CA1039608A - Pourable washing compositions containing aluminosilicates and non-ionics and method for their production - Google Patents
Pourable washing compositions containing aluminosilicates and non-ionics and method for their productionInfo
- Publication number
- CA1039608A CA1039608A CA220,615A CA220615A CA1039608A CA 1039608 A CA1039608 A CA 1039608A CA 220615 A CA220615 A CA 220615A CA 1039608 A CA1039608 A CA 1039608A
- Authority
- CA
- Canada
- Prior art keywords
- weight
- composition
- component
- premix
- powder
- 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.)
- Expired
Links
- 239000000203 mixture Substances 0.000 title claims abstract description 73
- 238000005406 washing Methods 0.000 title claims abstract description 25
- 238000000034 method Methods 0.000 title claims abstract description 12
- 238000004519 manufacturing process Methods 0.000 title claims abstract description 11
- 229910000323 aluminium silicate Inorganic materials 0.000 title claims description 31
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims abstract description 50
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 43
- 150000001875 compounds Chemical class 0.000 claims abstract description 43
- 239000000843 powder Substances 0.000 claims abstract description 43
- 229910001868 water Inorganic materials 0.000 claims abstract description 42
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 37
- -1 silicate com-pounds Chemical class 0.000 claims abstract description 36
- 239000000377 silicon dioxide Substances 0.000 claims abstract description 24
- 239000013543 active substance Substances 0.000 claims abstract description 18
- 238000001035 drying Methods 0.000 claims abstract description 18
- 229910052681 coesite Inorganic materials 0.000 claims abstract description 16
- 229910052906 cristobalite Inorganic materials 0.000 claims abstract description 16
- 229910052682 stishovite Inorganic materials 0.000 claims abstract description 16
- 229910052905 tridymite Inorganic materials 0.000 claims abstract description 16
- 238000004061 bleaching Methods 0.000 claims abstract description 15
- 235000012239 silicon dioxide Nutrition 0.000 claims abstract description 14
- 108010045403 Calcium-Binding Proteins Proteins 0.000 claims abstract description 13
- 102000005701 Calcium-Binding Proteins Human genes 0.000 claims abstract description 13
- 150000001768 cations Chemical class 0.000 claims abstract description 12
- 239000012190 activator Substances 0.000 claims abstract description 10
- 229910052782 aluminium Inorganic materials 0.000 claims abstract description 9
- ZOXJGFHDIHLPTG-UHFFFAOYSA-N Boron Chemical compound [B] ZOXJGFHDIHLPTG-UHFFFAOYSA-N 0.000 claims abstract description 8
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims abstract description 8
- 229910052796 boron Inorganic materials 0.000 claims abstract description 8
- 150000004760 silicates Chemical class 0.000 claims abstract description 3
- 239000000306 component Substances 0.000 claims description 80
- 150000003839 salts Chemical class 0.000 claims description 15
- 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 claims description 13
- 229910052708 sodium Inorganic materials 0.000 claims description 13
- 239000011734 sodium Substances 0.000 claims description 13
- KKCBUQHMOMHUOY-UHFFFAOYSA-N Na2O Inorganic materials [O-2].[Na+].[Na+] KKCBUQHMOMHUOY-UHFFFAOYSA-N 0.000 claims description 12
- 239000002245 particle Substances 0.000 claims description 11
- 125000000129 anionic group Chemical group 0.000 claims description 10
- 239000013078 crystal Substances 0.000 claims description 9
- HNPSIPDUKPIQMN-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Al]O[Al]=O HNPSIPDUKPIQMN-UHFFFAOYSA-N 0.000 claims description 9
- 239000004094 surface-active agent Substances 0.000 claims description 8
- 238000002156 mixing Methods 0.000 claims description 6
