium Substances 0.000 description 31
- 229910052708 sodium Inorganic materials 0.000 description 29
- -1 "soaps" Chemical class 0.000 description 28
- 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 28
- 239000000463 material Substances 0.000 description 26
- 229910000323 aluminium silicate Inorganic materials 0.000 description 20
- 150000003839 salts Chemical class 0.000 description 18
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 18
- 238000005342 ion exchange Methods 0.000 description 17
- 239000002245 particle Substances 0.000 description 16
- IAYPIBMASNFSPL-UHFFFAOYSA-N Ethylene oxide Chemical group C1CO1 IAYPIBMASNFSPL-UHFFFAOYSA-N 0.000 description 14
- 235000014113 dietary fatty acids Nutrition 0.000 description 12
- 239000000194 fatty acid Substances 0.000 description 12
- 229930195729 fatty acid Natural products 0.000 description 12
- 229920001296 polysiloxane Polymers 0.000 description 11
- 150000001875 compounds Chemical class 0.000 description 10
- 239000007859 condensation product Substances 0.000 description 9
- 150000004665 fatty acids Chemical class 0.000 description 9
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 8
- 239000003795 chemical substances by application Substances 0.000 description 8
- 238000001035 drying Methods 0.000 description 8
- 239000003760 tallow Substances 0.000 description 8
- 238000001816 cooling Methods 0.000 description 7
- 159000000001 potassium salts Chemical class 0.000 description 7
- 159000000000 sodium salts Chemical class 0.000 description 7
- 239000007787 solid Substances 0.000 description 7
- 229910002012 Aerosil® Inorganic materials 0.000 description 6
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 description 6
- 239000002253 acid Substances 0.000 description 6
- 229910052783 alkali metal Inorganic materials 0.000 description 6
- 150000001340 alkali metals Chemical class 0.000 description 6
- 230000000694 effects Effects 0.000 description 6
- 239000004615 ingredient Substances 0.000 description 6
- 239000011591 potassium Substances 0.000 description 6
- 229910052700 potassium Inorganic materials 0.000 description 6
- 239000002002 slurry Substances 0.000 description 6
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 description 5
- BHPQYMZQTOCNFJ-UHFFFAOYSA-N Calcium cation Chemical group [Ca+2] BHPQYMZQTOCNFJ-UHFFFAOYSA-N 0.000 description 5
- 235000013162 Cocos nucifera Nutrition 0.000 description 5
- 244000060011 Cocos nucifera Species 0.000 description 5
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 5
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 description 5
- 238000005054 agglomeration Methods 0.000 description 5
- 230000002776 aggregation Effects 0.000 description 5
- 150000001298 alcohols Chemical class 0.000 description 5
- 150000002191 fatty alcohols Chemical class 0.000 description 5
- 239000000344 soap Substances 0.000 description 5
- 239000000243 solution Substances 0.000 description 5
- 229910021653 sulphate ion Inorganic materials 0.000 description 5
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 4
- JLVVSXFLKOJNIY-UHFFFAOYSA-N Magnesium ion Chemical group [Mg+2] JLVVSXFLKOJNIY-UHFFFAOYSA-N 0.000 description 4
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 description 4
- 125000001931 aliphatic group Chemical group 0.000 description 4
- 229910001424 calcium ion Inorganic materials 0.000 description 4
- 239000003093 cationic surfactant Substances 0.000 description 4
- 235000019864 coconut oil Nutrition 0.000 description 4
- 239000003240 coconut oil Substances 0.000 description 4
- 229910052757 nitrogen Inorganic materials 0.000 description 4
- 230000000704 physical effect Effects 0.000 description 4
- 238000005086 pumping Methods 0.000 description 4
- 150000003467 sulfuric acid derivatives Chemical class 0.000 description 4
- DNIAPMSPPWPWGF-UHFFFAOYSA-N Propylene glycol Chemical compound CC(O)CO DNIAPMSPPWPWGF-UHFFFAOYSA-N 0.000 description 3
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- 229920013820 alkyl cellulose Polymers 0.000 description 3
- 150000008051 alkyl sulfates Chemical class 0.000 description 3
- 150000001412 amines Chemical class 0.000 description 3
- 229910000019 calcium carbonate Inorganic materials 0.000 description 3
- 229910002092 carbon dioxide Inorganic materials 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
- 125000001301 ethoxy group Chemical group [H]C([H])([H])C([H])([H])O* 0.000 description 3
- 125000002768 hydroxyalkyl group Chemical group 0.000 description 3
- 238000004519 manufacturing process Methods 0.000 description 3
- 239000011159 matrix material Substances 0.000 description 3
- 230000007935 neutral effect Effects 0.000 description 3
- 239000011164 primary particle Substances 0.000 description 3
- 239000007921 spray Substances 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- QAOWNCQODCNURD-UHFFFAOYSA-N sulfuric acid Substances OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 3
- NLXLAEXVIDQMFP-UHFFFAOYSA-N Ammonium chloride Substances [NH4+].[Cl-] NLXLAEXVIDQMFP-UHFFFAOYSA-N 0.000 description 2
- LSNNMFCWUKXFEE-UHFFFAOYSA-M Bisulfite Chemical compound OS([O-])=O LSNNMFCWUKXFEE-UHFFFAOYSA-M 0.000 description 2
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 2
- KRKNYBCHXYNGOX-UHFFFAOYSA-K Citrate Chemical compound [O-]C(=O)CC(O)(CC([O-])=O)C([O-])=O KRKNYBCHXYNGOX-UHFFFAOYSA-K 0.000 description 2
- 108090000790 Enzymes Proteins 0.000 description 2
- 102000004190 Enzymes Human genes 0.000 description 2
- OTMSDBZUPAUEDD-UHFFFAOYSA-N Ethane Chemical class CC OTMSDBZUPAUEDD-UHFFFAOYSA-N 0.000 description 2
- VZCYOOQTPOCHFL-OWOJBTEDSA-N Fumaric acid Chemical compound OC(=O)\C=C\C(O)=O VZCYOOQTPOCHFL-OWOJBTEDSA-N 0.000 description 2
- MBBZMMPHUWSWHV-BDVNFPICSA-N N-methylglucamine Chemical compound CNC[C@H](O)[C@@H](O)[C@H](O)[C@H](O)CO MBBZMMPHUWSWHV-BDVNFPICSA-N 0.000 description 2
- BPQQTUXANYXVAA-UHFFFAOYSA-N Orthosilicate Chemical compound [O-][Si]([O-])([O-])[O-] BPQQTUXANYXVAA-UHFFFAOYSA-N 0.000 description 2
- 125000002252 acyl group Chemical group 0.000 description 2
- 150000001335 aliphatic alkanes Chemical group 0.000 description 2
- 125000005907 alkyl ester group Chemical group 0.000 description 2
- 235000019270 ammonium chloride Nutrition 0.000 description 2
- 238000013459 approach Methods 0.000 description 2
- 239000007864 aqueous solution Substances 0.000 description 2
- 238000000889 atomisation Methods 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 230000015556 catabolic process Effects 0.000 description 2
- 239000007795 chemical reaction product Substances 0.000 description 2
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- 230000005494 condensation Effects 0.000 description 2
- 230000001143 conditioned effect Effects 0.000 description 2
- 238000010924 continuous production Methods 0.000 description 2
- 238000006731 degradation reaction Methods 0.000 description 2
- 238000013461 design Methods 0.000 description 2
- KPUWHANPEXNPJT-UHFFFAOYSA-N disiloxane Chemical class [SiH3]O[SiH3] KPUWHANPEXNPJT-UHFFFAOYSA-N 0.000 description 2
- 229940088598 enzyme Drugs 0.000 description 2
- 150000002148 esters Chemical class 0.000 description 2
- RTZKZFJDLAIYFH-UHFFFAOYSA-N ether Substances CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 2
- 238000001125 extrusion Methods 0.000 description 2
- 235000019387 fatty acid methyl ester Nutrition 0.000 description 2
- 239000010419 fine particle Substances 0.000 description 2
- 235000013305 food Nutrition 0.000 description 2
- 230000007062 hydrolysis Effects 0.000 description 2
- 238000006460 hydrolysis reaction Methods 0.000 description 2
- 238000010348 incorporation Methods 0.000 description 2
- 239000002563 ionic surfactant Substances 0.000 description 2
- 238000006386 neutralization reaction Methods 0.000 description 2
- 230000003472 neutralizing effect Effects 0.000 description 2
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 description 2
- 235000014366 other mixer Nutrition 0.000 description 2
