CN1174566A - 含有阳离子表面活性剂的洗涤剂组合物及其制备方法 - Google Patents
含有阳离子表面活性剂的洗涤剂组合物及其制备方法 Download PDFInfo
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- CN1174566A CN1174566A CN95197503.XA CN95197503A CN1174566A CN 1174566 A CN1174566 A CN 1174566A CN 95197503 A CN95197503 A CN 95197503A CN 1174566 A CN1174566 A CN 1174566A
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- 239000003599 detergent Substances 0.000 title claims abstract description 26
- 239000003093 cationic surfactant Substances 0.000 title abstract description 12
- 239000003945 anionic surfactant Substances 0.000 claims abstract description 29
- 239000007864 aqueous solution Substances 0.000 claims abstract description 12
- 239000000243 solution Substances 0.000 claims abstract description 10
- 229920006318 anionic polymer Polymers 0.000 claims abstract description 8
- 238000001035 drying Methods 0.000 claims abstract description 8
- 238000002156 mixing Methods 0.000 claims abstract description 4
- 239000007787 solid Substances 0.000 claims abstract description 3
- 241000282326 Felis catus Species 0.000 claims description 31
- 125000002091 cationic group Chemical group 0.000 claims description 14
- 239000013543 active substance Substances 0.000 claims description 12
- 238000005469 granulation Methods 0.000 claims description 9
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- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 claims description 7
- BPQQTUXANYXVAA-UHFFFAOYSA-N Orthosilicate Chemical compound [O-][Si]([O-])([O-])[O-] BPQQTUXANYXVAA-UHFFFAOYSA-N 0.000 claims description 6
- KRKNYBCHXYNGOX-UHFFFAOYSA-K Citrate Chemical compound [O-]C(=O)CC(O)(CC([O-])=O)C([O-])=O KRKNYBCHXYNGOX-UHFFFAOYSA-K 0.000 claims description 5
- 239000003795 chemical substances by application Substances 0.000 claims description 4
- 238000001704 evaporation Methods 0.000 claims description 4
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- JYIMWRSJCRRYNK-UHFFFAOYSA-N dialuminum;disodium;oxygen(2-);silicon(4+);hydrate Chemical compound O.[O-2].[O-2].[O-2].[O-2].[O-2].[O-2].[Na+].[Na+].[Al+3].[Al+3].[Si+4] JYIMWRSJCRRYNK-UHFFFAOYSA-N 0.000 claims description 2
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- 239000000047 product Substances 0.000 description 32
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- 238000005342 ion exchange Methods 0.000 description 17
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- 125000000217 alkyl group Chemical group 0.000 description 13
- 239000011734 sodium Substances 0.000 description 13
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- 159000000000 sodium salts Chemical class 0.000 description 10
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- 108090000322 Cholinesterases Proteins 0.000 description 8
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- 239000002253 acid Substances 0.000 description 8
- 229920001296 polysiloxane Polymers 0.000 description 8
- 229910052700 potassium Inorganic materials 0.000 description 8
- 239000011591 potassium Substances 0.000 description 8
- 239000000126 substance Substances 0.000 description 8
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical group [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 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
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- 125000001453 quaternary ammonium group Chemical group 0.000 description 5
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- BHPQYMZQTOCNFJ-UHFFFAOYSA-N Calcium cation Chemical group [Ca+2] BHPQYMZQTOCNFJ-UHFFFAOYSA-N 0.000 description 4
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- 125000003342 alkenyl group Chemical group 0.000 description 4
- 229910001424 calcium ion Inorganic materials 0.000 description 4
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- 239000013078 crystal Substances 0.000 description 4
- 150000004665 fatty acids Chemical class 0.000 description 4