- 239000003760 tallow Substances 0.000 claims description 6
- IAYPIBMASNFSPL-UHFFFAOYSA-N Ethylene oxide Chemical compound C1CO1 IAYPIBMASNFSPL-UHFFFAOYSA-N 0.000 claims description 5
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims description 5
- 229910052593 corundum Inorganic materials 0.000 claims description 5
- 239000007788 liquid Substances 0.000 claims description 5
- 239000011164 primary particle Substances 0.000 claims description 5
- 229910001845 yogo sapphire Inorganic materials 0.000 claims description 5
- 150000002191 fatty alcohols Chemical class 0.000 claims description 4
- 239000003381 stabilizer Substances 0.000 claims description 4
- BHPQYMZQTOCNFJ-UHFFFAOYSA-N Calcium cation Chemical compound [Ca+2] BHPQYMZQTOCNFJ-UHFFFAOYSA-N 0.000 claims description 3
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 claims description 3
- 229910001424 calcium ion Inorganic materials 0.000 claims description 3
- 238000009826 distribution Methods 0.000 claims description 3
- 230000014759 maintenance of location Effects 0.000 claims description 3
- 229910052700 potassium Inorganic materials 0.000 claims description 3
- 239000011591 potassium Substances 0.000 claims description 3
- 239000011163 secondary particle Substances 0.000 claims description 3
- 239000003352 sequestering agent Substances 0.000 claims description 2
- 229910003252 NaBO2 Inorganic materials 0.000 claims 1
- 229910000272 alkali metal oxide Inorganic materials 0.000 claims 1
- 239000004615 ingredient Substances 0.000 claims 1
- NVIFVTYDZMXWGX-UHFFFAOYSA-N sodium metaborate Chemical compound [Na+].[O-]B=O NVIFVTYDZMXWGX-UHFFFAOYSA-N 0.000 claims 1
- 239000012418 sodium perborate tetrahydrate Substances 0.000 claims 1
- IBDSNZLUHYKHQP-UHFFFAOYSA-N sodium;3-oxidodioxaborirane;tetrahydrate Chemical compound O.O.O.O.[Na+].[O-]B1OO1 IBDSNZLUHYKHQP-UHFFFAOYSA-N 0.000 claims 1
- 238000005507 spraying Methods 0.000 claims 1
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 abstract description 17
- 239000011575 calcium Substances 0.000 abstract description 17
- 229910052791 calcium Inorganic materials 0.000 abstract description 17
- 230000008569 process Effects 0.000 abstract description 4
- 239000000047 product Substances 0.000 description 31
- 239000002253 acid Substances 0.000 description 26
- 235000001465 calcium Nutrition 0.000 description 16
- 229960005069 calcium Drugs 0.000 description 16
- 244000228957 Ferula foetida Species 0.000 description 12
- 235000014113 dietary fatty acids Nutrition 0.000 description 12
- 239000000194 fatty acid Substances 0.000 description 12
- 229930195729 fatty acid Natural products 0.000 description 12
- 238000001556 precipitation Methods 0.000 description 10
- 239000000243 solution Substances 0.000 description 10
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 9
- 150000004665 fatty acids Chemical class 0.000 description 9
- 238000002360 preparation method Methods 0.000 description 9
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 8
- 125000004432 carbon atom Chemical group C* 0.000 description 8
- 239000000344 soap Substances 0.000 description 8
- 239000004753 textile Substances 0.000 description 8
- 150000007513 acids Chemical class 0.000 description 7
- 238000002425 crystallisation Methods 0.000 description 7
- 230000003287 optical effect Effects 0.000 description 7
- 239000000725 suspension Substances 0.000 description 7
- 229920002472 Starch Polymers 0.000 description 6
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical class CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 6
- 229910052783 alkali metal Inorganic materials 0.000 description 6
- 150000004645 aluminates Chemical class 0.000 description 6
- 239000007864 aqueous solution Substances 0.000 description 6
- 238000010586 diagram Methods 0.000 description 6
- 235000019698 starch Nutrition 0.000 description 6