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 description 2
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Chemical compound [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 description 2
- 238000002360 preparation method Methods 0.000 description 2
- 230000009467 reduction Effects 0.000 description 2
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- 238000009987 spinning Methods 0.000 description 2
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- 150000003871 sulfonates Chemical class 0.000 description 2
- AKEJUJNQAAGONA-UHFFFAOYSA-N sulfur trioxide Chemical compound O=S(=O)=O AKEJUJNQAAGONA-UHFFFAOYSA-N 0.000 description 2
- GETQZCLCWQTVFV-UHFFFAOYSA-N trimethylamine Chemical class CN(C)C GETQZCLCWQTVFV-UHFFFAOYSA-N 0.000 description 2
- 239000002888 zwitterionic surfactant Substances 0.000 description 2
- 239000001124 (E)-prop-1-ene-1,2,3-tricarboxylic acid Substances 0.000 description 1
- ZPFAVCIQZKRBGF-UHFFFAOYSA-N 1,3,2-dioxathiolane 2,2-dioxide Chemical compound O=S1(=O)OCCO1 ZPFAVCIQZKRBGF-UHFFFAOYSA-N 0.000 description 1
- GHPCICSQWQDZLM-UHFFFAOYSA-N 1-(4-chlorophenyl)sulfonyl-1-methyl-3-propylurea Chemical compound CCCNC(=O)N(C)S(=O)(=O)C1=CC=C(Cl)C=C1 GHPCICSQWQDZLM-UHFFFAOYSA-N 0.000 description 1
- JAHNSTQSQJOJLO-UHFFFAOYSA-N 2-(3-fluorophenyl)-1h-imidazole Chemical compound FC1=CC=CC(C=2NC=CN=2)=C1 JAHNSTQSQJOJLO-UHFFFAOYSA-N 0.000 description 1
- PSZAEHPBBUYICS-UHFFFAOYSA-N 2-methylidenepropanedioic acid Chemical compound OC(=O)C(=C)C(O)=O PSZAEHPBBUYICS-UHFFFAOYSA-N 0.000 description 1
- XYJLPCAKKYOLGU-UHFFFAOYSA-N 2-phosphonoethylphosphonic acid Chemical class OP(O)(=O)CCP(O)(O)=O XYJLPCAKKYOLGU-UHFFFAOYSA-N 0.000 description 1
- 239000004254 Ammonium phosphate Substances 0.000 description 1
- 102000013142 Amylases Human genes 0.000 description 1
- 108010065511 Amylases Proteins 0.000 description 1
- 108091005658 Basic proteases Proteins 0.000 description 1
- BVKZGUZCCUSVTD-UHFFFAOYSA-M Bicarbonate Chemical compound OC([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-M 0.000 description 1
- 102000005575 Cellulases Human genes 0.000 description 1
- 108010084185 Cellulases Proteins 0.000 description 1
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 1
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- WQZGKKKJIJFFOK-GASJEMHNSA-N Glucose Natural products OC[C@H]1OC(O)[C@H](O)[C@@H](O)[C@@H]1O WQZGKKKJIJFFOK-GASJEMHNSA-N 0.000 description 1
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- 108091005507 Neutral proteases Proteins 0.000 description 1
- SXKQTYJLWWQUKA-UHFFFAOYSA-N O.O.O.O.O.O.O.O.O.O.OB(O)O.OB(O)O.OB(O)O.OB(O)O Chemical compound O.O.O.O.O.O.O.O.O.O.OB(O)O.OB(O)O.OB(O)O.OB(O)O SXKQTYJLWWQUKA-UHFFFAOYSA-N 0.000 description 1
- 229910019142 PO4 Inorganic materials 0.000 description 1
- ABLZXFCXXLZCGV-UHFFFAOYSA-N Phosphorous acid Chemical class OP(O)=O ABLZXFCXXLZCGV-UHFFFAOYSA-N 0.000 description 1
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- 239000004965 Silica aerogel Substances 0.000 description 1
- PMZURENOXWZQFD-UHFFFAOYSA-L Sodium Sulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=O PMZURENOXWZQFD-UHFFFAOYSA-L 0.000 description 1
- 235000010724 Wisteria floribunda Nutrition 0.000 description 1
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- ZRIUUUJAJJNDSS-UHFFFAOYSA-N ammonium phosphates Chemical class [NH4+].[NH4+].[NH4+].[O-]P([O-])([O-])=O ZRIUUUJAJJNDSS-UHFFFAOYSA-N 0.000 description 1
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- 125000003187 heptyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
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- 125000001165 hydrophobic group Chemical group 0.000 description 1
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 description 1
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- 125000005341 metaphosphate group Chemical group 0.000 description 1
- 229920000609 methyl cellulose Polymers 0.000 description 1
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 1
- 239000001923 methylcellulose Substances 0.000 description 1
- 235000010981 methylcellulose Nutrition 0.000 description 1
- LVHBHZANLOWSRM-UHFFFAOYSA-N methylenebutanedioic acid Natural products OC(=O)CC(=C)C(O)=O LVHBHZANLOWSRM-UHFFFAOYSA-N 0.000 description 1
- HNEGQIOMVPPMNR-UHFFFAOYSA-N methylfumaric acid Natural products OC(=O)C(C)=CC(O)=O HNEGQIOMVPPMNR-UHFFFAOYSA-N 0.000 description 1
- 150000007522 mineralic acids Chemical class 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 239000003607 modifier Substances 0.000 description 1
- 239000003921 oil Substances 0.000 description 1
- 235000019198 oils Nutrition 0.000 description 1
- 150000007524 organic acids Chemical class 0.000 description 1
- 239000011368 organic material Substances 0.000 description 1
- 150000001282 organosilanes Chemical class 0.000 description 1
- MPQXHAGKBWFSNV-UHFFFAOYSA-N oxidophosphanium Chemical class [PH3]=O MPQXHAGKBWFSNV-UHFFFAOYSA-N 0.000 description 1
- 239000012188 paraffin wax Substances 0.000 description 1
- 239000010452 phosphate Substances 0.000 description 1
- 235000021317 phosphate Nutrition 0.000 description 1
- 239000011574 phosphorus Substances 0.000 description 1
- 229910052698 phosphorus Inorganic materials 0.000 description 1
- 229920002401 polyacrylamide Polymers 0.000 description 1
- 229920000058 polyacrylate Polymers 0.000 description 1
- 229920001223 polyethylene glycol Polymers 0.000 description 1
- 238000006116 polymerization reaction Methods 0.000 description 1
- 239000001205 polyphosphate Chemical class 0.000 description 1
- 235000011176 polyphosphates Nutrition 0.000 description 1
- 229920002689 polyvinyl acetate Polymers 0.000 description 1
- 239000011118 polyvinyl acetate Substances 0.000 description 1
- 229920002451 polyvinyl alcohol Polymers 0.000 description 1
- 235000019422 polyvinyl alcohol Nutrition 0.000 description 1
- 229910000027 potassium carbonate Inorganic materials 0.000 description 1
- 238000001556 precipitation Methods 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- KCXFHTAICRTXLI-UHFFFAOYSA-N propane-1-sulfonic acid Chemical class CCCS(O)(=O)=O KCXFHTAICRTXLI-UHFFFAOYSA-N 0.000 description 1
- LUIGSJYSMIUMPK-UHFFFAOYSA-N propane-1-sulfonoperoxoic acid Chemical class CCCS(=O)(=O)OO LUIGSJYSMIUMPK-UHFFFAOYSA-N 0.000 description 1
- 150000003856 quaternary ammonium compounds Chemical class 0.000 description 1
- 230000005855 radiation Effects 0.000 description 1
- 230000015227 regulation of liquid surface tension Effects 0.000 description 1
- 238000000518 rheometry Methods 0.000 description 1
- 238000007127 saponification reaction Methods 0.000 description 1
- 229920006395 saturated elastomer Polymers 0.000 description 1
- 229940071207 sesquicarbonate Drugs 0.000 description 1
- 150000004760 silicates Chemical class 0.000 description 1
- CDBYLPFSWZWCQE-UHFFFAOYSA-L sodium carbonate Substances [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 1
- 229910000029 sodium carbonate Inorganic materials 0.000 description 1
- 235000019812 sodium carboxymethyl cellulose Nutrition 0.000 description 1
- 229920001027 sodium carboxymethylcellulose Polymers 0.000 description 1
- 229910052938 sodium sulfate Inorganic materials 0.000 description 1
- 235000011152 sodium sulphate Nutrition 0.000 description 1
- 235000019832 sodium triphosphate Nutrition 0.000 description 1
- HSFQBFMEWSTNOW-UHFFFAOYSA-N sodium;carbanide Chemical group [CH3-].[Na+] HSFQBFMEWSTNOW-UHFFFAOYSA-N 0.000 description 1
- 241000894007 species Species 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
- 235000000346 sugar Nutrition 0.000 description 1
- 150000008163 sugars Chemical class 0.000 description 1
- 230000001180 sulfating effect Effects 0.000 description 1
- 125000001273 sulfonato group Chemical group [O-]S(*)(=O)=O 0.000 description 1
- 150000003462 sulfoxides Chemical class 0.000 description 1
- GTZCVFVGUGFEME-UHFFFAOYSA-N trans-aconitic acid Natural products OC(=O)CC(C(O)=O)=CC(O)=O GTZCVFVGUGFEME-UHFFFAOYSA-N 0.000 description 1
