CA2206326A1 - Detergent compositions comprising cationic surfactant and process for making the composition - Google Patents
Detergent compositions comprising cationic surfactant and process for making the compositionInfo
- Publication number
- CA2206326A1 CA2206326A1 CA002206326A CA2206326A CA2206326A1 CA 2206326 A1 CA2206326 A1 CA 2206326A1 CA 002206326 A CA002206326 A CA 002206326A CA 2206326 A CA2206326 A CA 2206326A CA 2206326 A1 CA2206326 A1 CA 2206326A1
- Authority
- CA
- Canada
- Prior art keywords
- weight
- cationic surfactant
- composition
- surfactant
- component
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Abandoned
Links
- 239000000203 mixture Substances 0.000 title claims abstract description 57
- 239000003093 cationic surfactant Substances 0.000 title claims abstract description 53
- 239000003599 detergent Substances 0.000 title claims abstract description 26
- 238000000034 method Methods 0.000 title claims abstract description 12
- 239000003945 anionic surfactant Substances 0.000 claims abstract description 30
- 239000007864 aqueous solution Substances 0.000 claims abstract description 12
- 239000000243 solution Substances 0.000 claims abstract description 12
- 229920006318 anionic polymer Polymers 0.000 claims abstract description 8
- 238000001035 drying Methods 0.000 claims abstract description 8
- 239000007787 solid Substances 0.000 claims abstract description 3
- HNPSIPDUKPIQMN-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Al]O[Al]=O HNPSIPDUKPIQMN-UHFFFAOYSA-N 0.000 claims description 27
- 229910000323 aluminium silicate Inorganic materials 0.000 claims description 24
- 239000003795 chemical substances by application Substances 0.000 claims description 8
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 claims description 5
- BPQQTUXANYXVAA-UHFFFAOYSA-N Orthosilicate Chemical compound [O-][Si]([O-])([O-])[O-] BPQQTUXANYXVAA-UHFFFAOYSA-N 0.000 claims description 5
- 229910019142 PO4 Inorganic materials 0.000 claims description 5
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 claims description 5
- KRKNYBCHXYNGOX-UHFFFAOYSA-K Citrate Chemical compound [O-]C(=O)CC(O)(CC([O-])=O)C([O-])=O KRKNYBCHXYNGOX-UHFFFAOYSA-K 0.000 claims description 4
- 239000010452 phosphate Substances 0.000 claims description 4
- 238000001704 evaporation Methods 0.000 claims description 3
- 230000008020 evaporation Effects 0.000 claims description 3
- 238000001694 spray drying Methods 0.000 claims description 2
- 229910000503 Na-aluminosilicate Inorganic materials 0.000 claims 1
- 235000012217 sodium aluminium silicate Nutrition 0.000 claims 1
- 239000000429 sodium aluminium silicate Substances 0.000 claims 1
- URGAHOPLAPQHLN-UHFFFAOYSA-N sodium aluminosilicate Chemical compound [Na+].[Al+3].[O-][Si]([O-])=O.[O-][Si]([O-])=O URGAHOPLAPQHLN-UHFFFAOYSA-N 0.000 claims 1
- 239000000463 material Substances 0.000 description 27
- 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 23
- -1 alkyl dimethyl ethoxy ammonium chloride Chemical compound 0.000 description 23
- 239000011734 sodium Substances 0.000 description 23
- 229910052708 sodium Inorganic materials 0.000 description 22
- 238000005342 ion exchange Methods 0.000 description 19
- 125000000217 alkyl group Chemical group 0.000 description 17
- 239000004927 clay Substances 0.000 description 17
- 125000004432 carbon atom Chemical group C* 0.000 description 15
- 150000003839 salts Chemical class 0.000 description 15
- 239000002245 particle Substances 0.000 description 12
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 10
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 9
- 125000002091 cationic group Chemical group 0.000 description 9
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 description 8
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 description 8
- 235000014113 dietary fatty acids Nutrition 0.000 description 8
- 150000002148 esters Chemical class 0.000 description 8
- 239000000194 fatty acid Substances 0.000 description 8
- 229930195729 fatty acid Natural products 0.000 description 8
- 150000005215 alkyl ethers Chemical class 0.000 description 7
- 229910052700 potassium Inorganic materials 0.000 description 7
- 239000011591 potassium Substances 0.000 description 7
- BHPQYMZQTOCNFJ-UHFFFAOYSA-N Calcium cation Chemical group [Ca+2] BHPQYMZQTOCNFJ-UHFFFAOYSA-N 0.000 description 6
- 229910021536 Zeolite Inorganic materials 0.000 description 6
- 229910052783 alkali metal Inorganic materials 0.000 description 6
- 150000001340 alkali metals Chemical class 0.000 description 6
- 150000004665 fatty acids Chemical class 0.000 description 6
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 6
- 239000000843 powder Substances 0.000 description 6
- 239000010457 zeolite Substances 0.000 description 6
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 description 5
- 150000001408 amides Chemical class 0.000 description 5
- 229910001424 calcium ion Inorganic materials 0.000 description 5
- 229960001231 choline Drugs 0.000 description 5
- 159000000001 potassium salts Chemical class 0.000 description 5
- 239000004094 surface-active agent Substances 0.000 description 5
- 239000003760 tallow Substances 0.000 description 5
- JLVVSXFLKOJNIY-UHFFFAOYSA-N Magnesium ion Chemical group [Mg+2] JLVVSXFLKOJNIY-UHFFFAOYSA-N 0.000 description 4
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 description 4
- 125000003342 alkenyl group Chemical group 0.000 description 4
- 229910000019 calcium carbonate Inorganic materials 0.000 description 4
- 235000010216 calcium carbonate Nutrition 0.000 description 4
- 150000001768 cations Chemical class 0.000 description 4
- 150000001875 compounds Chemical class 0.000 description 4
- 239000008187 granular material Substances 0.000 description 4
- 239000000377 silicon dioxide Substances 0.000 description 4
- 229910021647 smectite Inorganic materials 0.000 description 4
- 239000000344 soap Substances 0.000 description 4
- 229910021653 sulphate ion Inorganic materials 0.000 description 4
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical class C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 3
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical class CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 3
- 150000001298 alcohols Chemical class 0.000 description 3
- 150000001450 anions Chemical class 0.000 description 3
- 238000005341 cation exchange Methods 0.000 description 3
- 238000006243 chemical reaction Methods 0.000 description 3
- 239000007795 chemical reaction product Substances 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
- 150000004820 halides 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
- 229910000271 hectorite Inorganic materials 0.000 description 3
- JZMJDSHXVKJFKW-UHFFFAOYSA-M methyl sulfate(1-) Chemical compound COS([O-])(=O)=O JZMJDSHXVKJFKW-UHFFFAOYSA-M 0.000 description 3
- 239000003921 oil Substances 0.000 description 3
- 235000019198 oils Nutrition 0.000 description 3
- 235000021317 phosphate Nutrition 0.000 description 3
- 229920001296 polysiloxane Polymers 0.000 description 3
- 239000000047 product Substances 0.000 description 3
- 239000007921 spray Substances 0.000 description 3
- GETQZCLCWQTVFV-UHFFFAOYSA-N trimethylamine Chemical compound CN(C)C GETQZCLCWQTVFV-UHFFFAOYSA-N 0.000 description 3
- NLXLAEXVIDQMFP-UHFFFAOYSA-N Ammonium chloride Substances [NH4+].[Cl-] NLXLAEXVIDQMFP-UHFFFAOYSA-N 0.000 description 2
- CPELXLSAUQHCOX-UHFFFAOYSA-M Bromide Chemical compound [Br-] CPELXLSAUQHCOX-UHFFFAOYSA-M 0.000 description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 2
- 235000013162 Cocos nucifera Nutrition 0.000 description 2
- 244000060011 Cocos nucifera Species 0.000 description 2
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-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
- 239000002253 acid Substances 0.000 description 2
- 125000002252 acyl group Chemical group 0.000 description 2
- 150000001335 aliphatic alkanes Chemical group 0.000 description 2
- 150000004996 alkyl benzenes Chemical class 0.000 description 2
- 235000019270 ammonium chloride Nutrition 0.000 description 2
- 150000003863 ammonium salts Chemical class 0.000 description 2
- OEYIOHPDSNJKLS-UHFFFAOYSA-N choline Chemical compound C[N+](C)(C)CCO OEYIOHPDSNJKLS-UHFFFAOYSA-N 0.000 description 2
- 235000019864 coconut oil Nutrition 0.000 description 2
- 239000003240 coconut oil Substances 0.000 description 2
- 229910052681 coesite Inorganic materials 0.000 description 2
- 230000000052 comparative effect Effects 0.000 description 2
- 229910052906 cristobalite Inorganic materials 0.000 description 2
- 239000004205 dimethyl polysiloxane Substances 0.000 description 2
- 235000013870 dimethyl polysiloxane Nutrition 0.000 description 2
- 230000032050 esterification Effects 0.000 description 2
- 238000005886 esterification reaction Methods 0.000 description 2
- 239000004615 ingredient Substances 0.000 description 2
- 229910052500 inorganic mineral Inorganic materials 0.000 description 2
- 239000000693 micelle Substances 0.000 description 2
- 239000011707 mineral Substances 0.000 description 2
- 235000010755 mineral Nutrition 0.000 description 2
- 229910052901 montmorillonite Inorganic materials 0.000 description 2