- BDHFUVZGWQCTTF-UHFFFAOYSA-M sulfonate Chemical compound [O-]S(=O)=O BDHFUVZGWQCTTF-UHFFFAOYSA-M 0.000 description 6
- 229920002134 Carboxymethyl cellulose Polymers 0.000 description 5
- 102000004190 Enzymes Human genes 0.000 description 5
- 108090000790 Enzymes Proteins 0.000 description 5
- BPQQTUXANYXVAA-UHFFFAOYSA-N Orthosilicate Chemical compound [O-][Si]([O-])([O-])[O-] BPQQTUXANYXVAA-UHFFFAOYSA-N 0.000 description 5
- 239000004952 Polyamide Substances 0.000 description 5
- 238000007792 addition Methods 0.000 description 5
- 125000000217 alkyl group Chemical group 0.000 description 5
- 125000004429 atom Chemical group 0.000 description 5
- 235000010948 carboxy methyl cellulose Nutrition 0.000 description 5
- 230000008025 crystallization Effects 0.000 description 5
- 229940088598 enzyme Drugs 0.000 description 5
- 239000006260 foam Substances 0.000 description 5
- 229920002647 polyamide Polymers 0.000 description 5
- 239000007787 solid Substances 0.000 description 5
- 238000003756 stirring Methods 0.000 description 5
- 239000000126 substance Substances 0.000 description 5
- 108091005804 Peptidases Proteins 0.000 description 4
- 102000035195 Peptidases Human genes 0.000 description 4
- 239000004365 Protease Substances 0.000 description 4
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 description 4
- 125000001931 aliphatic group Chemical group 0.000 description 4
- 229910052799 carbon Inorganic materials 0.000 description 4
- 238000006243 chemical reaction Methods 0.000 description 4
- 230000002209 hydrophobic effect Effects 0.000 description 4
- 239000002689 soil Substances 0.000 description 4
- 239000008107 starch Substances 0.000 description 4
- AKEJUJNQAAGONA-UHFFFAOYSA-N sulfur trioxide Chemical compound O=S(=O)=O AKEJUJNQAAGONA-UHFFFAOYSA-N 0.000 description 4
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical class CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 3
- 108010065511 Amylases Proteins 0.000 description 3
- 102000013142 Amylases Human genes 0.000 description 3
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 3
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 3
- 244000060011 Cocos nucifera Species 0.000 description 3
- 235000013162 Cocos nucifera Nutrition 0.000 description 3
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 3
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 description 3
- 229910019142 PO4 Inorganic materials 0.000 description 3
- 150000001335 aliphatic alkanes Chemical class 0.000 description 3
- 239000003513 alkali Substances 0.000 description 3
- 150000001340 alkali metals Chemical class 0.000 description 3
- 235000019418 amylase Nutrition 0.000 description 3
- 229940025131 amylases Drugs 0.000 description 3
- 238000004380 ashing Methods 0.000 description 3
- 230000015572 biosynthetic process Effects 0.000 description 3
- 125000005587 carbonate group Chemical group 0.000 description 3
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 description 3
- 239000008367 deionised water Substances 0.000 description 3
- 229910021641 deionized water Inorganic materials 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 150000002148 esters Chemical class 0.000 description 3
- 238000010438 heat treatment Methods 0.000 description 3
- 150000002500 ions Chemical class 0.000 description 3
- 239000011777 magnesium Substances 0.000 description 3
- 229910052749 magnesium Inorganic materials 0.000 description 3
- 239000000155 melt Substances 0.000 description 3
- 150000007530 organic bases Chemical class 0.000 description 3
- 239000010452 phosphate Substances 0.000 description 3
- NTHWMYGWWRZVTN-UHFFFAOYSA-N sodium silicate Chemical compound [Na+].[Na+].[O-][Si]([O-])=O NTHWMYGWWRZVTN-UHFFFAOYSA-N 0.000 description 3
- 239000000758 substrate Substances 0.000 description 3
- ALSTYHKOOCGGFT-KTKRTIGZSA-N (9Z)-octadecen-1-ol Chemical compound CCCCCCCC\C=C/CCCCCCCCO ALSTYHKOOCGGFT-KTKRTIGZSA-N 0.000 description 2