- 239000000344 soap Substances 0.000 description 4
- 229910052938 sodium sulfate Inorganic materials 0.000 description 4
- 235000011152 sodium sulphate Nutrition 0.000 description 4
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- 235000013162 Cocos nucifera Nutrition 0.000 description 3
- 244000060011 Cocos nucifera Species 0.000 description 3
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 3
- 150000001447 alkali salts Chemical class 0.000 description 3
- 150000001408 amides Chemical class 0.000 description 3
- 150000003863 ammonium salts Chemical class 0.000 description 3
- 239000002585 base Substances 0.000 description 3
- 150000001721 carbon Chemical group 0.000 description 3
- 238000005341 cation exchange Methods 0.000 description 3
- 238000006243 chemical reaction Methods 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
- GUJOJGAPFQRJSV-UHFFFAOYSA-N dialuminum;dioxosilane;oxygen(2-);hydrate Chemical compound O.[O-2].[O-2].[O-2].[Al+3].[Al+3].O=[Si]=O.O=[Si]=O.O=[Si]=O.O=[Si]=O GUJOJGAPFQRJSV-UHFFFAOYSA-N 0.000 description 3
- 150000002148 esters Chemical class 0.000 description 3
- KWLMIXQRALPRBC-UHFFFAOYSA-L hectorite Chemical compound [Li+].[OH-].[OH-].[Na+].[Mg+2].O1[Si]2([O-])O[Si]1([O-])O[Si]([O-])(O1)O[Si]1([O-])O2 KWLMIXQRALPRBC-UHFFFAOYSA-L 0.000 description 3
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- 150000002430 hydrocarbons Chemical group 0.000 description 3
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- NLXLAEXVIDQMFP-UHFFFAOYSA-N Ammonia chloride Chemical compound [NH4+].[Cl-] NLXLAEXVIDQMFP-UHFFFAOYSA-N 0.000 description 2
- CPELXLSAUQHCOX-UHFFFAOYSA-M Bromide Chemical compound [Br-] CPELXLSAUQHCOX-UHFFFAOYSA-M 0.000 description 2
- OTMSDBZUPAUEDD-UHFFFAOYSA-N Ethane Chemical compound CC OTMSDBZUPAUEDD-UHFFFAOYSA-N 0.000 description 2
- 229910002651 NO3 Inorganic materials 0.000 description 2
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 description 2
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 2
- 229910004298 SiO 2 Inorganic materials 0.000 description 2
- 239000004990 Smectic liquid crystal Substances 0.000 description 2
- FKNQFGJONOIPTF-UHFFFAOYSA-N Sodium cation Chemical compound [Na+] FKNQFGJONOIPTF-UHFFFAOYSA-N 0.000 description 2
- 238000010521 absorption reaction Methods 0.000 description 2
- 239000003377 acid catalyst Substances 0.000 description 2
- 125000002252 acyl group Chemical group 0.000 description 2
- 150000001298 alcohols Chemical class 0.000 description 2
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- 125000002877 alkyl aryl group Chemical group 0.000 description 2
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- 239000011575 calcium Substances 0.000 description 2
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- OEYIOHPDSNJKLS-UHFFFAOYSA-N choline Chemical compound C[N+](C)(C)CCO OEYIOHPDSNJKLS-UHFFFAOYSA-N 0.000 description 2
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- 239000000084 colloidal system Substances 0.000 description 2
- 230000000052 comparative effect Effects 0.000 description 2
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- XMBWDFGMSWQBCA-UHFFFAOYSA-N hydrogen iodide Chemical compound I XMBWDFGMSWQBCA-UHFFFAOYSA-N 0.000 description 2
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 2
- JZMJDSHXVKJFKW-UHFFFAOYSA-M methyl sulfate(1-) Chemical compound COS([O-])(=O)=O JZMJDSHXVKJFKW-UHFFFAOYSA-M 0.000 description 2
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- 230000007935 neutral effect Effects 0.000 description 2
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- 239000011574 phosphorus Substances 0.000 description 2
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- 229920000435 poly(dimethylsiloxane) Polymers 0.000 description 2
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- GETQZCLCWQTVFV-UHFFFAOYSA-N trimethylamine Chemical compound CN(C)C GETQZCLCWQTVFV-UHFFFAOYSA-N 0.000 description 2