- 230000007935 neutral effect Effects 0.000 description 2
- 229910052760 oxygen Inorganic materials 0.000 description 2
- 229940055076 parasympathomimetics choline ester Drugs 0.000 description 2
- 229920000435 poly(dimethylsiloxane) Polymers 0.000 description 2
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Chemical compound [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 description 2
- 150000003856 quaternary ammonium compounds Chemical class 0.000 description 2
- 150000003248 quinolines Chemical class 0.000 description 2
- 235000012239 silicon dioxide Nutrition 0.000 description 2
- 229910052682 stishovite Inorganic materials 0.000 description 2
- 229910052905 tridymite Inorganic materials 0.000 description 2
- 125000004178 (C1-C4) alkyl group Chemical group 0.000 description 1
- QLAJNZSPVITUCQ-UHFFFAOYSA-N 1,3,2-dioxathietane 2,2-dioxide Chemical compound O=S1(=O)OCO1 QLAJNZSPVITUCQ-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
- JBVOQKNLGSOPNZ-UHFFFAOYSA-N 2-propan-2-ylbenzenesulfonic acid Chemical class CC(C)C1=CC=CC=C1S(O)(=O)=O JBVOQKNLGSOPNZ-UHFFFAOYSA-N 0.000 description 1
- ZCYVEMRRCGMTRW-UHFFFAOYSA-N 7553-56-2 Chemical compound [I] ZCYVEMRRCGMTRW-UHFFFAOYSA-N 0.000 description 1
- BVKZGUZCCUSVTD-UHFFFAOYSA-M Bicarbonate Chemical compound OC([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-M 0.000 description 1
- LSNNMFCWUKXFEE-UHFFFAOYSA-M Bisulfite Chemical compound OS([O-])=O LSNNMFCWUKXFEE-UHFFFAOYSA-M 0.000 description 1
- 125000006538 C11 alkyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- SGFBLYBOTWZDDE-UHFFFAOYSA-N Choline stearate Chemical compound CCCCCCCCCCCCCCCCCC(=O)OCC[N+](C)(C)C SGFBLYBOTWZDDE-UHFFFAOYSA-N 0.000 description 1
- OTMSDBZUPAUEDD-UHFFFAOYSA-N Ethane Chemical class CC OTMSDBZUPAUEDD-UHFFFAOYSA-N 0.000 description 1
- IAYPIBMASNFSPL-UHFFFAOYSA-N Ethylene oxide Chemical compound C1CO1 IAYPIBMASNFSPL-UHFFFAOYSA-N 0.000 description 1
- DBVJJBKOTRCVKF-UHFFFAOYSA-N Etidronic acid Chemical class OP(=O)(O)C(O)(C)P(O)(O)=O DBVJJBKOTRCVKF-UHFFFAOYSA-N 0.000 description 1
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 description 1
- UEEJHVSXFDXPFK-UHFFFAOYSA-N N-dimethylaminoethanol Chemical compound CN(C)CCO UEEJHVSXFDXPFK-UHFFFAOYSA-N 0.000 description 1
- 229910017974 NH40H Inorganic materials 0.000 description 1
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical class CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 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
- ABLZXFCXXLZCGV-UHFFFAOYSA-N Phosphorous acid Chemical class OP(O)=O ABLZXFCXXLZCGV-UHFFFAOYSA-N 0.000 description 1
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 1
- 229920000388 Polyphosphate Polymers 0.000 description 1
- 239000004614 Process Aid Substances 0.000 description 1
- GOOHAUXETOMSMM-UHFFFAOYSA-N Propylene oxide Chemical compound CC1CO1 GOOHAUXETOMSMM-UHFFFAOYSA-N 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
- OBNDGIHQAIXEAO-UHFFFAOYSA-N [O].[Si] Chemical group [O].[Si] OBNDGIHQAIXEAO-UHFFFAOYSA-N 0.000 description 1
- 239000003377 acid catalyst Substances 0.000 description 1
- 238000005054 agglomeration Methods 0.000 description 1
- 125000001931 aliphatic group Chemical group 0.000 description 1
- 229910000272 alkali metal oxide Inorganic materials 0.000 description 1
- 125000005210 alkyl ammonium group Chemical group 0.000 description 1
- 125000002877 alkyl aryl group Chemical group 0.000 description 1
- 125000005211 alkyl trimethyl ammonium group Chemical group 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 239000002518 antifoaming agent Substances 0.000 description 1
- 239000002585 base Substances 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 150000001642 boronic acid derivatives Chemical class 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 150000004649 carbonic acid derivatives Chemical class 0.000 description 1
- 239000003054 catalyst Substances 0.000 description 1
- 150000001767 cationic compounds Chemical class 0.000 description 1
- NEHMKBQYUWJMIP-NJFSPNSNSA-N chloro(114C)methane Chemical compound [14CH3]Cl NEHMKBQYUWJMIP-NJFSPNSNSA-N 0.000 description 1
- 150000001860 citric acid derivatives Chemical class 0.000 description 1
- 239000002734 clay mineral Substances 0.000 description 1
- 239000000084 colloidal system Substances 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 229960002887 deanol Drugs 0.000 description 1
- XPPKVPWEQAFLFU-UHFFFAOYSA-J diphosphate(4-) Chemical compound [O-]P([O-])(=O)OP([O-])([O-])=O XPPKVPWEQAFLFU-UHFFFAOYSA-J 0.000 description 1
- 235000011180 diphosphates Nutrition 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- 239000012153 distilled water Substances 0.000 description 1
- 238000000909 electrodialysis Methods 0.000 description 1
- 239000000839 emulsion Substances 0.000 description 1
- 239000003925 fat Substances 0.000 description 1
- 235000019197 fats Nutrition 0.000 description 1
- 125000005313 fatty acid group Chemical group 0.000 description 1
- 239000012530 fluid Substances 0.000 description 1
- 150000004673 fluoride salts Chemical class 0.000 description 1
- 235000021588 free fatty acids Nutrition 0.000 description 1
- 125000005456 glyceride group Chemical group 0.000 description 1
- 238000005469 granulation Methods 0.000 description 1
- 230000003179 granulation Effects 0.000 description 1
- 159000000011 group IA salts Chemical class 0.000 description 1
- 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
- 229930195733 hydrocarbon Natural products 0.000 description 1
- 150000002430 hydrocarbons Chemical class 0.000 description 1
- XMBWDFGMSWQBCA-UHFFFAOYSA-N hydrogen iodide Chemical compound I XMBWDFGMSWQBCA-UHFFFAOYSA-N 0.000 description 1
- 230000002209 hydrophobic effect Effects 0.000 description 1
- 239000003752 hydrotrope Substances 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-M hydroxide Chemical compound [OH-] XLYOFNOQVPJJNP-UHFFFAOYSA-M 0.000 description 1
- 125000002768 hydroxyalkyl group Chemical group 0.000 description 1
- 229910052816 inorganic phosphate Inorganic materials 0.000 description 1
- 239000011630 iodine Substances 0.000 description 1
- 229910052740 iodine Inorganic materials 0.000 description 1
- 150000002576 ketones Chemical class 0.000 description 1
- 238000004900 laundering Methods 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 229910001416 lithium ion Inorganic materials 0.000 description 1
- 150000004668 long chain fatty acids Chemical class 0.000 description 1
- 229910001425 magnesium ion Inorganic materials 0.000 description 1
- 239000000391 magnesium silicate Substances 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 239000011159 matrix material Substances 0.000 description 1
- 125000005341 metaphosphate group Chemical group 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
- 150000007522 mineralic acids Chemical class 0.000 description 1
- 238000006386 neutralization reaction Methods 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
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 description 1
- 150000007524 organic acids Chemical class 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 239000012188 paraffin wax Substances 0.000 description 1
- 150000003013 phosphoric acid derivatives Chemical class 0.000 description 1
- 150000003014 phosphoric acid esters Chemical class 0.000 description 1
- 239000011574 phosphorus Substances 0.000 description 1
- 229910052698 phosphorus Inorganic materials 0.000 description 1
- 238000006116 polymerization reaction Methods 0.000 description 1
- 239000001205 polyphosphate Substances 0.000 description 1
- 235000011176 polyphosphates Nutrition 0.000 description 1
- 229910000027 potassium carbonate Inorganic materials 0.000 description 1
- 229910001414 potassium ion Inorganic materials 0.000 description 1
- 230000005855 radiation Effects 0.000 description 1
- 230000015227 regulation of liquid surface tension Effects 0.000 description 1
- 239000011347 resin Substances 0.000 description 1
- 229920005989 resin Polymers 0.000 description 1
- 238000007127 saponification reaction Methods 0.000 description 1
- 229910000275 saponite Inorganic materials 0.000 description 1
- 229910000276 sauconite Inorganic materials 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
- 229910001415 sodium ion Inorganic materials 0.000 description 1
- 159000000000 sodium salts Chemical class 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
- 239000000126 substance Substances 0.000 description 1
- 230000001180 sulfating effect Effects 0.000 description 1
- QAOWNCQODCNURD-UHFFFAOYSA-N sulfuric acid Substances OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 1
- 150000003467 sulfuric acid derivatives Chemical class 0.000 description 1
- 239000000454 talc Substances 0.000 description 1
- 229910052623 talc Inorganic materials 0.000 description 1
- 238000004448 titration Methods 0.000 description 1
- QQOWHRYOXYEMTL-UHFFFAOYSA-N triazin-4-amine Chemical class 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
- 239000010455 vermiculite Substances 0.000 description 1
- 229910052902 vermiculite Inorganic materials 0.000 description 1
- 235000019354 vermiculite Nutrition 0.000 description 1
- 229910009112 xH2O Inorganic materials 0.000 description 1