- UNXRWKVEANCORM-UHFFFAOYSA-I triphosphate(5-) Chemical compound [O-]P([O-])(=O)OP([O-])(=O)OP([O-])([O-])=O UNXRWKVEANCORM-UHFFFAOYSA-I 0.000 description 1
- 239000001993 wax 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
- C11D3/37—Polymers
- C11D3/3746—Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds
- C11D3/3757—(Co)polymerised carboxylic acids, -anhydrides, -esters in solid and liquid compositions
- C11D3/3761—(Co)polymerised carboxylic acids, -anhydrides, -esters in solid and liquid compositions in solid compositions
-
- C—CHEMISTRY; METALLURGY
- C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
- C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
- C11D11/00—Special methods for preparing compositions containing mixtures of detergents
- C11D11/0082—Special methods for preparing compositions containing mixtures of detergents one or more of the detergent ingredients being in a liquefied state, e.g. slurry, paste or melt, and the process resulting in solid detergent particles such as granules, powders or beads
-
- C—CHEMISTRY; METALLURGY
- C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
- C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
- C11D17/00—Detergent materials or soaps characterised by their shape or physical properties
- C11D17/06—Powder; Flakes; Free-flowing mixtures; Sheets
- C11D17/065—High-density particulate detergent compositions
-
- C—CHEMISTRY; METALLURGY
- C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
- C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
- C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
- C11D3/02—Inorganic compounds ; Elemental compounds
- C11D3/12—Water-insoluble compounds
- C11D3/124—Silicon containing, e.g. silica, silex, quartz or glass beads
-
- C—CHEMISTRY; METALLURGY
- C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
- C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
- C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
- C11D3/16—Organic compounds
- C11D3/20—Organic compounds containing oxygen
- C11D3/22—Carbohydrates or derivatives thereof
- C11D3/222—Natural or synthetic polysaccharides, e.g. cellulose, starch, gum, alginic acid or cyclodextrin
-
- 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
- C11D3/22—Carbohydrates or derivatives thereof
- C11D3/222—Natural or synthetic polysaccharides, e.g. cellulose, starch, gum, alginic acid or cyclodextrin
- C11D3/225—Natural or synthetic polysaccharides, e.g. cellulose, starch, gum, alginic acid or cyclodextrin etherified, e.g. CMC
-
- 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
- C11D3/3746—Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds
- C11D3/3769—(Co)polymerised monomers containing nitrogen, e.g. carbonamides, nitriles or amines
- C11D3/3776—Heterocyclic compounds, e.g. lactam
-
- 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
- C11D3/3792—Amine oxide containing polymers
Definitions
- the present invention relates to a process for making granular detergent which have a high surfactant activity and which are free-flowing and rapidly dissolving.
- the invention relates to a pre ixed free- flowing powder which comprises hydrophobic silica and a hygroscopic powder which comprises a polymer.
- the invention relates to high active, high bulk density granular detergent compositions.
- Granular detergent granules comprising low levels of certain polymers which provide structure or strength to the granule are known and have been made by spray drying aqueous solutions or slurries comprising the polymer.
- spray dried granules have low bulk densities (for example 350-550 g/1) .
- Further treatment is necessary in order to increase the bulk density and various methods have been proposed to do this.
- One approach is to apply mechanical work to the spray dried powder in order to reduce its porosity and increase its bulk density.
- Another approach is to granulate a liquid or paste, typically in the presence of a powder. Polymers may be added to such a
- SUBSTITUT ⁇ SHEET(RULE26) process either as a component of the liquid/paste, or as a component of the powder. Examples in the prior art of the such processes include:
- compositions comprising polymer and water soluble inorganic component.
- Compositions comprising surfactants and hydrophobic silica are not foreseen.
- EPA 513 824 published on 19th November, 1992 describes a process for making granular detergents which comprise up to 60% by weight of nonionic surfactant. It suggests that various powder components may be premixed in order to improve physical properties, but it does not indicate which powders may be advantageously premixed.
- the hygroscopic nature of many polymers presents a problem.
- the component also comprises a high level of surfactant.
- Hygroscopic powders which are bound into the surface of the detergent component cause the component to readily absorb water which encourages gel formation, caking of the detergent powder and poor dispensing and dissolution properties.
- the present invention aims to solve this problem by providing a process in which the surface of hygroscopic powders which comprise polymers is modified before the high bulk density detergent granules are formed. This surface modification effect is provided by premixing the hygroscopic powder with hydrophobic silica.
- the present invention further aims to provide a high bulk density detergent coroosition which comprises high levels of detergent surfactant and polymers.
- a process for making a high active granular detergent component or composition having a bulk density of at least 650 g/1 which comprises the steps of: i) making a paste or liquid which comprises at least 40% by weight of a surfactant selected from anionic and nonionic surfactants, ii) mixing said surfactant paste or liquid with a powder to form a mixture which may be in the form of either a paste or a cohesive powder; iii) forming granules by fine dispersion mixing or granulation of said mixture,, optionally in the presence of an effective amount of one or more additional powders; wherein the powder used in step ii) comprises a free- flowing, premixed powder comprising from 0.5% to 10% by weight of a hydrophobic silica and from 75% to 99.5% by weight of a hygroscopic powder comprising a polymer.
- the first aspect of the present invention relates to a process for making a high active granular detergent component or composition having a bulk density of at least 650 g/1.
- the process comprises the steps of: i) making a paste or liquid which comprises at least 40% by weight of a surfactant selected from anionic and nonionic surfactants, ii) mixing said surfactant paste or liquid with a powder wherein the powder is a free-flowing, premixed powder comprising from 0.5% to 10% by weight of a hydrophobic silica and from 75% to 99.5% by weight of a hygroscopic powder comprising a polymer.
- the resulting mixture may be in the form of either a paste or a cohesive powder; and iii) forming granules by fine dispersion mixing or granulation of said mixture, optionally in the presence of an effective amount of one or more additional powders.
- the polymer component of the hygroscopic powder is chosen from the group consisting of polymers or co ⁇ polymers of acrylic and maleic acid, polyvinyl pyrrolidone, polyvinyl pyrridine N oxide, carboxymethyl cellulose, polyaspartate, and starch.
- the hydrophobic silica is used as a coating agent to coat, or partially coat the outer surfaces of the hygroscopic powder.
- One method of preparing the hygroscopic powder which is useful in the present invention is to use a spray drying technique, wherein a two fluid nozzle is used in the spray drying step. Most preferably compressed air is used as one of the fluids in the two fluid nozzle.
- the premixed hydrophobic silica and hygroscopic polymer is mixed with the surfactant paste prior to the fine dispersion mixing of step iii) .
- One way of doing this is to use an extruder, for example a twin screw extruder.