- MXYOPVWZZKEAGX-UHFFFAOYSA-N 1-phosphonoethylphosphonic acid Chemical compound OP(=O)(O)C(C)P(O)(O)=O MXYOPVWZZKEAGX-UHFFFAOYSA-N 0.000 description 1
- MPNXSZJPSVBLHP-UHFFFAOYSA-N 2-chloro-n-phenylpyridine-3-carboxamide Chemical compound ClC1=NC=CC=C1C(=O)NC1=CC=CC=C1 MPNXSZJPSVBLHP-UHFFFAOYSA-N 0.000 description 1
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- 239000005995 Aluminium silicate Substances 0.000 description 1
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- BTBUEUYNUDRHOZ-UHFFFAOYSA-N Borate Chemical compound [O-]B([O-])[O-] BTBUEUYNUDRHOZ-UHFFFAOYSA-N 0.000 description 1
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 description 1
- 239000004215 Carbon black (E152) Substances 0.000 description 1
- IAYPIBMASNFSPL-UHFFFAOYSA-N Ethylene oxide Chemical compound C1CO1 IAYPIBMASNFSPL-UHFFFAOYSA-N 0.000 description 1
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 description 1
- JLVVSXFLKOJNIY-UHFFFAOYSA-N Magnesium ion Chemical group [Mg+2] JLVVSXFLKOJNIY-UHFFFAOYSA-N 0.000 description 1
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- 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
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical class OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 1
- NPYPAHLBTDXSSS-UHFFFAOYSA-N Potassium ion Chemical compound [K+] NPYPAHLBTDXSSS-UHFFFAOYSA-N 0.000 description 1
- GOOHAUXETOMSMM-UHFFFAOYSA-N Propylene oxide Chemical compound CC1CO1 GOOHAUXETOMSMM-UHFFFAOYSA-N 0.000 description 1
- 150000007513 acids Chemical class 0.000 description 1
- 238000005054 agglomeration Methods 0.000 description 1
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- 125000001931 aliphatic group Chemical group 0.000 description 1
- 229910000272 alkali metal oxide Inorganic materials 0.000 description 1
- 150000001340 alkali metals Chemical class 0.000 description 1
- 150000001336 alkenes Chemical class 0.000 description 1
- 125000004183 alkoxy alkyl group Chemical group 0.000 description 1
- 125000005210 alkyl ammonium group Chemical group 0.000 description 1
- 150000005215 alkyl ethers Chemical class 0.000 description 1
- 125000005211 alkyl trimethyl ammonium group Chemical group 0.000 description 1
- 235000012211 aluminium silicate Nutrition 0.000 description 1
- 235000019270 ammonium chloride Nutrition 0.000 description 1
- ZRIUUUJAJJNDSS-UHFFFAOYSA-N ammonium phosphates Chemical group [NH4+].[NH4+].[NH4+].[O-]P([O-])([O-])=O ZRIUUUJAJJNDSS-UHFFFAOYSA-N 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 230000001458 anti-acid effect Effects 0.000 description 1
- 125000004429 atom Chemical group 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 229940077388 benzenesulfonate Drugs 0.000 description 1
- SRSXLGNVWSONIS-UHFFFAOYSA-N benzenesulfonic acid Chemical compound OS(=O)(=O)C1=CC=CC=C1 SRSXLGNVWSONIS-UHFFFAOYSA-N 0.000 description 1
- 229910052791 calcium Inorganic materials 0.000 description 1
- 150000001768 cations Chemical class 0.000 description 1
- 238000005660 chlorination reaction Methods 0.000 description 1
- 229960002887 deanol Drugs 0.000 description 1
- 239000013530 defoamer Substances 0.000 description 1
- FPAFDBFIGPHWGO-UHFFFAOYSA-N dioxosilane;oxomagnesium;hydrate Chemical compound O.[Mg]=O.[Mg]=O.[Mg]=O.O=[Si]=O.O=[Si]=O.O=[Si]=O.O=[Si]=O FPAFDBFIGPHWGO-UHFFFAOYSA-N 0.000 description 1
- XPPKVPWEQAFLFU-UHFFFAOYSA-J diphosphate(4-) Chemical class [O-]P([O-])(=O)OP([O-])([O-])=O XPPKVPWEQAFLFU-UHFFFAOYSA-J 0.000 description 1
- 239000012153 distilled water Substances 0.000 description 1
- 239000000428 dust Substances 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 125000004185 ester group Chemical group 0.000 description 1
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- 125000005313 fatty acid group Chemical group 0.000 description 1
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- 125000005908 glyceryl ester group Chemical group 0.000 description 1
- 239000008187 granular material Substances 0.000 description 1