- 239000008096 xylene Chemical class 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
- 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
- C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
- C11D1/00—Detergent compositions based essentially on surface-active compounds; Use of these compounds as a detergent
- C11D1/38—Cationic compounds
- C11D1/65—Mixtures of anionic with cationic compounds
-
- C—CHEMISTRY; METALLURGY
- C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
- C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
- 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
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- C—CHEMISTRY; METALLURGY
- C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
- C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
- C11D11/00—Special methods for preparing compositions containing mixtures of detergents
- C11D11/02—Preparation in the form of powder by spray drying
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- C—CHEMISTRY; METALLURGY
- C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
- C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
- C11D1/00—Detergent compositions based essentially on surface-active compounds; Use of these compounds as a detergent
- C11D1/02—Anionic compounds
- C11D1/12—Sulfonic acids or sulfuric acid esters; Salts thereof
- C11D1/14—Sulfonic acids or sulfuric acid esters; Salts thereof derived from aliphatic hydrocarbons or mono-alcohols
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- C—CHEMISTRY; METALLURGY
- C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
- C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
- C11D1/00—Detergent compositions based essentially on surface-active compounds; Use of these compounds as a detergent
- C11D1/02—Anionic compounds
- C11D1/12—Sulfonic acids or sulfuric acid esters; Salts thereof
- C11D1/29—Sulfates of polyoxyalkylene ethers
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- C—CHEMISTRY; METALLURGY
- C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
- C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
- C11D1/00—Detergent compositions based essentially on surface-active compounds; Use of these compounds as a detergent
- C11D1/38—Cationic compounds
- C11D1/62—Quaternary ammonium compounds
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Abstract
The present invention concerns a granular detergent composition or composition comprising anionic surfactant, at least 20 % by weight of water-soluble cationic surfactant, and less than 10 % by weight of anionic polymer wherein the molar ratio of anionic surfactant to cationic surfactant is less than 1:1, preferably less than 0.5:1. Another aspect of the present invention is a process for making the composition or component comprising the steps of: (i) mixing an aqueous solution comprising water-soluble cationic surfactant, anionic surfactant, and less than 10 % by weight of anionic polymer, (ii) drying the mixture to form a concentrated solution having a solids level of at least 50 % by weight, and (iii) granulating the concentrated solution; wherein the cationic surfactant is at a level of at least 20 % by weight of the composition or component and the molar ratio of anionic surfactant to cationic surfactant is less than 1:1.
Description
CA 02206326 1997-0~-28 O96/17042 PCT~S95/15548 DETERGENT COMPOSITIONS COMPRISING CATIONIC SURFACTANT AND
PROCESS FOR MAKING THE COMPOSITION
The invention relates to granular detergent compositions comprising cationic surfactant and anionic surfactant.
Water-soluble cationic surfactants are commercially available as aqueous solutions, typically up to 35% or 40%
active (by weight). However any attempts to granulate these aqueous solutions result in granular components having low cationic surfactant content.
EP-A 000 225, published on l0th January 1979, discloses compositions comprising water-soluble cationic surfactant and anionic surfactant. The surfactants are combined together with other detergent ingredients, such as builders, in a crutcher mix and spray-dried. It is an CA 02206326 1997-0~-28 W O 96/17042 PCTrUS95/15548 essential feature that there is a molar excess of anionic surfactant over cationic surfactant. The examples disclose up to a maximum of about 8% by weight of cationic surfactant in the spray dried component.
Attempts to increase cationic surfactant content of granular compositions by first concentrating the aqueous solution have proved very difficult because viscous gel phases of concentrated cationic surfactant make further processing extremely difficult on a commercial scale.
The present invention aims to provide granular detergent components or compositions having a higher level of water-soluble cationic surfactant than prior art components.
This is achieved by mixing small amounts of anionic surfactant with the aqueous solution of the cationic surfactant, and subsequently drying and granulating, either simultaneously or sequentially. The addition of the anionic surfactant permit more concentrated cationic solutions to be processed without entering a viscous gel phase.
Consequently more concentrated granular surfactant components or compositions can be produced.
CA 02206326 1997-0~-28 W O96/17042 PCTrUSg5/15548 Summary of the Invention The present invention concerns a granular detergent composition or component comprising anionic surfactant, at least 20g6 by weight of water-soluble cationic surfactant, and less than 10% by weight of anionic polymer wherein the molar ratio of anionic surfactant to cationic surfactant is less than 1:1, preferably less than 0.5:1.
The granular detergent composition or component preferably comprises the cationic surfactant at a level of at least 30% by weight of the composition or component, and the anionic surfactant at a level of from 1% to 20% by weight the composition or component.
Optionally the granular detergent composition or component further comprises from 10-~6 to 69% by weight of a detergent builder selected from the group consisting of aluminosilicate, silicate, carbonate, citrate, phosphate or mixtures thereof.
A highly preferred granular detergent composition or component is substantially free of anionic polymer, and comprises:
(a) from 35% to 50% by weight of water-soluble cationic surfactant;
(b) from 1% to 5% by weight of anionic surfactant; and (c) from 40% to 60% by weight of sodium CA 02206326 1997-0~-28 2 PCT~S95/15548 aluminosilicate.
Another aspect of the present invention is a process for making the composition or component comprising the steps of (i) mixing an aqueous solution comprising water-soluble cationic surfactant, anionic surfactant, and less than 10%
by weight of anionic polymer;
(ii) drying the mixture to form a concentrated solution having a solids level of at least 50% by weight, and (iii) granulating the concentrated solution;
wherein the cationic surfactant is at a level of at least 20% by weight of the composition or component and the molar ratio of anionic surfactant to cationic surfactant is less than 1:1.
Optionally a suds suppressing agent is added to the mixing step (i).
The drying step may be carried out by means of an evaporation step, and that the granulating step is subsequently carried out by mixing the concentrated solution with a detergent builder selected from the group consisting of aluminosilicate, silicate, carbonate, citrate, phosphate or mixtures thereof.
CA 02206326 1997-0~-28 W O 96/17042 PCTrUS95/15548 Alternatively the drying and granulating steps may be carried out simultaneously, preferably by means of spray drying.
Detailed Description of the Invention The cationic surfactant component of the composition is water-soluble. By water solubility we refer in this context to the solubility of cationic surfactant in monomeric form, the limit of solubility being determined by the onset of micellisation and measured in terms of the critical micelle concentration (CMC). The cationic surfactant should thus have a CMC for the pure material greater than about 200ppm and preferably greater than about 500ppm, specified at 30~C
and in distilled water (Critical Micelle Concentrations of Aqueous Surfactant Systems, P. Mukerjee and K.J. Mysels, NSRDS-NBS, (1971)).
Useful cationic surfactants include water-soluble quaternary ammonium compounds of the form R1R2R3R4N+X-, wherein R1 is alkyl having from 10 to 20, preferably from 12-18 carbon atoms, and R2, R3 and R4 are each C1 to C7 alkyl, or hydroxyalkyl, preferably methyl; X~ is an anion, e.g. chloride. Examples of such quaternary ammonium compounds include C12_14 alkyl trimethyl ammonium chloride, C12_14 alkyl dimethyl ethoxy ammonium chloride and cocalkyl CA 02206326 1997-0~-28 W O96tl7042 PCTAUS95/15548 trimethyl ammonium methosulfate. Other useful cationic surfactants are described in US Pat No. 4,222,905, Cockrell, issued Sept 16, 1990 and in US Pat No 4,239,659, Murphy, issued Dec. 16, 1980.
Another group of useful cationic compounds are the polyammonium salts of the general formula :
R3 N+ ~CH2)n N+ R4 , Z
- m wherein R3 is selected from C8 to C20 alkyl, alkenyl and alkaryl groups; each R4 is C1-C4 alkyl; n is from 1 to 6;
and m is from 1 to 3 .