- An example of a range of typical compositions of the premixed hydrophobic silica and hygroscopic polymer is: a) from 80% to 95% by weight of a polymer; b) from 1% to 5% by weight of hydrophobic silica; c) up to 20% by weight of zeolite
- the present invention relates to a granular detergent component having a bulk density of at least 650 g/1 and comprising: a) at least 35% (preferably at least 45%, more preferably at least 55%) by weight of surfactant; b) from 5% to 25% (preferably from 8% to 15%) by weight polymer; c) from 0.05% to 2.5% (preferably from 0.5% to 1%) by weight of hydrophobic silica;
- a high active surfactant paste is prepared.
- One or various aqueous pastes of the salts of anionic surfactants is preferred for use in the present invention, preferably the sodium salt of the anionic surfactant.
- the anionic surfactant is preferably as concentrated as possible, (that is, with the lowest possible moisture content possible that allows it to flow in the manner of a liquid) so that it can be pumped at temperatures at which it remains stable.
- an anionic surfactant should preferably be a part of the paste in a concentration of above 10% by weight, preferably from 10- 95%, more preferably from 20-95%, and most preferably from 40%-95% by weight. It is preferred that the moisture in the surfactant aqueous paste is as low as possible, while maintaining paste fluidity, since low moisture leads to a higher concentration of the surfactant in the finished particle.
- the paste contains between 5 and 40% water, more preferably between 5 and 30% water and most preferably between 5 and 20% water.
- high active surfactant pastes it is preferable to use high active surfactant pastes to minimize the total water level in the system during mixing, granulating and drying.
- Lower water levels allow for: (1) a higher active surfactant to builder ratio, e.g., 1:1; (2) higher levels of other liquids in the formula without causing dough or granular stickiness; (3) less cooling, due to higher allowable granulation temperatures; and (4) less granular drying to meet final moisture limits.
- Viscosity is a function, among others, of concentration and temperature, with a range in this application from about 5,000 cps to 10,000,000 cps.
- the viscosity of the paste entering the system is from about 20,000 to about 100,000 cps. and more preferably from about 30,000 to about 70,000 cps.
- the viscosity of the paste of this invention is measured at a temperature of 70°C and at a shear rate of from 10 to 50 sec" 1 , in particular, about 25 sec" 1 .
- the paste can be introduced into the mixer at an initial temperature between its softening point (generally in the range of 40-60°C) and its degradation point (depending on the chemical nature of the paste, e.g. alkyl sulphate pastes tend to degrade above 75-85°C) .
- High temperatures reduce viscosity simplifying the pumping of the paste but result in lower active agglomerates.
- the use of in-line moisture reduction steps e.g. flash drying), however, requi the use of higher temperatures (above 100°C) .
- the activity of the agglomerates is. maintained high due to the elimination of moisture.
- the introduction of the paste into the mixer can be done in many ways, from simply pouring to high pressure pumping through small holes at the end of the pipe, before the entrance to the mixer. While all these ways are viable to manufacture agglomerates with good physical properties, it has been found that in a preferred embodiment of the present invention the extrusion of the paste results in a better distribution in the mixer which improves the yield of particles with the desired size. Most preferably a twin screw extruder is used.
- the use of high imping pressures prior to the entrance in the mixer results in an increased activity in the final agglomerates.
- the activity of the aqueous surfactant paste is at least 30% and can go up to about 95%; preferred activities are : 60-90% and 70-80%.
- the balance of the paste is primarily water. At the higher active concentrations, little or no builder is required for cold granulation of the paste.
- the resultant concentrated surfactant granules can be added to dry builders or powders or used in conventional agglomeration operations.
- the aqueous surfactant paste contains an organic surfactant selected from the group consisting of anionic, nonionic, zwitterionic, ampholytic and cationic surfactants, and mixtures thereof. Anionic surfactants are preferred. Surfactants useful herein are listed in U.S. Pat. No.
- cationic surfactants are generally less compatible with the aluminosilicate materials herein, and thus are preferably used at low levels, if at all, in the present compositions.
- the following are representative examples of surfactants useful in the present compositions.
- Water-soluble salts of the higher fatty acids are useful anionic surfactants in the compositions herein.
- Soaps can be made by direct saponification of fats and oils or by the neutralization of free fatty acids.
- Particularly useful are the sodium and potassium salts of the mixtures of fatty acids derived from coconut oil and tallow, i.e., sodium or potassium tallow and coconut soap.
- Useful anionic surfactants also include the water- soluble salts, preferably the alkali metal, ammonium and alkylolammonium salts, of organic sulfuric reaction products having in their molecular structure an alkyl group containing from about 10 to about 20 carbon atoms in a linear or branched chain and a sulfonic acid or sulfuric acid ester group.
- alkyl is the alkyl portion of acyl groups.
- this group of synthetic or natural surfactants are the sodium and potassium alkyl sulfates, especially those obtained by sulfating the higher alcohols (C 8 -C 18 carbon atoms) such as those produced by reducing the glycerides of tallow or coconut oil; and the sodium and potassium alkyl benzene sulfonates in which the alkyl group contains from about 9 to about 15 carbon atoms, in straight or branched chain configuration, e.g., those of the type described in U.S.
- anionic surfactants herein are the sodium alkyl glyceryl ether sulfonates, especially those ethers of higher alcohols derived from tallow and coconut oil; sodium coconut oil fatty acid monoglyceride sulfonates and sulfates; sodium or potassium salts of alkyl phenol ethylene oxide ether sulfates containing from about 1 to about 10 units of ethylene oxide per molecule and wherein the alkyl groups contain from about 8 to about 12 carbon atoms; and sodium or potassium salts of alkyl ethylene oxide ether sulfates containing from about 1 to about 10 units of ethylene oxide per molecule and wherein the alkyl group contains from about 10 to about 20 carbon atoms.
- Other useful anionic surfactants herein include the water-soluble salts of esters of alpha-sulfonated fatty acids containing from about 6 to 20 carbon atoms in the fatty acid group and from about 1 to 10 carbon atoms in the ester group; water-soluble salts of 2-ac ,oxy-alkane-l- sulfonic acids containing from about 2 to 9 carbon atoms in the acyl group and from about 9 to about 23 carbon atoms in the alkane moiety; alkyl ether sulfates containing from about 10 to 20 carbon atoms in the alkyl group and from about 1 to 30 moles of ethylene oxide; watersoluble salts of olefin sulfonates contai"-ng from about 12 to 24 carbon atoms; and beta-alkyloxy al.
- ⁇ e sulfonates c ontaining from about 1 to 3 carbon atoms in the alkyl group and from about 8 to about 20 carbon atoms in the alkane moiety.
- the acid salts are typically discussed and used, the acid neutralization cam be performed as part of the fine dispersion mixing step.
- the preferred anionic surfactant pastes are mixtures of linear or branched alkylbenzene sulfonates having an alkyl of 10-16 carbon atoms and alkyl sulfates having an alkyl of 10-18 carbon atoms. These pastes are usually produced by reacting a liquid organic material with sulfur trioxide to produce a sulfonic or sulfuric acid and then neutralizing the acid to produce a salt of that acid.
- the salt is the surfactant paste discussed throughout this document.
- the sodium salt is preferred due to end performance benefits and cost of NaOH vs. other neutralizing agents, but is not required as other agents such as KOH may be used.
- Water-soluble nonionic surfactants are also useful as surfactants in the compositions of the invention. Indeed, preferred processes use anionic/nonionic blends.
- a particularly preferred paste comprises a blend of nonionic and anionic surfactants having a ratio of from about 0.01:1 to about 1:1, more preferably about 0.05:1.
- Nonionics can be used up to an equal amount of the primary organic surfactant.
- Such nonionic materials include compounds produced by the condensation of alkylene oxide groups (hydrophilic in nature) with an organic hydrophobic compound, which may be aliphatic or alkyl aromatic in nature.
- Suitable nonionic surfactants include the polyethylene oxide condensates of alkyl phenols, e.g., the condensation products of alkyl phenols having an alkyl group containing from about 6 to 16 carbon atoms, in either a straight chain or branched chain configuration, with from about 4 to 25 moles of ethylene oxide per mole of alkyl phenol.
- Preferred nonionics are the water-soluble condensation products of aliphatic alcohols containing from 8 to 22 carbon atoms, in either, straight chain or branched configuration, with from 4 to 25 moles of ethylene oxide per more of alcohol. Particularly preferred are the condensation products of alcohols having an alkyl group containing from about 9 to 15 carbon atoms with from about 4 to 25 moles of ethylene oxide per mole of alcohol; and condensation products of propylene glycol with ethylene oxide.