- 229930195733 hydrocarbon Natural products 0.000 description 1
- 230000002209 hydrophobic effect Effects 0.000 description 1
- 230000003165 hydrotropic effect Effects 0.000 description 1
- 125000002768 hydroxyalkyl group Chemical group 0.000 description 1
- 239000004615 ingredient Substances 0.000 description 1
- 229910052816 inorganic phosphate Inorganic materials 0.000 description 1
- 229910017053 inorganic salt Inorganic materials 0.000 description 1
- NLYAJNPCOHFWQQ-UHFFFAOYSA-N kaolin Chemical compound O.O.O=[Al]O[Si](=O)O[Si](=O)O[Al]=O NLYAJNPCOHFWQQ-UHFFFAOYSA-N 0.000 description 1
- 150000002576 ketones Chemical class 0.000 description 1
- 125000000400 lauroyl group Chemical group O=C([*])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 235000012204 lemonade/lime carbonate Nutrition 0.000 description 1
- 150000002632 lipids Chemical class 0.000 description 1
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- 229910001416 lithium ion Inorganic materials 0.000 description 1
- 229910001425 magnesium ion Inorganic materials 0.000 description 1
- HCWCAKKEBCNQJP-UHFFFAOYSA-N magnesium orthosilicate Chemical compound [Mg+2].[Mg+2].[O-][Si]([O-])([O-])[O-] HCWCAKKEBCNQJP-UHFFFAOYSA-N 0.000 description 1
- 239000000391 magnesium silicate Substances 0.000 description 1
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- 235000019792 magnesium silicate Nutrition 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- CXKWCBBOMKCUKX-UHFFFAOYSA-M methylene blue Chemical compound [Cl-].C1=CC(N(C)C)=CC2=[S+]C3=CC(N(C)C)=CC=C3N=C21 CXKWCBBOMKCUKX-UHFFFAOYSA-M 0.000 description 1
- 229960000907 methylthioninium chloride Drugs 0.000 description 1
- 239000000693 micelle Substances 0.000 description 1
- 238000000386 microscopy Methods 0.000 description 1
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- 239000008267 milk Substances 0.000 description 1
- 210000004080 milk Anatomy 0.000 description 1
- 229910052674 natrolite Inorganic materials 0.000 description 1
- QJGQUHMNIGDVPM-UHFFFAOYSA-N nitrogen group Chemical group [N] QJGQUHMNIGDVPM-UHFFFAOYSA-N 0.000 description 1
- 229910000273 nontronite Inorganic materials 0.000 description 1
- UHGIMQLJWRAPLT-UHFFFAOYSA-N octadecyl dihydrogen phosphate Chemical compound CCCCCCCCCCCCCCCCCCOP(O)(O)=O UHGIMQLJWRAPLT-UHFFFAOYSA-N 0.000 description 1
- 150000007524 organic acids Chemical class 0.000 description 1
- 238000006053 organic reaction Methods 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 125000001312 palmitoyl group Chemical group O=C([*])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 239000012188 paraffin wax Substances 0.000 description 1
- UEZVMMHDMIWARA-UHFFFAOYSA-M phosphonate Chemical compound [O-]P(=O)=O UEZVMMHDMIWARA-UHFFFAOYSA-M 0.000 description 1
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- 235000011176 polyphosphates Nutrition 0.000 description 1
- 229910001414 potassium ion Inorganic materials 0.000 description 1
- HNDXKIMMSFCCFW-UHFFFAOYSA-N propane-2-sulphonic acid Chemical compound CC(C)S(O)(=O)=O HNDXKIMMSFCCFW-UHFFFAOYSA-N 0.000 description 1
- 150000003856 quaternary ammonium compounds Chemical class 0.000 description 1
- 230000005855 radiation Effects 0.000 description 1
- 239000011347 resin Substances 0.000 description 1
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- 238000007127 saponification reaction Methods 0.000 description 1
- 229910000276 sauconite Inorganic materials 0.000 description 1
- 229940071207 sesquicarbonate Drugs 0.000 description 1
- 235000019832 sodium triphosphate Nutrition 0.000 description 1
- 238000005507 spraying Methods 0.000 description 1
- 239000000758 substrate Substances 0.000 description 1
- QAOWNCQODCNURD-UHFFFAOYSA-L sulfate group Chemical group S(=O)(=O)([O-])[O-] QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 description 1
- 230000019635 sulfation Effects 0.000 description 1
- 238000005670 sulfation reaction Methods 0.000 description 1