A specific example of a material in this group is :
fH3 Tallow N+ (CH2)3 N+ (CH3)3,(cH3cO2 )2 A further preferred type of cationic component, has the formula :
Rl R2 - (Z1)a ~ (R3)n - z2 - (CH2)m - I+ - R1 X~
CA 02206326 1997-0~-28 W O96/17042 PCTrUS95/lS548 wherein R1 is C1 to C4 alkyl; R2 is Cs to C30 straight or branched chain alkyl or alkenyl, alkyl benzene, or Rl X~ R1 - 1N - (CH2)s - ; wherein s is from 0 to 5, Rl , R3 is C1 to C20 alkyl or alkenyl; a is 0 or 1; n is 0 or l m is from 1 to 5; Z- and Z2 are each selected from the group consisting of :
O O O ) H H O O H H O
-C-O, O-C-, -O-, -O-C-O-, - -N-, -N-C, -O-C-N, -N-C-O-, and wherein at least one of said groups is selected from the group consisting of ester, reverse ester, amide and reverse amide; and X is an anion which makes the compound water-soluble, preferably selected from the group consisting of amide, methyl sulfate, hydroxide, and nitrate preferably chloride, bromide or iodine.
In addition to the advantages of the other cationic surfactants disclosed herein, this particular cationic component is evironmentally desirable, since it is biodegradable, both in terms of its long alkyl chain and its nitrogen containing segment.
Choline esters :
CA 02206326 1997-0~-28 W O96/17042 PCT~US95/15548 Preferred choline ester derivatives having the following formula :
Il I
R1 - C - O - CH2CH2 - N+ - CH3X-I
wherein R is a Cs to C30 straight chain or branched chain alkyl or alkenyl, group and X is an anion, which makes the compound at least water-dispersible, preferably selected from the group consisting of halide, methyl sulfate, sulfate, and nitrate, preferably methyl sulfate, chloride, bromide or iodide~
as well as those wherein the ester linkage in the above formula is replaced with a reverse ester, amide or reverse amide linkage.
Particularly preferred examples of this type of cationic surfactant include stearoyl choline ester quaternary ammonium halides (Rl=C17 alkyl), palmitoyl choline ester quaternary ammonium halides (R1=C1s alkyl), mystiroyl choline ester quaternary ammonium halides (R1=C13 alkyl), lauroyl choline ester ammonium halides (R1=C11 alkyl), as well as coconut and tallow choline ester quaternary CA 02206326 1997-0~-28 W O96/17042 PCTrUS95/15548 ammonium halides (R1=C1s_C17 alkyl and C1g_C13 alkyl, respectively).
Additional preferred cationic components of the choline ester variety are given by the structural formulas below, wherein p may be from 0 to 20.
Il 11 1 R1-0-C-(CH2)-C-0-CH2CH2-N+-CH3X-I
CH3 ~ ~ CH3 X-CH3-N-CH2-CH2-0-C-(CH2)-C-0-CH2-CH2-N+-CH3X+
The preferred choline-derivative cationic substances, discussed above, may be prepared by the direct esterification of a fatty acid of the desired chain length with dimethylaminoethanol, in the presence of an acid CA 02206326 1997-0~-28 W O96/17042 PCTrUS95/15548 catalyst. The reaction product is then quaternized with a methyl halide, forming the desired cationic material.
The choline-derived cationic materials may also be prepared by the direct esterification of a long chain fatty acid of the desired chain length together with 2-haloethanol, in the presence of an acid catalyst material. The reaction product is then used to quaternize.
Trimethylamine, forming the desired cationic component.
Other suitable choline esters for use herein have the formula:
Il I
Rl -O (CH2CH20) y- (CH2) -C-O-CH2-CH2-N+-CH3X-I
Il I
Rl-O (CH2CH20) y-c-cH2-N+-cH3x-I
CH3 ~ CH3 Rl-O-(CHCH20)y-c-cH2-N+-cH3x+
I
CA 02206326 1997-0~-28 WO96/17042 PCT~S95/15548 Rl-O(CHCH20)y-(CH2)-C-O-CH2-CH2-N+-CH3X-I
Il I
Rl-O(CH2CH20)y-C-(CH2)-C-O-CH2CH2-N+-CH3X-I
Il I 1 11 1 Rl-O(CH2CH20)y C = C - C - C -O-CH2CH2-N+-CH3X-I
Rl-O(CH2CH2CH2CH20)y C-CH2-N+-CH3X-I
CA 02206326 1997-0~-28 W O 96/17042 PCTrUS95/15548 Il I
Rl-O(CH2CH2CH2CH20)y-(CH2)-C-O-CH2CH2-N+-CH3X-wherein t is 0 or 1, y is from 1 to 20, and R and X are as defined above.
Anionic Surfactant The anionic surfactant component of the present invention include water-soluble salts of the higher fatty acids, i.e., "soaps". This includes alkali metal soaps such as the sodium, potassium, ammonium, and alkylammonium salts of higher fatty acids containing from about 8 to about 24 carbon atoms, and preferably from about 12 to about 18 carbon atoms. 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.
CA 02206326 1997-0~-28 WO96/17042 PCT~S95/15548 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 l0 to about 20 carbon atoms and a sulfonic acid or sulfuric acid ester group. (Included in the term "alkyl" is the alkyl portion of acyl groups.) Examples of this group of synthetic surfactants are the sodium and potassium alkyl sulfates, especially those obtained by sulfating the higher alcohols (Cg-Clg 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. Pat. Nos. 2,220,099 and 2,477,383. Especially valuable are linear straight chain alkyl benzene sulfonates in which the average number of carbon atoms in the alkyl group is from about ll to 13, abbreviated as Cll-C13 LAS.
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 l to l0 carbon atoms in the ester groupi water-soluble salts of 2-acyloxy-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 CA 02206326 1997-0~-28 W O96/17042 PCTrUS95/15548 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 containing from about 12 to 24 carbon atoms; and beta-alkyloxy alkane sulfonates containing from about 1 to 3 carbon atoms in the alkyl group and from about 8 to about 20 carbon atoms in the alkane moiety.
Also considered as anionic surfactants useful in the present invention are hydrotropes such as aryl sulphonates.
Preferred are sodium or potassium salts of benzene, toluene, xylene or cumene sulphonate.
Suds Suppressing Agent A suds suppressing agent is useful in the present invention as a process aid, to control suds at the stage of mixing the cationic surfactant solution with the anionic surfactant.
A wide variety of materials may be used as suds suppressing agents such as monocarboxylic fatty acids and their soluble salts, high molecular weight hydrocarbons such as paraffin, fatty acid esters, fatty acid esters of monovalent alcohols, aliphatic C1-C40 ketones, N-alkoxylated amino triazines, propylene oxide, and monstearyl phosphates and phosphate esters. Another preferred category of suds suppressing agents comprises silicone suds suppressors.
WO96/17042 PCT~S95/15548 This category includes the use of polyorganosiloxane oils, such as polydimethyl siloxane, dispersions or emulsions of polyorganosiloxane oils or resins, and combinations of polyorganosiloxane with silica particles wherein the polyorganosiloxane is chemisorbed or fused onto the silica.
Silicone suds suppressors are well-known in the art and are, for example, disclosed in US-A 4 265 779, issued May 5th 1981. Other silicone suds suppressors are disclosed in US-A 3 455 839 and German Patent Application DE-A 21 24 526.
Powders Many powders are suitable for use in the granulation step of the present process. Preferred powders for use in the process and compositions of the present invention are compatible detergency builder or combination of builders or powder.
The detergent compositions herein can contain crystalline aluminosilicate ion exchange material of the formula Naz[(Alo2)z-(slo2)y]-xH2o wherein z and y are at least about 6, the molar ratio of z to y is from about 1.0 to about 0.4 and z is from about 10 to about 264. Amorphous hydrated aluminosilicate materials useful herein have the empirical formula MZ(zAlO2 YSiO2) CA 02206326 1997-0~-28 W O 96/17042 PCTrUS95/15548 wherein M is sodium, potasslum, 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 CaCO3 hardness per gram of anhydrous aluminosilicate. Hydrated sodium Zeolite A with a particle size of from about l 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 eve~
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 CA 02206326 1997-0~-28 WO96/17042 PCT~S95/15548 CaCO3 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.
CaCO3/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., CA 02206326 1997-0~-28 W O96/17042 PCTrUS95/15548 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, Zeolite P, Zeolite MAP
and Zeolite X. In an especially preferred embodiment, the crystalline aluminosilicate ion exchange material has the formula Na12[(AlO2)12(SiO2)12] xH2O
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 organic 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.
Examples of 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 CA 02206326 1997-0~-28 WO96/17042 PCT~S95/15548 into the granular detergents of the present invention as long as it is chemically compatible with the rest of the agglomerate composition.
Other useful 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 phosphatesj polyphosphates, phosphonates, polyphosphonates, carbonates, silicates, borates, citrates, silicas and polyhyroxysulfonates. Preferred are the alkali metal, especially sodium, salts of the above.