- polyhydroxy fatty acid amides which may be produced by reacting a fatty acid ester and an N-alkyl polyhydroxy amine.
- the preferred amine for use in the present invention is N-(R1)-CH2(CH20H)4-CH2-OH and the preferred ester is a C12-C20 fatty acid methyl ester.
- Most preferred is the reaction product of N-methyl glucamine with C12-C20 fatty acid methyl ester.
- RO (C n H 2n O) tZ ⁇ wherein Z is a moiety derived from glucose; R is a saturated hydrophobic alkyl group that contains from 12 to 18 carbon atoms; t is from 0 to 10 and n is 2 or 3; x is from 1.3 to 4, the compounds including less than 10% unreacted fatty alcohol and less than 50% short chain alkyl polyglucosides.
- Compounds of this type and their use in detergent compositions are disclosed in EP-B 0070074, 0070077, 0075996 and 0094118.
- Semi-polar nonionic surfactants include water-soluble amine oxides containing one alkyl moiety of from about 10 to 18 carbon atoms and 2 moieties selected from the group consisting of alkyl groups and hydroxyalkyl groups containing from 1 to about 3 carbon atoms; water-soluble phosphine oxides containing one alkyl moiety of about 10 to 18 carbon atoms and 2 moieties selected from the group consisting of alkyl groups and hydroxyalkyl groups containing from about 1 to 3 carbon atoms; and water- soluble sulfoxides containing one alkyl moiety of from about 10 to 18 carbon atoms and a moiety selected from the group consisting of alkyl and hydroxyalkyl moieties of from about 1 to 3 carbon atoms.
- Ampholytic surfactants include derivatives of aliphatic or aliphatic derivatives of heterocyclic secondary and tertiary amines in which the aliphatic moiety can be either straight or branched chain and wherein one of the aliphatic substituents contains from about 8 to 18 carbon atoms and at least one aliphatic substituent contains an anionic water-solubilizing group.
- Zwitterionic surfactants include derivatives of aliphatic quaternary ammonium phosphonium, and sulfoniu compounds in which one of the aliphatic substituents contains fr»m about 8 to 18 carbon atoms.
- Particularly preferred surfactants herein include linear alkylbenzene sulfonates containing from about 11 to 14 carbon atoms in the alkyl group; alkyl sulfates containing from about 12 to 18 carbon atoms in the alkyl group; coconutalkyl glyceryl ether sulfonates; alkyl ether sulfates wherein the alkyl moiety contains from about 14 to 18 carbon atoms and wherein the average degree of ethoxylation is from about 1 to 4; olefin or paraffin sulfonates containing from about 14 to 16 carbon atoms; alkyldimethylamine oxides wherein the alkyl group contains from about 11 to 16 carbon atoms; alkyldimethylammonio propane sulfonates and alkyldimethylammonio hydroxy propane sulfonates wherein the alkyl group contains from about 14 to 18 carbon atoms; soaps of higher fatty acids containing from about 12 to 18 carbon atom
- Useful cationic surfactants include water-soluble quaternary ammonium compounds of the form R4R5RsR7N + X ⁇ , wherein R4 is alkyl having from 10 to 20, preferably from
- R5 12-18 carbon atoms, and R5, R Q and ' P.- j are each C ⁇ to C 7 alkyl preferably methyl;
- X" is an anion, e.g. chloride.
- trimethyl ammonium compounds include C 12 - 1 alkyl trimethyl ammonium chloride and cocalkyl trimethyl ammonium ethosulfate.
- Specific preferred surfactants for use herein include: sodium linear C ⁇ -C ⁇ alkylbenzene sulfonate; alpha-olefin sulphonates; triethanolam onium C 11 -C 13 alkylbenzene sulfonate; alkyl sulfates, (tallow, coconut, palm, synthetic origins, e.g.
- the surfactant paste described above is formed into granules by fine dispersion mixing in the presence of a powder.
- the surfactant paste is either intimately mixed with a component which is a free- flowing mixture of a hydrophobic silica and a hygroscopic powder comprising a polymer prior to granulation, or said free-flowing mixture is added directly to the mixer/granulator as one of the powder components of the granulation step.
- the hydrophobic silica which is present at a level of from 0.5% to 10% of the component is a highly dispersed amorphous silicon dioxide. It is commercially available in many forms. Most commonly silica has a tapped density of from 50 g/1 to 120 g/1. The specific surface area of the particles ranges from 25 square metres per gram to 800 square metres per gram.
- the surface of silica particles can be chemically modified to change their behaviour with respect to water. For example,silica particles may be treated with organosilanes to make the particles predominantly hydrophobic. It has been found that silicas must be hydrophobised to be useful in the present invention.
- silica is usually prepared by one of two techniques; either by precipitation or by high temperature flame hydrolysis.
- Precipitated silicas generally have an agglomerate size of from 3 micrometers to 100 micrometers
- fumed silicas made by flame hydrolysis
- fumed silicas usually have primary particles which are generally spherical and have an average diameter of from 7nm to 40nm. Fumed silicas having an average primary particle size of from 7 to 25 nanometers are preferred in the present invention.
- This silica is a hydrophobic, fumed silica which has a specific surface area of about 110 square metres per gram and an average primary particle size of 16 nanometers.
- the other essential feature of the powder is a hygroscopic powder which comprises a polymer.
- hygroscopic it is meant that the powder shows more than 50% moisture uptake at 80% relative humidity at 25°C.
- a 3 gram sample of the powder having an average particle size of 250 micrometers, is placed on an 80mm diameter petri dish.
- the sample is dried in a vacuum oven at 40°C for 48 hours, and the dry weight recorded.
- the sample is then placed in a relative humidity and temperature control unit. (That is, any sample chamber which has controllable % relative humidity (80+/-2%) and temperature (25+/-l°C)).
- the unit is set at 80% relative humidity and 25°C for at least 8 hours.
- the sample weight is then recorded again.
- a powder which absorbs more than 50% of its dry weight at 80% relative humidity and 25°C is considered to be hygroscopic.
- the powder may consist exclusively of a polymer, or, alternatively, the powder may further comprise other detergent ingredients such as surfactants, builders (especially zeolites) etc.
- the powder may be prepared by any suitable means including spray drying of an aqueous solution or slurry of the powder components.
- One particularly preferred method is spray drying using a two- fluid nozzle, the process of which is described in more detail below.
- Polymers which are particularly useful as components of the hygroscopic powder of the present invention include sodium carboxy-lower alkyl celluloses, sodium lower alkyl celluloses and sodium hydroxy-lower alkyl celluloses, such as sodium carboxymethyl cellulose, sodium methyl cellulose and sodium hydroxypropyl cellulose, polyvinyl alcohols (which often also include some polyvinyl acetate) , polyvinyl pyrrolidone, polyethylene glycol, polyaspartate, polyacrylamides, polyacrylates and various copolymers, such as those of maleic and acrylic acids. Molecular weights for such polymers vary widely but most are within the range of 2,000 to 100,000.
- polymeric polycarboxyate builders are set forth in U.S. Patent 3,308,067, Diehl, issued March 7, 1967.
- Such materials include the water-soluble salts of homo-and copolymers of aliphatic carboxylic acids such as maleic acid, itaconic acid, mesaconic acid, fumaric acid, aconitic acid, citraconic acid and methylenemalonic acid. 17
- the hygroscopic powder and the hydrophobic silica are thoroughly premixed before the granulation step with the surfactant paste. A process for this is described in more detail below.
- the detergent compositions herein can contain crystalline aluminosilicate ion exchange material of the formula
- Amorphous hydrated aluminosilicate materials useful herein have the empirical formula M z (zA10 2 -ySi0 2 ) wherein M is sodium, potassium, ammonium or substituted ammonium, z is from about 0.5 to about 2 and y is 1, said material having a magnesium ion exchange capacity of at least about 50 milligram equivalents of CaC0 3 hardness per gram of anhydrous aluminosilicate. Hydrated sodium Zeolite A with a particle size of from about 1 to 10 microns is preferred.