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- BVKZGUZCCUSVTD-UHFFFAOYSA-M Bicarbonate Chemical compound OC([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-M 0.000 description 2
- 239000004215 Carbon black (E152) Substances 0.000 description 2
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 description 2
- 241000518994 Conta Species 0.000 description 2
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 2
- 108090001060 Lipase Proteins 0.000 description 2
- 102000004882 Lipase Human genes 0.000 description 2
- 239000004367 Lipase Substances 0.000 description 2
- 102000004317 Lyases Human genes 0.000 description 2
- 108090000856 Lyases Proteins 0.000 description 2
- 229910000503 Na-aluminosilicate Inorganic materials 0.000 description 2
- 239000004115 Sodium Silicate Substances 0.000 description 2
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 2
- 239000004902 Softening Agent Substances 0.000 description 2
- 238000002441 X-ray diffraction Methods 0.000 description 2
- 150000003973 alkyl amines Chemical class 0.000 description 2
- 239000007900 aqueous suspension Substances 0.000 description 2
- 238000000889 atomisation Methods 0.000 description 2
- 230000008901 benefit Effects 0.000 description 2
- 239000007795 chemical reaction product Substances 0.000 description 2
- 239000000460 chlorine Substances 0.000 description 2
- 239000003599 detergent Substances 0.000 description 2
- 229940079919 digestives enzyme preparation Drugs 0.000 description 2
- 238000007046 ethoxylation reaction Methods 0.000 description 2
- NNYBQONXHNTVIJ-UHFFFAOYSA-N etodolac Chemical compound C1COC(CC)(CC(O)=O)C2=C1C(C=CC=C1CC)=C1N2 NNYBQONXHNTVIJ-UHFFFAOYSA-N 0.000 description 2
- 239000000835 fiber Substances 0.000 description 2
- 238000001914 filtration Methods 0.000 description 2
- 229930195733 hydrocarbon Natural products 0.000 description 2
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 2
- 230000006872 improvement Effects 0.000 description 2
- 235000019421 lipase Nutrition 0.000 description 2
- 229940063718 lodine Drugs 0.000 description 2
- 238000002844 melting Methods 0.000 description 2
- 230000008018 melting Effects 0.000 description 2
- 230000007935 neutral effect Effects 0.000 description 2
- 229940055577 oleyl alcohol Drugs 0.000 description 2
- XMLQWXUVTXCDDL-UHFFFAOYSA-N oleyl alcohol Natural products CCCCCCC=CCCCCCCCCCCO XMLQWXUVTXCDDL-UHFFFAOYSA-N 0.000 description 2
- 235000011837 pasties Nutrition 0.000 description 2
- 235000012217 sodium aluminium silicate Nutrition 0.000 description 2
- 229960001922 sodium perborate Drugs 0.000 description 2
- 229910052911 sodium silicate Inorganic materials 0.000 description 2
- 235000019832 sodium triphosphate Nutrition 0.000 description 2
- YKLJGMBLPUQQOI-UHFFFAOYSA-M sodium;oxidooxy(oxo)borane Chemical compound [Na+].[O-]OB=O YKLJGMBLPUQQOI-UHFFFAOYSA-M 0.000 description 2
- UNXRWKVEANCORM-UHFFFAOYSA-I triphosphate(5-) Chemical compound [O-]P([O-])(=O)OP([O-])(=O)OP([O-])([O-])=O UNXRWKVEANCORM-UHFFFAOYSA-I 0.000 description 2
- FBOUIAKEJMZPQG-AWNIVKPZSA-N (1E)-1-(2,4-dichlorophenyl)-4,4-dimethyl-2-(1,2,4-triazol-1-yl)pent-1-en-3-ol Chemical compound C1=NC=NN1/C(C(O)C(C)(C)C)=C/C1=CC=C(Cl)C=C1Cl FBOUIAKEJMZPQG-AWNIVKPZSA-N 0.000 description 1
- JIRHAGAOHOYLNO-UHFFFAOYSA-N (3-cyclopentyloxy-4-methoxyphenyl)methanol Chemical compound COC1=CC=C(CO)C=C1OC1CCCC1 JIRHAGAOHOYLNO-UHFFFAOYSA-N 0.000 description 1
- MOOUTZQHJHBHLT-UHFFFAOYSA-N 1-[2-[2-(1h-benzimidazol-2-yl)ethenyl]-1h-benzimidazol-4-yl]ethanol Chemical group C1=CC=C2NC(C=CC3=NC=4C=CC=C(C=4N3)C(O)C)=NC2=C1 MOOUTZQHJHBHLT-UHFFFAOYSA-N 0.000 description 1
- ZMPRRFPMMJQXPP-UHFFFAOYSA-N 2-sulfobenzoic acid Chemical compound OC(=O)C1=CC=CC=C1S(O)(=O)=O ZMPRRFPMMJQXPP-UHFFFAOYSA-N 0.000 description 1