Specific examples of inorganic phosphate builders are sodium and potassium tripolyphosphate, pyrophosphate, polymeric metaphosphate having a degree of polymerization of from about 6 to 21, and orthophosphate. Examples of polyphosphonate builders are the sodium and potassium salts of ethylene diphosphonic acid, the sodium and potassium salts of ethane 1-hydroxy-1,1-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; 3,422,021i 3,422,137;
3,400,176 and 3,400,148, incorporated herein by reference.
Examples of nonphosphorus, inorganic builders are sodium and potassium carbonate, bicarbonate, sesquicarbonate, tetraborate decahydrate, and silicate having a molar ratio CA 02206326 1997-0~-28 W O 96/17042 PCT~US95/15548 of SiO2 to alkali metal oxide of from about 0.5 to about 4.0, preferably from about 1.0 to about 2.4. The compositions made by the process of the present invention does not require excess carbonate for processing, and preferably does not contain over 2~ finely divided calcium carbonate as disclosed in U.S. Pat. No. 4,196,093, Clarke et al., issued Apr.1, 1980, and is preferably free of the latter.
Softening Clay Softening clay is a particularly useful component which may be optionally incorporated into the compositions of the present invention. When used, the clay may be incorporated into the cationic surfactant containing particle of the present invention, however it is preferred that the clay is incorporated into a particle separate from the cationic surfactant. The cationic surfactant containing particles and the clay containing particles may then be mixed together, usually with other particulate components comprising conventional detergent ingredients to give a finished commerial laundry detergent product.
Softening clays may be either unmodified or organically modified. Those clays which are not organically modified can be described as expandable, three-layered clays, i.e., aluminosilicates and-magnesium silicates, having an ion exchange capacity of at least 50 meq/lOOg. of clay and CA 02206326 1997-0~-28 W O96/17042 PCTrUS95/15548 preferabiy at least 60 meq/100 g. of clay. The starting clays for the organically modified clays can be similarly described. The term "expandable" as used to describe clays relates to the ability of the layered clay structure to be swollen, or expanded, on contact with water. The three-layer expandable clays used herein are those materials classified geologically as smectites.
There are two distinct classes of smectite-type clays that can be broadly differentiated on the basis of the numbers of octahedral metal-oxygen arrangements in the central layer for a given number of silicon-oxygen atoms in outer layers. A more complete description of clay minerals is given in "Clay Colloid Chemistry" by H. van Olphen, John Wiley & Sons (Interscience Publishers), New York, 1963.
Chapter 6, especially pages 66-69.
The family of smectite (or montmorillonoid) clays includes the following trioctahedral minerals: talc; hectorite;
saponite; sauconite; vermiculite; and the following dioctahedral minerals: prophyllite; montmorillonite;
volchonskoite and nontronite.
The clays employed in these compositions contain cationic counterions such as protons, sodium ions, potassium ions, calcium ions, and lithium ions. It is customary to distinguish between clays on the basis of one cation predominantly or exclusively absorbed. For example, a sodium clay is one in which the absorbed cation is CA 02206326 1997-0~-28 W096/17042 PCT~S95/15548 predominantly sodium. Such absorbed cations can become involved in exchange reactions with cations present in aqueous solutions. A typical exchange reaction involving a smectite-type clay is expressed by the following equation :
smectite clay (Na~+ + NH40H => smectite clay (NH4)+ + NaOH.
Since in the foregoing equilibrium reaction, an equivalent weight of ammonium ion replaces an equivalent weight of sodium, it is customary to measure cation exchange capacity (sometimes termed "base exchange capacity") in terms of milliequivalents per lOO g. of clay (meq/lOOg). The cation exchange capacity of clays can be measured in several ways, including by electrodialysis, by exchange with ammonium ion followed by titration, or by a methylene blue procedure, all as fully set forth in Grimshaw, "The Chemistry and Physics of Clays", pp. 264-265, Interscience (1971).
The cation exchange capacity of a clay material relates to such factors as the expandable properties of the clay, the charge of the clay (which in turn is determined at least in part by the lattice structure), and the like. The ion exchange capacity of clays varies widely in the range form about 2 meq/lOO g. of kaolinites to about 150 meq/lOO g., and greater, for certain smectite clays.
Preferred smectite-type clays are sodium montmorillonite, potassium montmorillonite, sodium hectorite and potassium W O 96/17042 PCTrUS95/15548 hectorite. The clays used herein have a particle size range of up to about 1 micron.
Any of the clays used herein may be either naturally or synthetically derived.
CA 02206326 1997-0~-28 W O96/17042 PCT~US95/15548 Examples In the following examples Cationic surfactant is C12-14 alkyl dimethyl hydroxyethyl ammonium chloride Sodium (Cl2-14) alkyl ether (3) sulphate is the sodium salt of a C12-14 ethoxylated alcohol having an average of 3 moles of ether per mole.
Suds Suppressing Agent is poly dimethyl siloxane ( 85~o ) and hydrophobic silica (15~o) The following composition was made :
% by weight Cal~onic Surfactant 40 Sodium (C12-14) alkyl sulphate 1.6 Sodium (C12-14) alkyl ether (3) 0.4 sulphate Zeolite A (hydrated) 54 . 9 Suds Suppressing Agent 0.1 Water 3 Example 1 The above composition was prepared by mixing a 40% aqueous solution of the cationic surfactant with a 79% aqueous CA 02206326 1997-0~-28 WO96/17042 PCT~S95/15548 paste of the mixture of anionic surfactants, and with the antifoam. The mixture was then evaporated to form a 60%
cationic surfactant active paste. The paste was fed into a high shear mixer (a Loedige CB~) where it was granulated with the Zeolite A. The resulting granules were further treated in a low shear mixer (a Loedige KM~) and subsequently dried in a fluid bed dryer to a moisture level of 3% (free) water.
Example 2 The above composition was prepared by mixing a 40% aqueous solution of the cationic surfactant with a 79% aqueous paste of the mixture of anionic surfactants. The Zeolite A
was also added to the mixture and a homogeneous crutcher mix formed. The crutcher mix was then spray dried using hot air in a conventional counter-current spray dry tower to give the finished granular composition.
Comparative Example A
A 40~ aqueous solution of the cationic surfactant was fed into a high shear-mixer (Loedige CB~) and agglomerated with a fixed amount of Zeolite A powder. The feed was stopped just before over-agglomeration occurred (the point where the liquid level exceeds the capacity of the powder, CA 02206326 1997-0~-28 W O96/17042 PCT~US95/15548 leading to the formation of an un-processable 'dough'). The resultant wet agglomerate was then dried in a fluid-bed dryer giving a product with the following composition :-% by weight Cationic Surfactant 15 Sodium (C12-14) alkyl sulphate Sodium (C12-14) alkyl ether (3) sulphate Zeolite A (hydrated) 82 Water 3 This particle is not suitable for inclusion in 'compact-type' products due to the low cationic surfactant activity.
Comparative Example B
A 40% aqueous solution OL the cationic surfactant was dried by evaporation to form a 60% cationic surfactant active paste. The paste became a highly viscous gel and no further useful processing was possible.
PROCESS FOR MAKING THE COMPOSITION
The invention relates to granular detergent compositions comprising cationic surfactant and anionic surfactant.
Water-soluble cationic surfactants are commercially available as aqueous solutions, typically up to 35% or 40%
active (by weight). However any attempts to granulate these aqueous solutions result in granular components having low cationic surfactant content.
EP-A 000 225, published on l0th January 1979, discloses compositions comprising water-soluble cationic surfactant and anionic surfactant. The surfactants are combined together with other detergent ingredients, such as builders, in a crutcher mix and spray-dried. It is an CA 02206326 1997-0~-28 W O 96/17042 PCTrUS95/15548 essential feature that there is a molar excess of anionic surfactant over cationic surfactant. The examples disclose up to a maximum of about 8% by weight of cationic surfactant in the spray dried component.
Attempts to increase cationic surfactant content of granular compositions by first concentrating the aqueous solution have proved very difficult because viscous gel phases of concentrated cationic surfactant make further processing extremely difficult on a commercial scale.
The present invention aims to provide granular detergent components or compositions having a higher level of water-soluble cationic surfactant than prior art components.
This is achieved by mixing small amounts of anionic surfactant with the aqueous solution of the cationic surfactant, and subsequently drying and granulating, either simultaneously or sequentially. The addition of the anionic surfactant permit more concentrated cationic solutions to be processed without entering a viscous gel phase.
Consequently more concentrated granular surfactant components or compositions can be produced.
CA 02206326 1997-0~-28 W O96/17042 PCTrUSg5/15548 Summary of the Invention The present invention concerns a granular detergent composition or component comprising anionic surfactant, at least 20g6 by weight of water-soluble cationic surfactant, and less than 10% by weight of anionic polymer wherein the molar ratio of anionic surfactant to cationic surfactant is less than 1:1, preferably less than 0.5:1.
The granular detergent composition or component preferably comprises the cationic surfactant at a level of at least 30% by weight of the composition or component, and the anionic surfactant at a level of from 1% to 20% by weight the composition or component.