- 230000008961 swelling Effects 0.000 description 1
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- 235000012222 talc Nutrition 0.000 description 1
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- QQOWHRYOXYEMTL-UHFFFAOYSA-N triazin-4-amine Chemical compound N=C1C=CN=NN1 QQOWHRYOXYEMTL-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
- 229940048102 triphosphoric acid Drugs 0.000 description 1
- 239000010455 vermiculite Substances 0.000 description 1
- 229910052902 vermiculite Inorganic materials 0.000 description 1
- 235000019354 vermiculite Nutrition 0.000 description 1
- 238000007601 warm air drying Methods 0.000 description 1
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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
- C11D10/00—Compositions of detergents, not provided for by one single preceding group
- C11D10/04—Compositions of detergents, not provided for by one single preceding group based on mixtures of surface-active non-soap compounds and soap
- C11D10/047—Compositions of detergents, not provided for by one single preceding group based on mixtures of surface-active non-soap compounds and soap based on cationic surface-active compounds and soap
-
- C—CHEMISTRY; METALLURGY
- C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
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Abstract
本发明涉及一种粒状洗涤剂组合物或包含阴离 子表面活性剂和至少20%(重量)的水溶性阳离子表面活性剂以 及少于10%(重量)的阴离子聚合物的组合物,其中阴离子表面 活性剂与阳离子表面活性剂的摩尔比小于1∶1,优选小于0.5∶ 1。本发明的另一方面涉及一种制备组合物或组分的方法,该方 法包括下列步骤:(i)将含有水溶性阳离子表面活性剂、阴离子表 面活性剂和少于10%(重量)的阴离子聚合物的水溶液混合,(ii) 干燥混合物,使之形成至少包含50%(重量)固体含量的浓溶 液,(iii)粒化浓溶液;其中阳离子表面活性剂的量至少为组合物 或组分重量的20%,阴离子表面活性剂与阳离子表面活性剂的 摩尔比小于1∶1。
Description
本发明涉及含有阳离子表面活性剂和阴离子表面活性剂的粒状洗涤剂组合物。
水溶性阳离子表面活性剂可在市场上以水溶液形式购得,其活性一般高达35%或40%(重量)。然而不论如何粒化此水溶液,都会导致产生低阳离子表面活性剂含量的粒状组分。
1979年1月10日公开的欧洲专利申请EP-A000225公开了含有水溶性阳离子表面活性剂和阴离子表面活性剂的组合物。将表面活性剂与其它洗涤剂成分如助洗剂在一搅和机中混合在一起,并喷雾干燥。其主要特征是阴离子表面活性剂的摩尔数多于阳离子表面活性剂。该实例公开了在喷雾干燥组分中,阳离子表面活性剂的最大含量为约8%(重量)。
通过初次浓缩水溶液,试图提高粒状组合物中阳离子表面活性剂含量已被证实是很难的,这是因为浓缩的阳离子表面活性剂的粘稠凝胶相,使得进一步大规模加工变得相当困难。
本发明的目的在于提供水溶性阳离子表面活性剂的含量比现有技术组分高的粒状洗涤剂组分或组合物。
通过把少量阴离子表面活性剂和阳离子表面活性剂的水溶液进行混合,然后同时或依次地进行干燥和粒化,已实现了此目的。加入阴离子表面活性剂使得可以对更浓的阳离子溶液进行处理,而避开了粘稠的凝胶相。从而,就可以生产更浓的粒状表面活性剂组分或组合物了。
发明概述
本发明涉及一种包含阴离子表面活性剂和至少20%(重量)的水溶性阳离子表面活性剂以及少于10%(重量)的阴离子聚合物的粒状洗涤剂组合物或组分,其中阴离子表面活性剂与阳离子表面活性剂的摩尔比小于1∶1,优选小于0.5∶1。
粒状洗涤剂组合物或组分优选包含:含量至少为组合物或组分重量的30%的阳离子表面活性剂和含量为组合物或组分重量的1%~20%的阴离子表面活性剂。
粒状洗涤剂组合物或组分还任选包含10%~69%的选自硅铝酸盐、硅酸盐、碳酸盐、柠檬酸盐、磷酸盐或其混合物的洗涤剂助洗剂。
一种高度优选的粒状洗涤剂组合物或组分应基本上不含阴离子聚合物,其包括:
(a)35%~50%(重量)的水溶性阳离子表面活性剂;
(b)1%~5%(重量)的阴离子表面活性剂;和
(c)40%~60%(重量)的硅铝酸钠。
本发明的另一方面是一种制备组合物或组分的方法,该方法的步骤包括:
(i)将包含水溶性阳离子表面活性剂、阴离子表面活性剂和少于10%(重量)阴离子聚合物的水溶液混合;
(ii)干燥混合物,使之形成至少包含50%(重量)固体含量的浓溶液,和
(iii)粒化浓溶液;
其中阳离子表面活性剂的量为组合物或组分重量的至少20%,阴离子表面活性剂与阳离子表面活性剂的摩尔比小于1∶1。
可任选地在混合步骤(i)中加入一种抑泡剂。
干燥步骤可通过蒸发法完成,随后粒化步骤可通过将浓溶液和选自硅铝酸盐、硅酸盐、碳酸盐、柠檬酸盐、磷酸盐或其混合物的洗涤剂助洗剂混合来完成。
另外,干燥和粒化步骤可以同时进行,优选采用喷雾干燥法。发明详述
组合物的阳离子表面活性剂组分是水溶性的。本文中我们所指的水溶性是单体形式的阳离子表面活性剂的溶解度,溶解度的极限自胶束化作用开始出现时测定,用临界胶束浓度(CMC)表示。因此在30℃条件下和在蒸馏水中时,阳离子表面活性剂纯物质的CMC应当大于约200ppm,优选大于约500ppm(1971年NSRDS-NBS出版,由P.Mukerjee和K.J.Mysels编著的《水相表面活性剂体系的临界胶束浓度》(Critical MicelleConcentrations of Aqueous Surfactant Systems))。
适用的阳离子表面活性剂包括式为R1R2R3R4N+X-的水溶性季铵盐化合物,其中R1为具有10~20个碳原子,优选具有12~18个碳原子的烷基,和R2、R3和R4分别为C1~C7的烷基、或羟烷基,优选甲基;X为阴离子,如氯化物。这类季铵盐化合物的实例包括C12-14烷基三甲基氯化铵、C12~14烷基二甲基乙氧基氯化铵和椰子烷基三甲基铵甲基硫酸酯。其它适用的阳离子表面活性剂被描述于1990年9月16日授权的Cockrell的美国专利4,222,905和1980年12月16日授权的Murphy的美国专利4,239,659中。
其中,R3选自C8~C20的烷基、链烯基和烷芳基;每一个R4均为C1~C4的烷基;n为1~6;和m为1~3。
这组化合物中物质的一个具体实例为:
其中,R1为C1~C4烷基;R2为C5~C30直链或支链烷基或链烯基、烷基苯、或
R3为C1~C20烷基或链烯基;a为0或1;n为0或1;m为1~5;Z-和Z2分别选自:
其中,至少有一个所说的基团选自酯、反(reverse)酯、酰胺和反酰胺;和X为一种能使化合物水溶的阴离子,优选选自酰胺、甲基硫酸盐、氢氧化物和硝酸盐,优选氯化物、溴化物或碘化物。
除了本发明所公开的其它阳离子表面活性剂的优点外,这种特殊的阳离子组分还是合乎环境需求的,因为就其长烷基链和含氮部分而言,均为生物可降解的。胆碱酯:
其中R为一C5~C30的直链或支链烷基或链烯基基团,X为一阴离子,它使化合物至少可以水分散,X优选选自卤化物、甲基硫酸盐、硫酸盐和硝酸盐,优选甲基硫酸盐、氯化物、溴化物或碘化物,以及其中上式中的酯键被反酯、酰胺或反酰胺键取代的那些基团。
特别优选的这类阳离子表面活性剂的实例包括卤化硬脂酰基胆碱酯季铵(R1=C17烷基)、卤化棕榈酰基胆碱酯季铵(R1=C15烷基)、卤化mystiroyl胆碱酯季铵(R1=C13烷基)、卤化月桂酰基胆碱酯季铵(R1=C11烷基)以及卤化椰子和牛脂胆碱酯季铵(R1分别为C15~C17烷基和C19~C13烷基)。