- the aluminosilicate ion exchange builder materials herein are in hydrated form and contain from about 10% to about 28% of water by weight if crystalline, and potentially even higher amounts of water if amorphous. Highly preferred crystalline aluminosilicate ion exchange materials contain from about 18% to about 22% water in their crystal matrix.
- the crystalline aluminosilicate ion exchange materials are further characterized by a particle size diameter of from about 0.1 micron to about 10 microns. Amorphous materials are often smaller, e.g., down to less than about 0.01 micron.
- Preferred ion exchange materials have a particle size diameter of from about 0.2 micron to about 4 microns.
- the term "particle size diameter" herein represents the average particle size diameter by weight of a given ion exchange material as determined by conventional analytical techniques such as, for example, microscopic determination utilizing a scanning electron microscope.
- the crystalline aluminosilicate ion exchange materials herein are usually further characterized by their calcium ion exchange capacity, which is at least about 200 mg equivalent of CaC0 3 water hardness/g of aluminosilicate, calculated on an anhydrous basis, and which generally is in the range of from about 300 mg eq./g to about 352 mg eq./g.
- the aluminosilicate ion exchange materials herein are still further characterized by their calcium ion exchange rate which is at least about 2 grains
- Ca ++ /gallon/minute/gram/gallon of aluminosilicate (anhydrous basis) , and generally lies within the range of from about 2 grains/gallon/minute/gram/gallon to about 6 grains/gallon/minute/gram/gallon, based on calcium ion hardness.
- Optimum aluminosilicate for builder purposes exhibit a calcium ion exchange rate of at least about 4 grains/gallon/minute/gram/gallon.
- the amorphous aluminosilicate ion exchange materials usually have a Mg ++ exchange of at least about 50 mg eq. CaC0 3 /g (12 mg Mg ++ /g) and a Mg ++ exchange rate of at least about 1 grain/gallon/minute/gram/gallon. Amorphous materials do not exhibit an observable diffraction pattern when examined by Cu radiation (1.54 Angstrom Units).
- Aluminosilicate ion exchange materials useful in the practice of this invention are commercially available.
- the aluminosilicates useful in this invention can be crystalline or amorphous in structure and can be naturally occurring aluminosilicates or synthetically derived.
- a method for producing aluminosilicate ion exchange materials is discussed in U.S. Pat. No. 3,985,669, Krummel et al., issued Oct. 12, 1976, incorporated herein by reference.
- Preferred synthetic crystalline aluminosilicate ion exchange materials useful herein are available under the designations Zeolite A, Zeolite B, and Zeolite X.
- the crystalline aluminosilicate ion exchange material has the formula Na 12 [(A10 2 ) 12 (Si02) 12 ]-xH 2 0 wherein x is from about 20 to about 30, especially about 27 and has a particle size generally less than about 5 microns.
- the granular detergents of the present invention can contain neutral or alkaline salts which have a pH in solution of seven or greater, and can be either crganic or inorganic in nature.
- the builder salt assists in providing the desired density and bulk to the detergent granules herein. While some of the salts are inert, many of them also function as detergency builder materials in the laundering solution.
- neutral water-soluble salts include the alkali metal, ammonium or substituted ammonium chlorides, fluorides and sulfates.
- the alkali metal, and especially sodium, salts of the above are preferred.
- Sodium sulfate is typically used in detergent granules and is a particularly preferred salt, citric acid and, in general, any other organic or inorganic acid may be incorporated into the granular detergents of the present invention as long as it is chemically compatible with the rest of the agglomerate composition.
- water-soluble salts include the compounds commonly known as detergent builder materials.
- Builders are generally selected from the various water-soluble, alkali metal, ammonium or substituted ammonium phosphates, polyphosphates, phosphonates, polyphosphonates, carbonates, silicates, borates, and polyhydroxysulfonates.
- alkali metal especially sodium, salts of the above.
- inorganic phosphate builders are sodium and potassium tripolyphosphate, pyrophosphate, polymeric metaphosphate having a degree of polymerization of from about 6 to 21, and orthophosphate.
- polyphosphonate builders are the sodium and potassium salts of ethylene diphosphonic acid, the sodium and potassium salts of ethane l-hydroxy-l,l-diphosphonic acid and the sodium and potassium salts of ethane, 1,1,2-triphosphonic acid.
- Other phosphorus builder compounds are disclosed in U.S. Pat. Nos. 3,159,581; 3,213,030; 3,422,021; 3,422,137; 3,400,176 and 3,400,148, incorporated herein by reference.
- nonphosphorus, inorganic builders are sodium and potassium carbonate, bicarbonate, sesquicarbonate, tetraborate decahydrate, and silicate having a molar ratio of Si0 2 to alkali metal oxide of from about 0.5 to about 4.0, preferably from about 1.0 to about 2.4.
- powders normally used in detergents such as zeolite, carbonate, silica, silicate, citrate, phosphate, perborate, etc. and process acids such as starch and sugars, can be used in preferred embodiments of the present invention.
- other components may be added at any one of the stages of the process of the present invention, or they may be mixed with or sprayed on to the granular detergents of the present invention.
- Another optional detergent composition ingredient is a suds suppressor, exemplified by silicones, and silica- silicone mixtures.
- Silicones can be generally represented by alkylated polysiloxane materials while silica is
- SUBSTITUTE SHEET (FRiLE 26) normally used in finely divided forms, exemplified by silica aerogels and xerogels and hydrophobic silicas of various types. These materials can be incorporated as particulates in which the suds suppressor is advantageously releasably incorporated in a water-soluble or water- dispersible, substantially non-surface-active detergent- impermeable carrier. Alternatively the suds suppressor can be dissolved or dispersed in a liquid carrier and applied by spraying on to one or more of the other components.
- useful silicone suds controlling agents can comprise a mixture of an alkylated siloxane, of the type referred to hereinbefore, and solid silica. Such mixtures are prepared by affixing the silicone to the surface of the solid silica.
- a preferred silicone suds controlling agent is represented by a hydrophobic silanated (most preferably tri ethyl-silanated) silica having a particle size in the range from 10 nanometers to 20 nanometers and a specific surface area above 50 m 2 /g, intimately admixed with dimethyl silicone fluid having a molecular weight in the range from about 500 to about 200,000 at a weight ratio of silicone to silanated silica of from about 1:1 to about 1:2.
- a preferred silicone suds controlling agent is disclosed in Bartollota et al. US Patent 3,933,672.
- Other particularly useful suds suppressors are the self-emulsifying silicone suds suppressors, described in German Patent Application DTOS 2,646,126 published April 28, 1977.
- An example of such a compound is DC0544, commercially available from Dow Corning, which is a siloxane/glycol copolymer.
- the suds suppressors described above are normally employed at levels of from 0.001% to 0.5% by weight of the composition, preferably from 0.01% to 0.1% by weight.
- the preferred methods of incorporation comprise either application of the suds suppressors in liquid form by spray-on to one or more of the major components of the composition or alternatively the formation of the suds suppressors into separate particulates that can then be mixed with the other solid components of the composition.
- the incorporation of the suds modifiers as separate particulates also permits the inclusion therein of other suds controlling materials such as C 2 o-C 24 fatty acids, macrocrystalline waxes and high MWt copolymers of ethylene oxide and propylene oxide which would otherwise adversely affect the dispersibility of the matrix. Techniques for forming such suds modifying particulates are disclosed in the previously mentioned Bartolotta et al US Patent No. 3,933,672.
- Another optional ingredient useful in the present invention is one or more enzymes.
- Preferred enzymatic materials include the commercially available amylases, neutral and alkaline proteases, lipases, esterases and cellulases conventionally incorporated into detergent compositions. Suitable enzymes are discussed in US Patents 3,519,570 and 3,533,139.
- fine dispersion mixing and/or granulation means mixing and/or granulation of the mixture in a fine dispersion mixer at a blade tip speed of from about 5m/sec. to about 50 m/sec. , unless otherwise specified.
- the total residence time of the mixing and granulation process is preferably in the order of from 0.1 to 10 minutes, more preferably 0.1-5 and most preferably 0.2-4 minutes.
- the more preferred mixing and granulation tip speeds are about 10-45 m/sec. and about 15-40 m/sec.
- Suitable apparatus includes, for example, falling film sulphonating reactors, digestion tanks, esterification reactors, etc.