Optionally the granular detergent composition or component further comprises from 10-~6 to 69% by weight of a detergent builder selected from the group consisting of aluminosilicate, silicate, carbonate, citrate, phosphate or mixtures thereof.
A highly preferred granular detergent composition or component is substantially free of anionic polymer, and comprises:
(a) from 35% to 50% by weight of water-soluble cationic surfactant;
(b) from 1% to 5% by weight of anionic surfactant; and (c) from 40% to 60% by weight of sodium CA 02206326 1997-0~-28 2 PCT~S95/15548 aluminosilicate.
Another aspect of the present invention is a process for making the composition or component comprising the steps of (i) mixing an aqueous solution comprising water-soluble cationic surfactant, anionic surfactant, and less than 10%
by weight of anionic polymer;
(ii) drying the mixture to form a concentrated solution having a solids level of at least 50% by weight, and (iii) granulating the concentrated solution;
wherein the cationic surfactant is at a level of at least 20% by weight of the composition or component and the molar ratio of anionic surfactant to cationic surfactant is less than 1:1.
Optionally a suds suppressing agent is added to the mixing step (i).
The drying step may be carried out by means of an evaporation step, and that the granulating step is subsequently carried out by mixing the concentrated solution with a detergent builder selected from the group consisting of aluminosilicate, silicate, carbonate, citrate, phosphate or mixtures thereof.
CA 02206326 1997-0~-28 W O 96/17042 PCTrUS95/15548 Alternatively the drying and granulating steps may be carried out simultaneously, preferably by means of spray drying.
Detailed Description of the Invention The cationic surfactant component of the composition is water-soluble. By water solubility we refer in this context to the solubility of cationic surfactant in monomeric form, the limit of solubility being determined by the onset of micellisation and measured in terms of the critical micelle concentration (CMC). The cationic surfactant should thus have a CMC for the pure material greater than about 200ppm and preferably greater than about 500ppm, specified at 30~C
and in distilled water (Critical Micelle Concentrations of Aqueous Surfactant Systems, P. Mukerjee and K.J. Mysels, NSRDS-NBS, (1971)).
Useful cationic surfactants include water-soluble quaternary ammonium compounds of the form R1R2R3R4N+X-, wherein R1 is alkyl having from 10 to 20, preferably from 12-18 carbon atoms, and R2, R3 and R4 are each C1 to C7 alkyl, or hydroxyalkyl, preferably methyl; X~ is an anion, e.g. chloride. Examples of such quaternary ammonium compounds include C12_14 alkyl trimethyl ammonium chloride, C12_14 alkyl dimethyl ethoxy ammonium chloride and cocalkyl CA 02206326 1997-0~-28 W O96tl7042 PCTAUS95/15548 trimethyl ammonium methosulfate. Other useful cationic surfactants are described in US Pat No. 4,222,905, Cockrell, issued Sept 16, 1990 and in US Pat No 4,239,659, Murphy, issued Dec. 16, 1980.
Another group of useful cationic compounds are the polyammonium salts of the general formula :
R3 N+ ~CH2)n N+ R4 , Z
- m wherein R3 is selected from C8 to C20 alkyl, alkenyl and alkaryl groups; each R4 is C1-C4 alkyl; n is from 1 to 6;
and m is from 1 to 3 .
A specific example of a material in this group is :
fH3 Tallow N+ (CH2)3 N+ (CH3)3,(cH3cO2 )2 A further preferred type of cationic component, has the formula :
Rl R2 - (Z1)a ~ (R3)n - z2 - (CH2)m - I+ - R1 X~
CA 02206326 1997-0~-28 W O96/17042 PCTrUS95/lS548 wherein R1 is C1 to C4 alkyl; R2 is Cs to C30 straight or branched chain alkyl or alkenyl, alkyl benzene, or Rl X~ R1 - 1N - (CH2)s - ; wherein s is from 0 to 5, Rl , R3 is C1 to C20 alkyl or alkenyl; a is 0 or 1; n is 0 or l m is from 1 to 5; Z- and Z2 are each selected from the group consisting of :
O O O ) H H O O H H O
-C-O, O-C-, -O-, -O-C-O-, - -N-, -N-C, -O-C-N, -N-C-O-, and wherein at least one of said groups is selected from the group consisting of ester, reverse ester, amide and reverse amide; and X is an anion which makes the compound water-soluble, preferably selected from the group consisting of amide, methyl sulfate, hydroxide, and nitrate preferably chloride, bromide or iodine.
In addition to the advantages of the other cationic surfactants disclosed herein, this particular cationic component is evironmentally desirable, since it is biodegradable, both in terms of its long alkyl chain and its nitrogen containing segment.
Choline esters :
CA 02206326 1997-0~-28 W O96/17042 PCT~US95/15548 Preferred choline ester derivatives having the following formula :
Il I
R1 - C - O - CH2CH2 - N+ - CH3X-I
wherein R is a Cs to C30 straight chain or branched chain alkyl or alkenyl, group and X is an anion, which makes the compound at least water-dispersible, preferably selected from the group consisting of halide, methyl sulfate, sulfate, and nitrate, preferably methyl sulfate, chloride, bromide or iodide~
as well as those wherein the ester linkage in the above formula is replaced with a reverse ester, amide or reverse amide linkage.
Particularly preferred examples of this type of cationic surfactant include stearoyl choline ester quaternary ammonium halides (Rl=C17 alkyl), palmitoyl choline ester quaternary ammonium halides (R1=C1s alkyl), mystiroyl choline ester quaternary ammonium halides (R1=C13 alkyl), lauroyl choline ester ammonium halides (R1=C11 alkyl), as well as coconut and tallow choline ester quaternary CA 02206326 1997-0~-28 W O96/17042 PCTrUS95/15548 ammonium halides (R1=C1s_C17 alkyl and C1g_C13 alkyl, respectively).
Additional preferred cationic components of the choline ester variety are given by the structural formulas below, wherein p may be from 0 to 20.
Il 11 1 R1-0-C-(CH2)-C-0-CH2CH2-N+-CH3X-I
CH3 ~ ~ CH3 X-CH3-N-CH2-CH2-0-C-(CH2)-C-0-CH2-CH2-N+-CH3X+
The preferred choline-derivative cationic substances, discussed above, may be prepared by the direct esterification of a fatty acid of the desired chain length with dimethylaminoethanol, in the presence of an acid CA 02206326 1997-0~-28 W O96/17042 PCTrUS95/15548 catalyst. The reaction product is then quaternized with a methyl halide, forming the desired cationic material.
The choline-derived cationic materials may also be prepared by the direct esterification of a long chain fatty acid of the desired chain length together with 2-haloethanol, in the presence of an acid catalyst material. The reaction product is then used to quaternize.
Trimethylamine, forming the desired cationic component.
Other suitable choline esters for use herein have the formula:
Il I
Rl -O (CH2CH20) y- (CH2) -C-O-CH2-CH2-N+-CH3X-I
Il I
Rl-O (CH2CH20) y-c-cH2-N+-cH3x-I
CH3 ~ CH3 Rl-O-(CHCH20)y-c-cH2-N+-cH3x+
I
CA 02206326 1997-0~-28 WO96/17042 PCT~S95/15548 Rl-O(CHCH20)y-(CH2)-C-O-CH2-CH2-N+-CH3X-I
Il I
Rl-O(CH2CH20)y-C-(CH2)-C-O-CH2CH2-N+-CH3X-I
Il I 1 11 1 Rl-O(CH2CH20)y C = C - C - C -O-CH2CH2-N+-CH3X-I
Rl-O(CH2CH2CH2CH20)y C-CH2-N+-CH3X-I
CA 02206326 1997-0~-28 W O 96/17042 PCTrUS95/15548 Il I
Rl-O(CH2CH2CH2CH20)y-(CH2)-C-O-CH2CH2-N+-CH3X-wherein t is 0 or 1, y is from 1 to 20, and R and X are as defined above.
Anionic Surfactant The anionic surfactant component of the present invention include water-soluble salts of the higher fatty acids, i.e., "soaps". This includes alkali metal soaps such as the sodium, potassium, ammonium, and alkylammonium salts of higher fatty acids containing from about 8 to about 24 carbon atoms, and preferably from about 12 to about 18 carbon atoms. 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.
CA 02206326 1997-0~-28 WO96/17042 PCT~S95/15548 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 l0 to about 20 carbon atoms and a sulfonic acid or sulfuric acid ester group. (Included in the term "alkyl" is the alkyl portion of acyl groups.) Examples of this group of synthetic surfactants are the sodium and potassium alkyl sulfates, especially those obtained by sulfating the higher alcohols (Cg-Clg 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. Pat. Nos. 2,220,099 and 2,477,383. Especially valuable are linear straight chain alkyl benzene sulfonates in which the average number of carbon atoms in the alkyl group is from about ll to 13, abbreviated as Cll-C13 LAS.