上面所讨论的优选胆碱衍生的阳离子物质可在酸催化剂存在下,用二甲氨基乙醇直接酯化所需链长的脂肪酸制备。然后将反应产物用甲基卤季铵化,形成所需的阳离子物质。胆碱衍生的阳离子物质也可在酸催化剂物质存在下,用二卤代乙醇直接酯化所需链长的长链脂肪酸制备。然后将反应产物用于季铵化。三甲胺,形成所需的阳离子组分。其它适用于本发明的胆碱酯具有式: 其中t为0或1,y为1~20,R和X如上所定义。阴离子表面活性剂
本发明的阴离子表面活性剂组分包括高级脂肪酸的水溶性盐,即“皂”。其包括碱金属皂,如含有约8~约24个碳原子,优选含有约12~约18个碳原子的高级脂肪酸的钠盐、钾盐、铵盐和烷基铵盐。皂可由脂肪和油直接皂化制备,或通过中和游离脂肪酸制备。特别适用的是衍生于椰子油和牛脂的脂肪酸混合物的钠盐和钾盐,即牛脂钠或牛脂钾和椰子皂。
适用的阴离子表面活性剂还包括有机硫反应产物的水溶性盐,优选碱金属盐、铵盐和烷基醇铵盐,其分子结构中含有一约含10~约20个碳原子的烷基和一磺酸基或硫酸酯基。(术语“烷基”包括酰基中的烷基部分)。这组合成表面活性剂的实例为烷基硫酸钠和烷基硫酸钾,特别是硫酸化高级醇(C8~C18碳原子)所得的产物,如通过还原牛脂或椰子油甘油酯所得的产物;和烷基苯磺酸钠和烷基苯磺酸钾,其中烷基为含有约9~约15个碳原子的直链构型或支链构型,如描述于美国专利2,220,099和2,477,383中的那些类型。特别有价值的是直链烷基苯磺酸盐,其中烷基基团中碳原子的平均数为约11~13,简写为C11~C13LAS。
本发明中适用的其它阴离子表面活性剂包括α-磺化脂肪酸酯的水溶性盐,其脂肪酸基团中含有约6~20个碳原子,和酯基中含有约1~10个碳原子;2-酰氧基-链烷烃-1-磺酸的水溶性盐,其酰基中含有约2~9个碳原子,链烷烃部分中含有约9~约23个碳原子;烷基中含有约10~20个碳原子,并含有约1~30摩尔环氧乙烷的烷基醚硫酸盐;和含有约12~24个碳原子的烯烃磺酸的水溶性盐;和β-烷氧基链烷烃磺酸盐,其烷基中含有约1~3个碳原子,链烷烃部分中含有约8~约20个碳原子。
还可被认为适用于本发明的阴离子表面活性剂是水溶助长剂,如芳基磺酸盐。优选苯磺酸、甲苯磺酸、二甲苯磺酸或异丙苯磺酸的钠盐或钾盐。抑泡剂
适用于本发明的抑泡剂作为一种操作助剂,用来控制混合阳离子表面活性剂溶液和阴离子表面活性剂阶段的泡沫。
有多种物质可用作抑泡剂,如单羧酸脂肪酸及其可溶性盐、高分子量的烃,如石蜡、脂肪酸酯、一价醇的脂肪酸酯、脂族C1~C40酮、N-烷氧基化氨基三嗪、氧化丙烯、一硬脂酰磷酸酯和磷酸酯。另一类优选的抑泡剂包括聚硅氧烷抑泡剂。这类化合物包括聚有机硅氧烷油,如聚二甲基硅氧烷,聚有机硅氧烷油或树脂的分散体或乳状液,聚有机硅氧烷和二氧化硅颗粒的混合物,其中聚有机硅氧烷被化学吸附或熔合到二氧化硅上。硅氧烷抑泡剂在本领域中已众所周知,并被公开于例如1981年5月5日授权的美国专利申请US-A4265779中。其它的硅氧烷抑泡剂被公开于美国专利申请US-A3455839和德国专利申请DE-A2124526中。粉末
有多种粉末适用于本发明方法的粒化步骤。优选用于本发明方法和组合物的粉末为:相容的脱垢助洗剂或助洗剂混合物或粉末。
本发明的洗涤剂组合物可包含下式的晶体硅铝酸盐离子交换材料:
Naz[(AlO2)z·(SiO2)y]·xH2O
其中,z和y至少为约6,z与y的摩尔比为约1.0~约0.4,z为约10~约264。适用于本发明的无定形水合硅铝酸盐材料的经验式为:
Mz(zAlO2·ySiO2)
其中M为钠、钾、铵或取代铵,z为约0.5~约2,和y为1,所说的材料的镁离子交换容量至少为每克无水硅铝酸盐约50毫克当量CaCO3硬度。优选水合钠沸石A的粒径为约1~10微米。
本发明的硅铝酸盐离子交换助洗剂材料为水合形式,若其为晶体,则约含10%~约28%(重量)的水,若其为无定形的,则甚至会含有更多量的水。高度优选的晶体硅铝酸盐离子交换材料,其晶体基质中含有约18%~约22%的水。晶体硅铝酸盐离子交换材料的特征还在于其粒径为约0.1微米~约10微米。无定形材料通常更小,例如小到小于约0.01微米。优选的离子交换材料的粒径为约0.2微米~约4微米。本发明的术语"粒径"是指一定重量离子交换材料的平均粒子直径,可用传统的分析方法测定,如使用扫描电子显微镜的显微测定法。本发明的晶体硅铝酸盐离子交换材料的特征通常还在于,其钙离子交换容量以无水基计算至少为约200毫克当量CaCO3水硬度/克硅铝酸盐,一般其范围为约300毫克当量/克~约352毫克当量/克。本发明的硅铝酸盐离子交换材料的特征还在于以钙离子硬度计其钙离子交换速率至少为约2格令Ca++/加仑/分钟/克/加仑硅铝酸盐(无水基),一般是在约2格令/加仑/分钟/克/加仑~约6格令/加仑/分钟/克/加仑的范围内。用于助洗剂的最佳硅铝酸盐所具有的钙离子交换速率至少为约4格令/加仑/分钟/克/加仑。
无定形硅铝酸盐离子交换材料的Mg++交换量通常至少为约50毫克当量CaCO3/克(12毫克Mg++/克),Mg++交换速率至少为约1格令/加仑/分钟/克/加仑。当用Cu辐射法(1.54埃单位)检验时,无定形材料不呈现可见的衍射花样。
适用于本发明实践的硅铝酸盐离子交换材料可在市场上购得。适用于本发明的硅铝酸盐结构可以为晶体或无定形,可以是天然存在的硅铝酸盐或合成衍生的。1976年10月12日授权Krummel等人的美国专利3,985,669讨论了一种生产硅铝酸盐离子交换材料的方法,在此引入作为参考。优选适用于本发明的合成晶体硅铝酸盐离子交换材料可以以名称沸石A、沸石B、沸石P、沸石MAP和沸石X购得。在一个特别优选的实施方案中,晶体硅铝酸盐离子交换材料的化学式为:
Na12[(AlO2)12(SiO2)12]·xH2O
其中x为约20~约30,特别是约为27,其粒径一般小于约5微米。
本发明的粒状洗涤剂中可含有中性盐或碱性盐,其溶液的pH为7或更大,就性质而言,可以是有机盐或无机盐。助洗剂盐类有助于为本发明的洗涤剂颗粒提供所需的密度和体积。尽管有些盐是惰性的,但多数盐类在洗涤溶液中仍可起脱垢助洗剂材料的作用。
中性水溶性盐类的实例包括碱金属、铵或取代铵的氯化物、氟化物和硫酸盐。上述盐中,优选碱金属盐,特别是钠盐。一般在洗涤剂颗粒中使用硫酸钠,它是一种特别优选的盐。通常,柠檬酸和任何其它的有机酸或无机酸也可被加到本发明的粒状洗涤剂中,只要它能与其它附聚物组合物化学相容。
其它适用的水溶性盐类包括通常所称的洗涤剂助洗剂材料的化合物。助洗剂一般选自多种水溶性的碱金属、铵或取代的铵磷酸盐、聚磷酸盐、膦酸盐、聚膦酸盐、碳酸盐、硅酸盐、硼酸盐、柠檬酸盐、二氧化硅和聚羟基磺酸盐。优选上述盐中的碱金属盐,特别是钠盐。
无机磷酸盐助洗剂的具体实例是钠和钾的三聚磷酸盐、焦磷酸盐、聚合度为约6~21的聚偏磷酸盐,和正磷酸盐。聚膦酸盐助洗剂的实例是亚乙基二膦酸的钠盐和钾盐,乙烷1-羟基-1,1-二膦酸的钠盐和钾盐,和乙烷1,1,2-三磷酸的钠盐和钾盐。其它的磷助洗剂化合物公开于美国专利3,159,581;3,213,030;3,422,021;3,422,137;3,400,176和3,400,148中,在此引入作为参考。
非磷无机助洗剂的实例是钠和钾的碳酸盐、碳酸氢盐、倍半碳酸盐、四硼酸盐十水合物和SiO2与碱金属氧化物的摩尔比为约0.5~约4.0,优选约1.0~约2.4的硅酸盐。用本发明方法所制备的组合物加工时不需过量的碳酸盐,优选不包含2%以上细分散的碳酸钙,如1980年4月1日授权的Clarke等人的美国专利4,196,093所公开,优选不包含后者。柔软粘土
柔软粘土是一种特别有用的组分,可被任选地掺入到本发明的组合物中。使用时,可将粘土掺入到含有本发明颗粒的阳离子表面活性剂中,但优选将粘土掺入到与阳离子表面活性剂分开的颗粒中。然后可将含有颗粒的阳离子表面活性剂和含有颗粒的粘土混合在一起,通常与其它含有传统洗涤剂成分的粒状组分混合在一起,制成商业化的洗衣用洗涤剂成品。
柔软粘土可未经改性或经过有机改性。未经有机改性的粘土可被描述为可膨胀的三层粘土,即硅铝酸盐和硅酸镁,其离子交换容量至少为50毫克当量/100克粘土,优选至少60毫克当量/100克粘土。可以类似地描述制备有机改性粘土的原始粘土。用于描述粘土的术语“可膨胀的”涉及层状粘土结构与水接触后溶胀或膨胀的能力。本发明所用的三层可膨胀的粘土是地质学上分类为绿土的那些材料。
有两种不同类型的绿土粘土,对于外层上给定数量的硅氧原子而言,粘土的主要区别在于中间层八面体的金属氧排列数目。1963年,JohnWiley & Sons(Interscience Publishers),New York出版的H.van Olphen编著的《粘土胶体化学》(Clay Colloid Chemistry)第六章,特别是第66~69页,对粘土物质给出了更全面的描述。
绿土(或蒙脱石类)粘土家族包括下述三八面体矿物质:滑石、水辉石、滑石粉、锌蒙脱石、蛭石;和下述二八面体矿物质:青磐岩、蒙脱石、铬蒙脱石和绿脱石。
这些组合物中所用的粘土含有阳荷性反离子,如质子、钠离子、钾离子、钙离子和锂离子。习惯于用主要吸收一种阳离子或只吸收一种阳离子来区分粘土。例如钠粘土是一种吸收的阳离子主要是钠的粘土。这类被吸收的阳离子处于与存在于水溶液中的阳离子的交换反应之中。绿土型粘土参加的典型交换反应可用下式表示:
由于在上述平衡反应中,等当量重的铵离子取代了等当量重的钠离子,所以习惯于用每100克粘土的毫克当量(meq/100g)来测量阳离子交换容量(有时称作"碱交换容量")。粘土的阳离子交换容量可以用几种方法测定,包括电渗析法,通过与铵离子交换,然后滴定的方法,或亚甲基兰方法,这些方法被详细地阐述于1971年Interscience出版的Grimshaw编著的《粘土化学与物理学》(The Chemistry and Physics of Clays)第264~265页。粘土材料的阳离子交换容量涉及这样的因素,如粘土的膨胀性质、粘土的电荷(依次至少部分地用点阵结构测定)等。粘土的离子交换容量大范围地在约2毫克当量/100克高岭土~约150毫克当量/100克高岭土的范围内变化,某些绿土粘土的该变化范围更大。
优选的绿土型粘土为钠蒙脱石、钾蒙脱石、钠水辉石和钾水辉石。本发明所用的粘土的粒径可高达约1微米。
本发明所用的粘土或者是天然存在的,或者是人工合成衍生的。
实施例
在下述实施例中,阳离子表面活性剂为氯化C12~C14烷基二甲基羟乙基铵
(C12~14)烷基醚(3)硫酸钠是C12~14乙氧化醇的钠盐,平均每摩尔钠盐中有3摩尔醚。
抑泡剂为聚二甲基硅氧烷(85%)和憎水二氧化硅(15%)。
制备了下述组合物:
%(重量)
阳离子表面活性剂 40
(C12~14)烷基硫酸钠 1.6
(C12~14)烷基醚(3)硫酸钠 0.4
沸石A(水合) 54.9
抑泡剂 0.1
水 3实施例1
把40%的阳离子表面活性剂水溶液、79%的阴离子表面活性剂混合物含水膏体和消泡剂混合,制备上述组合物。然后将混合物蒸发,形成60%阳离子表面活性剂的活性膏体。将膏体填入高剪切混合机(Loe digeCB)中,与沸石A成粒。将所得颗粒再用低剪切混合机(Loe digeKM)处理,然后在流化床干燥器中将其干燥到含水量为3%(游离)。实施例2
把40%的阳离子表面活性剂水溶液与79%的阴离子表面活性剂混合物含水膏体混合,制备上述组合物。将沸石A也加到混合物中,形成一均匀的搅和机混合物。然后将搅和机混合物在传统的逆流式喷雾干燥塔中用热风干燥,制成粒状组合物成品。比较实施例A
把40%的阳离子表面活性剂水溶液进料到高剪切混合机(Loe digeCB)中,与一定数量的沸石A粉末附聚。在刚发生过附聚作用(当液体量超过粉末容量点处,导致形成一不可加工的“捏塑体”)时,停止进料。然后将所得的湿附聚物在流化床中干燥,得到一包含下述组合物的产品。
%(重量)
阳离子表面活性剂 15
(C12~C14)烷基硫酸钠 -
(C12~C14)烷基醚(3)硫酸钠 -
沸石A(水合) 82
水 3
由于低的阳离子表面活性剂活性,所以不适于将该颗粒加到“紧密型”产品中。比较实施例B
把40%的阳离子表面活性剂水溶液用蒸发法干燥,形成60%的阳离子表面活性剂的活性膏体。膏体变成一种高粘度的凝胶,可以不再进行有效加工。
Claims (8)
1.一种包含阴离子表面活性剂、水溶性阳离子表面活性剂和少于10%(重量)的阴离子聚合物的粒状洗涤剂组合物或组分,
其特征在于:
阳离子表面活性剂的量为组合物或组分重量的至少20%,阴离子表面活性剂与阳离子表面活性剂的摩尔比小于1∶1。
2.一种根据权利要求1的粒状洗涤剂组合物或组分,其中阳离子表面活性剂的量为组合物或组分重量的至少30%,阴离子表面活性剂的量为组合物或组分重量的1%~20%,阴离子表面活性剂与阳离子表面活性剂的摩尔比小于0.5∶1。
3.一种根据权利要求2的粒状洗涤剂组合物或组分,还包含10%~69%(重量)的选自硅铝酸盐、硅酸盐、碳酸盐、柠檬酸盐、磷酸盐或其混合物的洗涤剂助洗剂。
4.一种根据权利要求3的粒状洗涤剂组合物或组分,其基本上不含阴离子聚合物,其包括:
(a)35%~50%(重量)的水溶性阳离子表面活性剂;
(b)1%~5%(重量)的阴离子表面活性剂;和
(c)40%~60%(重量)的硅铝酸钠。
5.一种制备组合物或组分的方法,该方法的步骤包括:
(i)将包含水溶性阳离子表面活性剂、阴离子表面活性剂和少于10%(重量)阴离子聚合物的水溶液混合;
(ii)干燥混合物,使之形成至少包含50%(重量)固体含量的浓溶液,和
(iii)粒化浓溶液;
其特征在于:
阳离子表面活性剂的量为组合物或组分重量的至少20%,阴离
子表面活性剂与阳离子表面活性剂的摩尔比小于1∶1。
6.一种根据权利要求5的方法,其中在混合步骤(i)中加入一种抑泡剂。
7.一种根据权利要求5或6之一的方法,其中干燥步骤可用蒸发法完成,粒化步骤随后可通过混合浓溶液和洗涤剂助洗剂来完成,洗涤剂助洗剂选自硅铝酸盐、硅酸盐、碳酸盐、柠檬酸盐、磷酸盐或其混合物。
8.一种根据权利要求5的方法,其中干燥和粒化步骤同时进行,优选采用喷雾干燥法。
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EP94308960A EP0714976B2 (en) | 1994-12-02 | 1994-12-02 | Detergent compositions comprising cationic surfactant and process for making the composition |
EP94308960.7 | 1994-12-02 |
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EP (1) | EP0714976B2 (zh) |
JP (1) | JPH10511713A (zh) |
CN (1) | CN1174566A (zh) |
AT (1) | ATE193051T1 (zh) |
AU (1) | AU4371496A (zh) |
BR (1) | BR9509843A (zh) |
CA (1) | CA2206326A1 (zh) |
DE (1) | DE69424551T3 (zh) |
MA (1) | MA23734A1 (zh) |
MX (1) | MX9704078A (zh) |
TR (1) | TR199501509A2 (zh) |
WO (1) | WO1996017042A1 (zh) |
ZA (1) | ZA9510227B (zh) |
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CN100475944C (zh) * | 2000-04-20 | 2009-04-08 | 荷兰联合利华有限公司 | 粒状洗涤剂组分及其制备方法 |
CN103298920A (zh) * | 2011-01-12 | 2013-09-11 | 宝洁公司 | 用于控制水溶性膜塑化的方法 |
CN115895790A (zh) * | 2022-11-30 | 2023-04-04 | 四川科宏达集团有限责任公司 | 一种阴-阳离子表面活性剂复配清洗剂及制备方法 |
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DE19721885A1 (de) † | 1997-05-26 | 1998-12-03 | Henkel Kgaa | Verfahren zur Herstellung kationtensidhaltiger Granulate |
EP0971030A1 (en) * | 1998-07-10 | 2000-01-12 | The Procter & Gamble Company | Surfactant agglomerates |
GB0009029D0 (en) | 2000-04-12 | 2000-05-31 | Unilever Plc | Laundry wash compositions |
DE102004018751A1 (de) * | 2004-04-17 | 2005-11-03 | Clariant Gmbh | Verfahren zur Herstellung von quaternären Hydroxyalkylammonium Granulaten |
US20080262129A1 (en) * | 2007-04-06 | 2008-10-23 | Kao Corporation | Process for producing powder |
WO2011142424A1 (ja) * | 2010-05-14 | 2011-11-17 | ユケン工業株式会社 | 水系洗浄剤組成物 |
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ZA755347B (en) † | 1974-09-06 | 1977-04-27 | Colgate Palmolive Co | Fabric softening composition containing molecular sieve zeolite |