- any of a number of mixers/agglomerators can be used.
- the process of the invention is continuously carried out.
- mixers of the Fukae R FS-G series manufactured by Fukae Powtech Kogyo Co., Japan are especially preferred.
- this apparatus is essentially in the form of a bowl-shaped vessel accessible via a top port, provided near its base with a stirrer having a substantially vertical axis, and a cutter positioned on a side wall.
- the stirrer and cutter may be operated independently of one another and at separately variable speeds.
- the vessel can be fitted with a cooling jacket or, if necessary, a cryogenic unit.
- mixers found to be suitable for use in the process of the invention include Diosna R V series ex Dierks & S ⁇ hne, Germany; and the Phar a Matrix R ex T K Fielder Ltd., England.
- Other mixers believed to be suitable for use in the process of the invention are the Fuji R VG-C series ex Fuji Sangyo Co., Japan; and the Roto R ex Zanchetta & Co srl. Italy.
- Other preferred suitable equipment can include Eirich R , series RV, manufactured by Gustau Eirich Hardheim, Germany; Lodige R , series FM for batch mixing, series Baud KM for continuous mixing/agglomeration, manufactured by L ⁇ dige Machinenbau GmbH, Paderborn Germany; Drais R T160 series, manufactured by Drais Werke GmbH, Mannheim Germany; and Winkworth R RT 25 series, manufactured by Winkworth Machinery Ltd., Berkshire, England.
- the preferred operating temperatures for the agglomeration step should also be as low as possible since this leads to a higher surfactant concentration in the finished particle.
- the temperature during the agglomeration is less than 100°C, more preferably between 10 and 90°C, and most preferably between 20 and 8 °C.
- Lower operating temperatures useful in the process of the present invention may be achieved by a variety of methods known in the art such as nitrogen cooling, cool water jacketing of the equipment, addition of solid C0 2 , and the like; with a preferred method being solid C0 2 , and the most preferred method being nitrogen cooling.
- the granules formed in the high speed mixer may still have a higher moisture content than desired.
- the desired moisture content of the free flowing granules of this invention can be adjusted to levels adequate for the intended application by drying in conventional powder drying equipment such as fluid bed dryers. If a hot air fluid bed dryer is used, care must be exercised to avoid degradation of heat sensitive components of the granules. It is also advantageous to have a cooling step prior to large scale storage. This step can also be done in a conventional fluid bed operated with cool air. The drying/cooling of the agglomerates can also be done in any other equipment suitable for powder drying such as rotary dryers, etc.
- the final moisture of the agglomerates needs to be maintained below levels at which the agglomerates can be stored and transported in bulk.
- the exact moisture level depends on the composition of the agglomerate but is typically achieved at levels of 1-8% free water (i.e. water not associated to any crystalline species in the agglomerate) and most typically at 2-4%.
- a preferred process for the preparation of the hygroscopic powder is by spray drying.
- a most preferred process uses a two fluid nozzle or spinning disk. These nozzles are particularly useful to make polymer containing granules for use in the present invention, wherein the concentrated polymer-containing slurry or solution has a high viscosity and/or a non-Newtonian rheology. Such a slurry is difficult to spray dry through a conventional pressure nozzle.
- Suitable two fluid nozzles and disks are supplied by Delavan, and described in their "Spray Drying Manual” and by Spraying Systems Co., and described in their Technical Manual No. 402.
- the atomisation in two-fluid nozzles is derived from energy in compressed air, gas or pressurised steam. Preferably air-atomising nozzles are used.
- the atomisation in spinning disks is derived from the kinetic energy of the disk on to which the slurry or solution is sprayed.
- the slurry or solution may comprise other detergent ingredients, such as those described herein, as well as polymer.
- One preferred composition is polymer and aluminosilicate, especially zeolite A. Compositions of this type, as well as processes for making them have been described in DE 33 16 513, published on 8th November, 1984.
- hydrophobic silica When the hygroscopic powder has been prepared, it is the necessary to coat the surface with hydrophobic silica. Suitable hydrophobic silicas have been described above.
- the hygroscopic powders can be added placed in a low shear mixer or rotating drum.
- the hydrophobic silica can then be added to the drum or mixer while it is in motion.
- the hydrophobic silica coats the hygroscopic powder and makes the particles free flowing.
- the flow aid creates a hydrophobic layer which protects against moisture.
- the invention can be practised as a batch or a continuous process.
- another process which is suited to the present invention is that of fluidised bed coating. In a fluidised bed process the solid particles are largely separate from one another, i.e. in a fluidised state, and can therefore be effectively coated by the hydrophobic silica.
- the extruder fulfils the functions of pumping and mixing the viscous surfactant paste on a continuous basis.
- a basic extruder consists of a barrel with a smooth inner cylindrical surface. Mounted within this barrel is the extruder screw. There is an inlet port for the high active paste which, when the screw is rotated, causes the paste to be moved along the length of the barrel.
- the detailed design of the extruder allows various functions to be carried out. Firstly additional ports in the barrel may allow other ingredients, including the chemical structuring agents to be added directly into the barrel. Secondly a vacuum pump and a seal around the shaft of the screw allows a vacuum to be drawn which enables the moisture level to be reduced. Thirdly means for heating or cooling ⁇ ay be installed in the wall of the barrel for temperature control. Fourthly, careful design of the extruder screw promotes mixing of the paste both with itself and with other additives.
- a preferred extruder is the twin screw extruder. This type of extruder has two screws mounted in parallel within the same barrel, which are made to rotate either in the same direction (co-rotation) or in opposite directions (counter- rotation) .
- the co-rotating twin screw extruder is the most preferred piece of equipment for use in this invention.
- An extruder is particularly useful in a preferred embodiment of the present it ention because the hygroscopic powder/hydrophobic silica can be added to the surfactant paste via e&n inlet port in the extruder and can be considered as chemical structuring agents.
- the extruder helps to ensure thorough and intimate mixing of the paste and the powder.
- the extruder conveys the conditioned paste which now comprises polymer and hydrophobic silica into the mixer where fine dispersion and granulation takes place. Suitable mixers have been defined above.
- Suitable twin screw extruders for use in the present invention include those supplied by : APV Baker, (CP series) ; Werner and Pfleiderer, (Continua Series) ; Wenger, (TF Series); Leistritz, (ZSE Series); and Buss, (LR Series) .
- the extruder allows the paste to be conditioned by moisture and temperature reduction. Moisture may be removed under vacuum, prefe: bly between 0 mmHg (gauge) and -55 mmHg (gauge), (0 - '. ,,3 kPa below atmospheric pressure).
- Temperature may be reduced by the addition of solid carbon dioxide or liquid nitrogen directly into the extruder barrel.
- liquid nitrogen is used at up to 30% by weight of the paste.
- An aqueous surfactant paste comprising:
- sodium alkyl ester sulphate having substantially C13 to C15 alkyl chains and an average of 3 ethoxy groups per molecule;
- a powder premix was prepared by mixing the sodium salt of a co-polymer of maleic and acrylic acid with 2% by weight of hydrophobic silica (Aerosil R972, trade name, supplied by Degussa) in a Loedige FM130D (trade name) mixer for 30 seconds.
- aqueous surfactant paste and the premixed co-polymer / hydrophobic silica were then intimately mixed in a twin screw extruder with a barrel in 6 sections (manufactured by Werner & Pfleiderer, C58) .
- the resulting viscous paste was
- the resulting agglomerates were transferred to a fluid bed drier and then classified through mesh sieves to remove oversize and fine particles.
- the agglomerates formed had a surfactant content of 40% by weight, a polymer level of 12% by weight, a silica level of
- the granules formed have excellent flow and handling properties.
- example l The process of example l was repeated, except that the co- polymer of maleic and acrylic acid was not mixed with 2% of hydrophobic silica.
- the silica level in the finished agglomerates was 0%, and the agglomerates after granulation, drying and classification showed poor handling and flow properties.
- An aqueous surfactant paste comprising:
- sodium alkyl ester sulphate having substantially C13 to C15 alkyl chains and an average of 3 ethoxy groups per molecule;
- a powder premix was prepared by mixing the sodium salt of a co-polymer of maleic and acrylic acid with 2% by weight of hydrophobic silica (Aerosil R972, trade name, supplied by Degussa) batchwise in a ribbon blender.