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 l to l0 carbon atoms in the ester groupi water-soluble salts of 2-acyloxy-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 CA 02206326 1997-0~-28 W O96/17042 PCTrUS95/15548 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 containing from about 12 to 24 carbon atoms; and beta-alkyloxy alkane sulfonates containing from about 1 to 3 carbon atoms in the alkyl group and from about 8 to about 20 carbon atoms in the alkane moiety.
Also considered as anionic surfactants useful in the present invention are hydrotropes such as aryl sulphonates.
Preferred are sodium or potassium salts of benzene, toluene, xylene or cumene sulphonate.
Suds Suppressing Agent A suds suppressing agent is useful in the present invention as a process aid, to control suds at the stage of mixing the cationic surfactant solution with the anionic surfactant.
A wide variety of materials may be used as suds suppressing agents such as monocarboxylic fatty acids and their soluble salts, high molecular weight hydrocarbons such as paraffin, fatty acid esters, fatty acid esters of monovalent alcohols, aliphatic C1-C40 ketones, N-alkoxylated amino triazines, propylene oxide, and monstearyl phosphates and phosphate esters. Another preferred category of suds suppressing agents comprises silicone suds suppressors.
WO96/17042 PCT~S95/15548 This category includes the use of polyorganosiloxane oils, such as polydimethyl siloxane, dispersions or emulsions of polyorganosiloxane oils or resins, and combinations of polyorganosiloxane with silica particles wherein the polyorganosiloxane is chemisorbed or fused onto the silica.
Silicone suds suppressors are well-known in the art and are, for example, disclosed in US-A 4 265 779, issued May 5th 1981. Other silicone suds suppressors are disclosed in US-A 3 455 839 and German Patent Application DE-A 21 24 526.
Powders Many powders are suitable for use in the granulation step of the present process. Preferred powders for use in the process and compositions of the present invention are compatible detergency builder or combination of builders or powder.
The detergent compositions herein can contain crystalline aluminosilicate ion exchange material of the formula Naz[(Alo2)z-(slo2)y]-xH2o wherein z and y are at least about 6, the molar ratio of z to y is from about 1.0 to about 0.4 and z is from about 10 to about 264. Amorphous hydrated aluminosilicate materials useful herein have the empirical formula MZ(zAlO2 YSiO2) CA 02206326 1997-0~-28 W O 96/17042 PCTrUS95/15548 wherein M is sodium, potasslum, 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 CaCO3 hardness per gram of anhydrous aluminosilicate. Hydrated sodium Zeolite A with a particle size of from about l 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 eve~
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 CA 02206326 1997-0~-28 WO96/17042 PCT~S95/15548 CaCO3 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.
CaCO3/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., CA 02206326 1997-0~-28 W O96/17042 PCTrUS95/15548 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, Zeolite P, Zeolite MAP
and Zeolite X. In an especially preferred embodiment, the crystalline aluminosilicate ion exchange material has the formula Na12[(AlO2)12(SiO2)12] xH2O
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 organic 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.
Examples of 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 CA 02206326 1997-0~-28 WO96/17042 PCT~S95/15548 into the granular detergents of the present invention as long as it is chemically compatible with the rest of the agglomerate composition.
Other useful 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 phosphatesj polyphosphates, phosphonates, polyphosphonates, carbonates, silicates, borates, citrates, silicas and polyhyroxysulfonates. Preferred are the alkali metal, especially sodium, salts of the above.
Specific examples of inorganic phosphate builders are sodium and potassium tripolyphosphate, pyrophosphate, polymeric metaphosphate having a degree of polymerization of from about 6 to 21, and orthophosphate. Examples of polyphosphonate builders are the sodium and potassium salts of ethylene diphosphonic acid, the sodium and potassium salts of ethane 1-hydroxy-1,1-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; 3,422,021i 3,422,137;
3,400,176 and 3,400,148, incorporated herein by reference.
Examples of nonphosphorus, inorganic builders are sodium and potassium carbonate, bicarbonate, sesquicarbonate, tetraborate decahydrate, and silicate having a molar ratio CA 02206326 1997-0~-28 W O 96/17042 PCT~US95/15548 of SiO2 to alkali metal oxide of from about 0.5 to about 4.0, preferably from about 1.0 to about 2.4. The compositions made by the process of the present invention does not require excess carbonate for processing, and preferably does not contain over 2~ finely divided calcium carbonate as disclosed in U.S. Pat. No. 4,196,093, Clarke et al., issued Apr.1, 1980, and is preferably free of the latter.
Softening Clay Softening clay is a particularly useful component which may be optionally incorporated into the compositions of the present invention. When used, the clay may be incorporated into the cationic surfactant containing particle of the present invention, however it is preferred that the clay is incorporated into a particle separate from the cationic surfactant. The cationic surfactant containing particles and the clay containing particles may then be mixed together, usually with other particulate components comprising conventional detergent ingredients to give a finished commerial laundry detergent product.
Softening clays may be either unmodified or organically modified. Those clays which are not organically modified can be described as expandable, three-layered clays, i.e., aluminosilicates and-magnesium silicates, having an ion exchange capacity of at least 50 meq/lOOg. of clay and CA 02206326 1997-0~-28 W O96/17042 PCTrUS95/15548 preferabiy at least 60 meq/100 g. of clay. The starting clays for the organically modified clays can be similarly described. The term "expandable" as used to describe clays relates to the ability of the layered clay structure to be swollen, or expanded, on contact with water. The three-layer expandable clays used herein are those materials classified geologically as smectites.
There are two distinct classes of smectite-type clays that can be broadly differentiated on the basis of the numbers of octahedral metal-oxygen arrangements in the central layer for a given number of silicon-oxygen atoms in outer layers. A more complete description of clay minerals is given in "Clay Colloid Chemistry" by H. van Olphen, John Wiley & Sons (Interscience Publishers), New York, 1963.
Chapter 6, especially pages 66-69.
The family of smectite (or montmorillonoid) clays includes the following trioctahedral minerals: talc; hectorite;
saponite; sauconite; vermiculite; and the following dioctahedral minerals: prophyllite; montmorillonite;
volchonskoite and nontronite.
The clays employed in these compositions contain cationic counterions such as protons, sodium ions, potassium ions, calcium ions, and lithium ions. It is customary to distinguish between clays on the basis of one cation predominantly or exclusively absorbed. For example, a sodium clay is one in which the absorbed cation is CA 02206326 1997-0~-28 W096/17042 PCT~S95/15548 predominantly sodium. Such absorbed cations can become involved in exchange reactions with cations present in aqueous solutions. A typical exchange reaction involving a smectite-type clay is expressed by the following equation :
smectite clay (Na~+ + NH40H => smectite clay (NH4)+ + NaOH.
Since in the foregoing equilibrium reaction, an equivalent weight of ammonium ion replaces an equivalent weight of sodium, it is customary to measure cation exchange capacity (sometimes termed "base exchange capacity") in terms of milliequivalents per lOO g. of clay (meq/lOOg). The cation exchange capacity of clays can be measured in several ways, including by electrodialysis, by exchange with ammonium ion followed by titration, or by a methylene blue procedure, all as fully set forth in Grimshaw, "The Chemistry and Physics of Clays", pp. 264-265, Interscience (1971).
The cation exchange capacity of a clay material relates to such factors as the expandable properties of the clay, the charge of the clay (which in turn is determined at least in part by the lattice structure), and the like. The ion exchange capacity of clays varies widely in the range form about 2 meq/lOO g. of kaolinites to about 150 meq/lOO g., and greater, for certain smectite clays.
Preferred smectite-type clays are sodium montmorillonite, potassium montmorillonite, sodium hectorite and potassium W O 96/17042 PCTrUS95/15548 hectorite. The clays used herein have a particle size range of up to about 1 micron.
Any of the clays used herein may be either naturally or synthetically derived.
CA 02206326 1997-0~-28 W O96/17042 PCT~US95/15548 Examples In the following examples Cationic surfactant is C12-14 alkyl dimethyl hydroxyethyl ammonium chloride Sodium (Cl2-14) alkyl ether (3) sulphate is the sodium salt of a C12-14 ethoxylated alcohol having an average of 3 moles of ether per mole.
Suds Suppressing Agent is poly dimethyl siloxane ( 85~o ) and hydrophobic silica (15~o) The following composition was made :
% by weight Cal~onic Surfactant 40 Sodium (C12-14) alkyl sulphate 1.6 Sodium (C12-14) alkyl ether (3) 0.4 sulphate Zeolite A (hydrated) 54 . 9 Suds Suppressing Agent 0.1 Water 3 Example 1 The above composition was prepared by mixing a 40% aqueous solution of the cationic surfactant with a 79% aqueous CA 02206326 1997-0~-28 WO96/17042 PCT~S95/15548 paste of the mixture of anionic surfactants, and with the antifoam. The mixture was then evaporated to form a 60%
cationic surfactant active paste. The paste was fed into a high shear mixer (a Loedige CB~) where it was granulated with the Zeolite A. The resulting granules were further treated in a low shear mixer (a Loedige KM~) and subsequently dried in a fluid bed dryer to a moisture level of 3% (free) water.