DE2449354B2 (de) * | 1974-10-17 | 1979-08-23 | Basf Ag, 6700 Ludwigshafen | Verwendung von Orthophosphorsäureestern als Schaumdämpfer in kationischen Tensidformulierungen |
US3936537A (en) † | 1974-11-01 | 1976-02-03 | The Procter & Gamble Company | Detergent-compatible fabric softening and antistatic compositions |
NL7815052A (nl) * | 1977-11-17 | 1980-01-31 | Procter & Gamble | Korrelvormige wasmiddelen ter betere verwijdering van vet vuil. |
US4292035A (en) † | 1978-11-13 | 1981-09-29 | The Procter & Gamble Company | Fabric softening compositions |
EP0011333B1 (en) † | 1978-11-16 | 1982-12-01 | THE PROCTER & GAMBLE COMPANY | Particulate detergent additive comprising insoluble, anionic-cationic softener complex and detergent compositions containing the same |
JPS598392B2 (ja) * | 1979-06-29 | 1984-02-24 | 花王株式会社 | 洗浄剤組成物 |
ATE10646T1 (de) * | 1979-09-29 | 1984-12-15 | The Procter & Gamble Company | Reinigungsmittelzusammensetzungen. |
JPS57137397A (en) * | 1981-02-20 | 1982-08-24 | Kao Corp | Detergent composition |
US4430244A (en) * | 1982-03-04 | 1984-02-07 | Colgate-Palmolive Company | Silicate-free bleaching and laundering composition |
US4622173A (en) * | 1984-12-31 | 1986-11-11 | Colgate-Palmolive Co. | Non-aqueous liquid laundry detergents containing three surfactants including a polycarboxylic acid ester of a non-ionic |
US4637890A (en) * | 1986-01-23 | 1987-01-20 | The Procter & Gamble Company | Detergent composition providing rinse cycle suds and turbidity control containing a soap, quaternary ammonium salt and a silicone |
US4686060A (en) † | 1986-01-23 | 1987-08-11 | The Procter & Gamble Company | Detergent composition providing rinse cycle suds control containing a soap, a quaternary ammonium salt and a silicone |
US5071594A (en) * | 1989-10-02 | 1991-12-10 | Ethyl Corporation | Free flowing granular laundry detergent comprising tert-amine oxide dihydrate |
AU662780B2 (en) * | 1991-12-18 | 1995-09-14 | Colgate-Palmolive Company, The | Free-flowing powder fabric softening composition and process for its manufacture |
-
1994
- 1994-12-02 EP EP94308960A patent/EP0714976B2/en not_active Expired - Lifetime
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1995
- 1995-11-29 TR TR95/01509A patent/TR199501509A2/xx unknown
- 1995-11-30 JP JP8519046A patent/JPH10511713A/ja active Pending
- 1995-11-30 MX MX9704078A patent/MX9704078A/es unknown
- 1995-11-30 WO PCT/US1995/015548 patent/WO1996017042A1/en not_active Application Discontinuation
- 1995-11-30 CN CN95197503.XA patent/CN1174566A/zh active Pending
- 1995-11-30 CA CA002206326A patent/CA2206326A1/en not_active Abandoned
- 1995-11-30 BR BR9509843A patent/BR9509843A/pt not_active Application Discontinuation
- 1995-11-30 AU AU43714/96A patent/AU4371496A/en not_active Abandoned
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Cited By (4)
Publication number | Priority date | Publication date | Assignee | Title |
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CN100475944C (zh) * | 2000-04-20 | 2009-04-08 | 荷兰联合利华有限公司 | 粒状洗涤剂组分及其制备方法 |
CN103298920A (zh) * | 2011-01-12 | 2013-09-11 | 宝洁公司 | 用于控制水溶性膜塑化的方法 |
CN103298920B (zh) * | 2011-01-12 | 2015-11-25 | 宝洁公司 | 用于控制水溶性膜塑化的方法 |
CN115895790A (zh) * | 2022-11-30 | 2023-04-04 | 四川科宏达集团有限责任公司 | 一种阴-阳离子表面活性剂复配清洗剂及制备方法 |
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Publication number | Publication date |
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DE69424551T3 (de) | 2005-12-29 |
EP0714976B1 (en) | 2000-05-17 |
MX9704078A (es) | 1997-08-30 |
DE69424551T2 (de) | 2001-01-18 |
AU4371496A (en) | 1996-06-19 |
EP0714976A1 (en) | 1996-06-05 |
MA23734A1 (fr) | 1996-07-01 |
JPH10511713A (ja) | 1998-11-10 |
TR199501509A2 (tr) | 1996-07-21 |
WO1996017042A1 (en) | 1996-06-06 |
BR9509843A (pt) | 1997-11-25 |
DE69424551D1 (de) | 2000-06-21 |
ATE193051T1 (de) | 2000-06-15 |
EP0714976B2 (en) | 2005-03-23 |
CA2206326A1 (en) | 1996-06-06 |
ZA9510227B (en) | 1996-06-12 |
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