- QWZHDKGQKYEBKK-UHFFFAOYSA-N 3-aminochromen-2-one Chemical class C1=CC=C2OC(=O)C(N)=CC2=C1 QWZHDKGQKYEBKK-UHFFFAOYSA-N 0.000 description 1
- REJHVSOVQBJEBF-OWOJBTEDSA-N 5-azaniumyl-2-[(e)-2-(4-azaniumyl-2-sulfonatophenyl)ethenyl]benzenesulfonate Chemical class OS(=O)(=O)C1=CC(N)=CC=C1\C=C\C1=CC=C(N)C=C1S(O)(=O)=O REJHVSOVQBJEBF-OWOJBTEDSA-N 0.000 description 1
- VKRZNAWSCAUDRQ-BQYQJAHWSA-N 5-methyl-2-[(e)-2-(5-methyl-1,3-benzoxazol-2-yl)ethenyl]-1,3-benzoxazole Chemical group CC1=CC=C2OC(/C=C/C=3OC4=CC=C(C=C4N=3)C)=NC2=C1 VKRZNAWSCAUDRQ-BQYQJAHWSA-N 0.000 description 1
- GZEYLLPOQRZUDF-UHFFFAOYSA-N 7-(dimethylamino)-4-methylchromen-2-one Chemical compound CC1=CC(=O)OC2=CC(N(C)C)=CC=C21 GZEYLLPOQRZUDF-UHFFFAOYSA-N 0.000 description 1
- ZCYVEMRRCGMTRW-UHFFFAOYSA-N 7553-56-2 Chemical compound [I] ZCYVEMRRCGMTRW-UHFFFAOYSA-N 0.000 description 1
- 101150034533 ATIC gene Proteins 0.000 description 1
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- 125000000738 acetamido group Chemical group [H]C([H])([H])C(=O)N([H])[*] 0.000 description 1
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- 125000004450 alkenylene group Chemical group 0.000 description 1
- 150000004996 alkyl benzenes Chemical class 0.000 description 1
- 125000005037 alkyl phenyl group Chemical group 0.000 description 1
- 125000002947 alkylene group Chemical group 0.000 description 1
- 229940037003 alum Drugs 0.000 description 1
- AZDRQVAHHNSJOQ-UHFFFAOYSA-N alumane Chemical compound [AlH3] AZDRQVAHHNSJOQ-UHFFFAOYSA-N 0.000 description 1
- WNROFYMDJYEPJX-UHFFFAOYSA-K aluminium hydroxide Chemical compound [OH-].[OH-].[OH-].[Al+3] WNROFYMDJYEPJX-UHFFFAOYSA-K 0.000 description 1
- 229910021502 aluminium hydroxide Inorganic materials 0.000 description 1
- 150000001408 amides Chemical class 0.000 description 1
- 150000001412 amines Chemical class 0.000 description 1
- 125000004397 aminosulfonyl group Chemical group NS(=O)(=O)* 0.000 description 1
- XKMRRTOUMJRJIA-UHFFFAOYSA-N ammonia nh3 Chemical compound N.N XKMRRTOUMJRJIA-UHFFFAOYSA-N 0.000 description 1
- 150000003863 ammonium salts Chemical class 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 239000002585 base Substances 0.000 description 1
- SRSXLGNVWSONIS-UHFFFAOYSA-N benzenesulfonic acid Chemical class OS(=O)(=O)C1=CC=CC=C1 SRSXLGNVWSONIS-UHFFFAOYSA-N 0.000 description 1
- 229940092714 benzenesulfonic acid Drugs 0.000 description 1
- 239000004305 biphenyl Substances 0.000 description 1
- 150000001642 boronic acid derivatives Chemical class 0.000 description 1
- 239000001110 calcium chloride Substances 0.000 description 1
- 235000011148 calcium chloride Nutrition 0.000 description 1
- 229910001628 calcium chloride Inorganic materials 0.000 description 1
- 229940003871 calcium ion Drugs 0.000 description 1
- 239000004202 carbamide Substances 0.000 description 1
- 108010089934 carbohydrase Proteins 0.000 description 1
- 150000001721 carbon Chemical group 0.000 description 1
- 239000001768 carboxy methyl cellulose Substances 0.000 description 1
- 150000007942 carboxylates Chemical class 0.000 description 1
- 150000001735 carboxylic acids Chemical class 0.000 description 1
- 239000008112 carboxymethyl-cellulose Substances 0.000 description 1
- 239000000969 carrier Substances 0.000 description 1
- 239000001913 cellulose Substances 0.000 description 1
- 229920002678 cellulose Polymers 0.000 description 1
- 229910052801 chlorine Inorganic materials 0.000 description 1
- 238000004140 cleaning Methods 0.000 description 1
- 239000012459 cleaning agent Substances 0.000 description 1
- 239000000084 colloidal system Substances 0.000 description 1
- 239000013065 commercial product Substances 0.000 description 1
- 239000000470 constituent Substances 0.000 description 1
- 125000005265 dialkylamine group Chemical group 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
- 239000000428 dust Substances 0.000 description 1
- 239000000975 dye Substances 0.000 description 1