Example 2 The above composition was prepared by mixing a 40% aqueous solution of the cationic surfactant with a 79% aqueous paste of the mixture of anionic surfactants. The Zeolite A
was also added to the mixture and a homogeneous crutcher mix formed. The crutcher mix was then spray dried using hot air in a conventional counter-current spray dry tower to give the finished granular composition.
Comparative Example A
A 40~ aqueous solution of the cationic surfactant was fed into a high shear-mixer (Loedige CB~) and agglomerated with a fixed amount of Zeolite A powder. The feed was stopped just before over-agglomeration occurred (the point where the liquid level exceeds the capacity of the powder, CA 02206326 1997-0~-28 W O96/17042 PCT~US95/15548 leading to the formation of an un-processable 'dough'). The resultant wet agglomerate was then dried in a fluid-bed dryer giving a product with the following composition :-% by weight Cationic Surfactant 15 Sodium (C12-14) alkyl sulphate Sodium (C12-14) alkyl ether (3) sulphate Zeolite A (hydrated) 82 Water 3 This particle is not suitable for inclusion in 'compact-type' products due to the low cationic surfactant activity.
Comparative Example B
A 40% aqueous solution OL the cationic surfactant was dried by evaporation to form a 60% cationic surfactant active paste. The paste became a highly viscous gel and no further useful processing was possible.
Claims (8)
1. A granular detergent composition or component comprising anionic surfactant, water-soluble cationic surfactant, and less than 10% by weight of anionic polymer characterised in that the cationic surfactant is at a level of at least 20% by weight of the composition or component and the molar ratio of anionic surfactant to cationic surfactant is less than 1:1.
2. A granular detergent composition or component according to claim 1 wherein the cationic surfactant is at a level of at least 30% by weight of the composition or component, and the anionic surfactant is at a level of from 1% to 20% by weight the composition or component and the molar ratio of anionic surfactant to cationic surfactant is less than 0.5:1.
3. A granular detergent composition or component according to claim 2, further comprising from 10% to 69% by weight of a detergent builder selected from the group consisting of aluminosilicate, silicate, carbonate, citrate, phosphate or mixtures thereof.
4. A granular detergent composition or component according to claim 3, which is substantially free of anionic polymer, comprising:
(a) from 35% to 50% by weight of water-soluble cationic surfactant;
(b) from 1% to 5% by weight of anionic surfactant; and (c) from 40% to 60% by weight of sodium aluminosilicate.
(a) from 35% to 50% by weight of water-soluble cationic surfactant;
(b) from 1% to 5% by weight of anionic surfactant; and (c) from 40% to 60% by weight of sodium aluminosilicate.
5. A process for making the composition or component comprising the steps of (i) mixing an aqueous solution comprising water-soluble cationic surfactant, anionic surfactant, and less than 10%
by weight of anionic polymer (ii) drying the mixture to form a concentrated solution having a solids level of at least 50% by weight, and (iii) granulating the concentrated solution;
characterised in that the cationic surfactant is at a level of at least 20% by weight of the composition or component and the molar ratio of anionic surfactant to cationic surfactant is less than 1:1.
by weight of anionic polymer (ii) drying the mixture to form a concentrated solution having a solids level of at least 50% by weight, and (iii) granulating the concentrated solution;
characterised in that the cationic surfactant is at a level of at least 20% by weight of the composition or component and the molar ratio of anionic surfactant to cationic surfactant is less than 1:1.
6. A process according to claim 5 wherein a suds suppressing agent is added to the mixing step (i).
7. A process according to either of claims 5 or 6 wherein the drying step is carried out by means of an evaporation step, and that the granulating step is subsequently carried out by mixing the concentrated solution with a detergent builder selected from the group consisting of aluminosilicate, silicate, carbonate, citrate, phosphate or mixtures thereof.
8. A process according to claim 5 wherein the drying and granulating steps are carried out simultaneously, preferably by means of spray drying.
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| 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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| CA2206326A1 true CA2206326A1 (en) | 1996-06-06 |
Family
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| CA002206326A Abandoned CA2206326A1 (en) | 1994-12-02 | 1995-11-30 | Detergent compositions comprising cationic surfactant and process for making the composition |
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| Country | Link |
|---|---|
| EP (1) | EP0714976B2 (en) |
| JP (1) | JPH10511713A (en) |
| CN (1) | CN1174566A (en) |
| AT (1) | ATE193051T1 (en) |
| AU (1) | AU4371496A (en) |
| BR (1) | BR9509843A (en) |
| CA (1) | CA2206326A1 (en) |
| DE (1) | DE69424551T3 (en) |
| MA (1) | MA23734A1 (en) |
| MX (1) | MX9704078A (en) |
| TR (1) | TR199501509A2 (en) |
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| DE19721885A1 (en) † | 1997-05-26 | 1998-12-03 | Henkel Kgaa | Process for the production of granules containing cationic surfactants |
| 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 |
| GB0009877D0 (en) | 2000-04-20 | 2000-06-07 | Unilever Plc | Granular detergent component and process for its preparation |
| DE102004018751A1 (en) * | 2004-04-17 | 2005-11-03 | Clariant Gmbh | Process for the preparation of quaternary hydroxyalkylammonium granules |
| US20080262129A1 (en) * | 2007-04-06 | 2008-10-23 | Kao Corporation | Process for producing powder |
| WO2011142424A1 (en) * | 2010-05-14 | 2011-11-17 | ユケン工業株式会社 | Aqueous cleaning agent composition |
| EP2821474A1 (en) * | 2011-01-12 | 2015-01-07 | The Procter and Gamble Company | Method for controlling the plasticization of a water soluble film |
| CN115895790A (en) * | 2022-11-30 | 2023-04-04 | 四川科宏达集团有限责任公司 | Anion-cation surfactant compound cleaning agent and preparation method thereof |
Family Cites Families (15)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| ZA755347B (en) † | 1974-09-06 | 1977-04-27 | Colgate Palmolive Co | Fabric softening composition containing molecular sieve zeolite |
| DE2449354B2 (en) * | 1974-10-17 | 1979-08-23 | Basf Ag, 6700 Ludwigshafen | Use of orthophosphoric acid esters as foam suppressors in cationic surfactant formulations |
| US3936537A (en) † | 1974-11-01 | 1976-02-03 | The Procter & Gamble Company | Detergent-compatible fabric softening and antistatic compositions |
| NL7815052A (en) * | 1977-11-17 | 1980-01-31 | Procter & Gamble | Granular detergents for better grease removal. |
| 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 (en) * | 1979-06-29 | 1984-02-24 | 花王株式会社 | cleaning composition |
| ATE10646T1 (en) * | 1979-09-29 | 1984-12-15 | The Procter & Gamble Company | DETERGENT COMPOSITIONS. |
| 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
- 1994-12-02 AT AT94308960T patent/ATE193051T1/en not_active IP Right Cessation
- 1994-12-02 DE DE69424551T patent/DE69424551T3/en not_active Expired - Lifetime
-
1995
- 1995-11-29 TR TR95/01509A patent/TR199501509A2/en unknown
- 1995-11-30 JP JP8519046A patent/JPH10511713A/en active Pending
- 1995-11-30 MX MX9704078A patent/MX9704078A/en unknown
- 1995-11-30 WO PCT/US1995/015548 patent/WO1996017042A1/en not_active Application Discontinuation
- 1995-11-30 CN CN95197503.XA patent/CN1174566A/en active Pending
- 1995-11-30 CA CA002206326A patent/CA2206326A1/en not_active Abandoned
- 1995-11-30 BR BR9509843A patent/BR9509843A/en not_active Application Discontinuation
- 1995-11-30 AU AU43714/96A patent/AU4371496A/en not_active Abandoned
- 1995-12-01 ZA ZA9510227A patent/ZA9510227B/en unknown
- 1995-12-01 MA MA24083A patent/MA23734A1/en unknown
Also Published As
| Publication number | Publication date |
|---|---|
| CN1174566A (en) | 1998-02-25 |
| DE69424551T3 (en) | 2005-12-29 |
| EP0714976B1 (en) | 2000-05-17 |
| MX9704078A (en) | 1997-08-30 |
| DE69424551T2 (en) | 2001-01-18 |
| AU4371496A (en) | 1996-06-19 |
| EP0714976A1 (en) | 1996-06-05 |
| MA23734A1 (en) | 1996-07-01 |
| JPH10511713A (en) | 1998-11-10 |
| TR199501509A2 (en) | 1996-07-21 |
| WO1996017042A1 (en) | 1996-06-06 |
| BR9509843A (en) | 1997-11-25 |
| DE69424551D1 (en) | 2000-06-21 |
| ATE193051T1 (en) | 2000-06-15 |
| EP0714976B2 (en) | 2005-03-23 |
| ZA9510227B (en) | 1996-06-12 |
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Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| EEER | Examination request | ||
| FZDE | Discontinued |