- aqueous surfactant paste and the premixed co-polymer / hydrophobic silica were then intimately mixed in a twin screw extruder (manufactured by Werner & Pfleiderer, C170) .
- the resulting viscous paste was extruded directly into a Loedige CB30 (trade name) high speed mixer containing a mixture of 1 part zeolite A to 1 part finely divided light carbonate.
- the mixer operates on a continuous basis and discharges directly into a Loedige KM (trade name) continuous ploughshare mixer.
- the resulting agglomerates were transferred to a fluid bed drier, cooled in a fluid bed cooler and then classified through mesh sieves to remove oversize and fine particles.
- the agglomerates formed had a surfactant content of 40% by weight, a polymer level of 11.2% by weight, a silica level of 0.22% by weight and an equilibrium relative humidity level of 10% at room temperature.
- the granules formed have excellent flow and handling properties.
- This example describes the process in batch mode in a lab scale high shear mixer (food processcr) .
- the sodium salt of the copolymer of maleic and acrylic acid is premixed with the hydrophobic silica.
- the mixer is first charged with a mixture of powders to be used, in this case:
- a nonionic surfactant paste containing a GA/C25E3 mixture at a ratio of 50/50 was added at 25 percent by weight before starting the mixer.
- the mixer was then operated until granulation took place.
- the mixer was then stopped and the agglomerates were cooled in a fluid bed and classified through mesh sieves.
- the resulting agglomerates had excellent physical pr perties including flowability and had a bulk density of 700 g/1.
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Abstract
Procédé de préparation d'une composition détergente en granules extrêmement active possédant une densité volumique de 650 g/l. Ledit procédé comprend les étapes suivantes: i) préparation d'une pâte ou d'un liquide comprenant au moins 40 % en poids d'un tensio-actif sélectionné à partir de tensio-actifs anioniques et non ioniques; ii) mélange de ladite pâte ou dudit liquide avec une poudre afin d'obtenir un mélange pouvant se présenter sous forme de pâte ou de poudre homogène; iii) préparation de granules par mélange à dispersion fine ou granulation dudit mélange éventuellement en présence d'une quantité d'une ou plusieurs poudres supplémentaires, la poudre utilisée dans l'étape ii) étant composée d'une poudre coulante, prémélangée comprenant de 0,5 % à 10 % en poids de dioxyde de silicium hydrophobe et de 75 % à 99,5 % en poids de poudre hygroscopique comprenant un polymère.
Priority Applications (1)
Application Number | Priority Date | Filing Date | Title |
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JP7507178A JPH09509436A (ja) | 1993-08-18 | 1994-08-18 | 洗剤組成物の製法 |
Applications Claiming Priority (2)
Application Number | Priority Date | Filing Date | Title |
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EP93870174.5 | 1993-08-18 | ||
EP93870174A EP0639638A1 (fr) | 1993-08-18 | 1993-08-18 | Procédé de préparation de compositions détergentes |
Publications (1)
Publication Number | Publication Date |
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WO1995005449A1 true WO1995005449A1 (fr) | 1995-02-23 |
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ID=8215387
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Application Number | Title | Priority Date | Filing Date |
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PCT/US1994/009325 WO1995005449A1 (fr) | 1993-08-18 | 1994-08-18 | Procede de preparation de compositions detergentes |
Country Status (5)
Country | Link |
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EP (1) | EP0639638A1 (fr) |
JP (1) | JPH09509436A (fr) |
CN (1) | CN1133059A (fr) |
CA (1) | CA2169770A1 (fr) |
WO (1) | WO1995005449A1 (fr) |
Cited By (2)
Publication number | Priority date | Publication date | Assignee | Title |
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US6221832B1 (en) * | 1998-11-11 | 2001-04-24 | Stockhausen Gmbh & Co. Kg | Compacted granulate, process for making same and use as disintegrating agent for pressed detergent tablets, cleaning agent tablets for dishwashers, water softening tablets or scouring salt tablets |
US6232285B1 (en) * | 1998-11-11 | 2001-05-15 | Stockhausen Gmbh & Co. Kg | Compacted granulate, process for making same and use as disintegrating agent for pressed detergent tablets, cleaning agent tablets for dishwashers, water softening tablets and scouring salt tablets |
Families Citing this family (14)
Publication number | Priority date | Publication date | Assignee | Title |
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US5691297A (en) * | 1994-09-20 | 1997-11-25 | The Procter & Gamble Company | Process for making a high density detergent composition by controlling agglomeration within a dispersion index |
US5574005A (en) * | 1995-03-07 | 1996-11-12 | The Procter & Gamble Company | Process for producing detergent agglomerates from high active surfactant pastes having non-linear viscoelastic properties |
EP0888450B2 (fr) † | 1996-07-08 | 2003-01-15 | Henkel Kommanditgesellschaft auf Aktien | Additif pour produits de lavage ou de nettoyage, et procede de fabrication associe |
ES2282115T3 (es) * | 1999-06-14 | 2007-10-16 | Kao Corporation | Granulos para portar tensioactivos y metodo para producir los mismos. |
DE19961333B4 (de) * | 1999-12-17 | 2006-12-14 | Henkel Kgaa | Verfahren zur Herstellung von Zuckertensidgranulaten |
FR2868079B1 (fr) * | 2004-03-29 | 2007-06-08 | Seppic Sa | Tensioactifs sous forme de poudre utilisables dans des comprimes ou des gelules procede de preparation et compositions les contenant |
EP2028261B1 (fr) * | 2007-08-16 | 2013-01-16 | The Procter & Gamble Company | Processus de fabrication d'une composition de détergent |
US9376648B2 (en) | 2008-04-07 | 2016-06-28 | The Procter & Gamble Company | Foam manipulation compositions containing fine particles |
WO2012117024A1 (fr) * | 2011-03-01 | 2012-09-07 | Basf Se | Polymères actifs dans l'inhibition de transfert de couleurs et présentant une durée de conservation accrue et une aptitude à la mise en oeuvre améliorée pour des produits de lavage et de nettoyage |
WO2012117030A1 (fr) * | 2011-03-01 | 2012-09-07 | Basf Se | Polymères à teneur en groupes carboxyliques présentant une durée de conservation accrue et une aptitude à la mise en oeuvre améliorée |
EP2740534A1 (fr) * | 2012-12-04 | 2014-06-11 | Total Raffinage Marketing | Particules de type envelope-noyau avec une activité catalytique et procédé de préparation. Le procédé de préparation d'un catalyseur Fischer-Tropsch à la base de cettes particules. |
CN103480297B (zh) * | 2013-09-23 | 2016-01-06 | 安徽安庆南风日化有限责任公司 | 一种节能降耗的洗衣粉生产线 |
WO2016164296A1 (fr) * | 2015-04-08 | 2016-10-13 | Dow Corning Corporation | Émulsions pituiteuses de silicone |
JP6956557B2 (ja) * | 2016-12-20 | 2021-11-02 | 共同印刷株式会社 | 光透過性吸湿フィルム及びその製造方法 |
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- 1994-08-18 WO PCT/US1994/009325 patent/WO1995005449A1/fr active Application Filing
- 1994-08-18 CA CA 2169770 patent/CA2169770A1/fr not_active Abandoned
- 1994-08-18 CN CN 94193705 patent/CN1133059A/zh active Pending
- 1994-08-18 JP JP7507178A patent/JPH09509436A/ja active Pending
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Cited By (2)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US6221832B1 (en) * | 1998-11-11 | 2001-04-24 | Stockhausen Gmbh & Co. Kg | Compacted granulate, process for making same and use as disintegrating agent for pressed detergent tablets, cleaning agent tablets for dishwashers, water softening tablets or scouring salt tablets |
US6232285B1 (en) * | 1998-11-11 | 2001-05-15 | Stockhausen Gmbh & Co. Kg | Compacted granulate, process for making same and use as disintegrating agent for pressed detergent tablets, cleaning agent tablets for dishwashers, water softening tablets and scouring salt tablets |
Also Published As
Publication number | Publication date |
---|---|
JPH09509436A (ja) | 1997-09-22 |
CA2169770A1 (fr) | 1995-02-23 |
EP0639638A1 (fr) | 1995-02-22 |
CN1133059A (zh) | 1996-10-09 |
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