- 238000002003 electron diffraction Methods 0.000 description 1
- 125000004494 ethyl ester group Chemical group 0.000 description 1
- 229940093476 ethylene glycol Drugs 0.000 description 1
- MJEMIOXXNCZZFK-UHFFFAOYSA-N ethylone Chemical compound CCNC(C)C(=O)C1=CC=C2OCOC2=C1 MJEMIOXXNCZZFK-UHFFFAOYSA-N 0.000 description 1
- JEIPFZHSYJVQDO-UHFFFAOYSA-N ferric oxide Chemical compound O=[Fe]O[Fe]=O JEIPFZHSYJVQDO-UHFFFAOYSA-N 0.000 description 1
- 239000000945 filler Substances 0.000 description 1
- 239000012065 filter cake Substances 0.000 description 1
- 239000000706 filtrate Substances 0.000 description 1
- 238000005187 foaming Methods 0.000 description 1
- 125000002485 formyl group Chemical class [H]C(*)=O 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 229920000159 gelatin Polymers 0.000 description 1
- 239000008273 gelatin Substances 0.000 description 1
- 235000019322 gelatine Nutrition 0.000 description 1
- 235000011852 gelatine desserts Nutrition 0.000 description 1
- 229910001679 gibbsite Inorganic materials 0.000 description 1
- 239000003292 glue Substances 0.000 description 1
- VPVSTMAPERLKKM-UHFFFAOYSA-N glycoluril Chemical compound N1C(=O)NC2NC(=O)NC21 VPVSTMAPERLKKM-UHFFFAOYSA-N 0.000 description 1
- 239000008187 granular material Substances 0.000 description 1
- 238000005469 granulation Methods 0.000 description 1
- 230000003179 granulation Effects 0.000 description 1
- 125000005842 heteroatom Chemical group 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 125000004435 hydrogen atom Chemical class [H]* 0.000 description 1
- 230000007062 hydrolysis Effects 0.000 description 1
- 238000006460 hydrolysis reaction Methods 0.000 description 1
- 230000003301 hydrolyzing effect Effects 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-M hydroxide Chemical compound [OH-] XLYOFNOQVPJJNP-UHFFFAOYSA-M 0.000 description 1
- 239000003112 inhibitor Substances 0.000 description 1
- 230000005764 inhibitory process Effects 0.000 description 1
- 229910052740 iodine Inorganic materials 0.000 description 1
- 239000011630 iodine Substances 0.000 description 1
- 150000003903 lactic acid esters Chemical class 0.000 description 1
- 229910052744 lithium Inorganic materials 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 125000001160 methoxycarbonyl group Chemical group [H]C([H])([H])OC(*)=O 0.000 description 1
- 150000004702 methyl esters Chemical class 0.000 description 1
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 1
- 125000000250 methylamino group Chemical group [H]N(*)C([H])([H])[H] 0.000 description 1
- 150000005673 monoalkenes Chemical class 0.000 description 1
- 150000004682 monohydrates Chemical class 0.000 description 1
- 125000004573 morpholin-4-yl group Chemical group N1(CCOCC1)* 0.000 description 1
- 238000006386 neutralization reaction Methods 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 239000003921 oil Substances 0.000 description 1
- 125000001117 oleyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])/C([H])=C([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
- 150000002894 organic compounds Chemical class 0.000 description 1
- 150000002926 oxygen Chemical class 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 239000012188 paraffin wax Substances 0.000 description 1
- 239000002304 perfume Substances 0.000 description 1
- 235000014786 phosphorus Nutrition 0.000 description 1
- 229920006149 polyester-amide block copolymer Polymers 0.000 description 1
- 239000001205 polyphosphate Substances 0.000 description 1
- 235000011176 polyphosphates Nutrition 0.000 description 1
- 229920001296 polysiloxane Polymers 0.000 description 1
- 239000001267 polyvinylpyrrolidone Substances 0.000 description 1
- 229920000036 polyvinylpyrrolidone Polymers 0.000 description 1
- 235000013855 polyvinylpyrrolidone Nutrition 0.000 description 1
- 159000000001 potassium salts Chemical class 0.000 description 1
- 235000019353 potassium silicate Nutrition 0.000 description 1
- 230000001376 precipitating effect Effects 0.000 description 1
- 150000003138 primary alcohols Chemical class 0.000 description 1
- 239000001294 propane Substances 0.000 description 1
- QQONPFPTGQHPMA-UHFFFAOYSA-N propylene Natural products CC=C QQONPFPTGQHPMA-UHFFFAOYSA-N 0.000 description 1
- 125000004805 propylene group Chemical group [H]C([H])([H])C([H])([*:1])C([H])([H])[*:2] 0.000 description 1
- NQLVQOSNDJXLKG-UHFFFAOYSA-N prosulfocarb Chemical compound CCCN(CCC)C(=O)SCC1=CC=CC=C1 NQLVQOSNDJXLKG-UHFFFAOYSA-N 0.000 description 1
- 108090000623 proteins and genes Proteins 0.000 description 1
- 125000001453 quaternary ammonium group Chemical group 0.000 description 1
- 230000005855 radiation Effects 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- IOVGROKTTNBUGK-SJCJKPOMSA-N ritodrine Chemical compound N([C@@H](C)[C@H](O)C=1C=CC(O)=CC=1)CCC1=CC=C(O)C=C1 IOVGROKTTNBUGK-SJCJKPOMSA-N 0.000 description 1
- 229920006395 saturated elastomer Polymers 0.000 description 1
- 150000003333 secondary alcohols Chemical class 0.000 description 1
- 238000004062 sedimentation Methods 0.000 description 1
- 239000010865 sewage Substances 0.000 description 1
- 229910052710 silicon Inorganic materials 0.000 description 1
- 239000010703 silicon Substances 0.000 description 1
- 239000010802 sludge Substances 0.000 description 1
- 239000000429 sodium aluminium silicate Substances 0.000 description 1
- URGAHOPLAPQHLN-UHFFFAOYSA-N sodium aluminosilicate Chemical compound [Na+].[Al+3].[O-][Si]([O-])=O.[O-][Si]([O-])=O URGAHOPLAPQHLN-UHFFFAOYSA-N 0.000 description 1
- 239000011780 sodium chloride Substances 0.000 description 1
- 239000001509 sodium citrate Substances 0.000 description 1
- NLJMYIDDQXHKNR-UHFFFAOYSA-K sodium citrate Chemical compound O.O.[Na+].[Na+].[Na+].[O-]C(=O)CC(O)(CC([O-])=O)C([O-])=O NLJMYIDDQXHKNR-UHFFFAOYSA-K 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
- RBWSWDPRDBEWCR-RKJRWTFHSA-N sodium;(2r)-2-[(2r)-3,4-dihydroxy-5-oxo-2h-furan-2-yl]-2-hydroxyethanolate Chemical compound [Na+].[O-]C[C@@H](O)[C@H]1OC(=O)C(O)=C1O RBWSWDPRDBEWCR-RKJRWTFHSA-N 0.000 description 1
- 239000007921 spray Substances 0.000 description 1
- 239000007858 starting material Substances 0.000 description 1
- 125000001424 substituent group Chemical group 0.000 description 1
- 150000003871 sulfonates Chemical class 0.000 description 1
- 238000006277 sulfonation reaction Methods 0.000 description 1
- 150000003460 sulfonic acids Chemical class 0.000 description 1
- 150000003467 sulfuric acid derivatives Chemical class 0.000 description 1
- 239000000375 suspending agent Substances 0.000 description 1
- 239000011975 tartaric acid Substances 0.000 description 1
- 235000002906 tartaric acid Nutrition 0.000 description 1
- VZGDMQKNWNREIO-UHFFFAOYSA-N tetrachloromethane Chemical compound ClC(Cl)(Cl)Cl VZGDMQKNWNREIO-UHFFFAOYSA-N 0.000 description 1
- 150000004685 tetrahydrates Chemical class 0.000 description 1
- 125000000383 tetramethylene group Chemical group [H]C([H])([*:1])C([H])([H])C([H])([H])C([H])([H])[*:2] 0.000 description 1
- 230000009466 transformation Effects 0.000 description 1
- 230000001131 transforming effect Effects 0.000 description 1
- 150000003626 triacylglycerols 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
- C11D11/00—Special methods for preparing compositions containing mixtures of detergents
- C11D11/0082—Special methods for preparing compositions containing mixtures of detergents one or more of the detergent ingredients being in a liquefied state, e.g. slurry, paste or melt, and the process resulting in solid detergent particles such as granules, powders or beads
-
- C—CHEMISTRY; METALLURGY
- C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
- C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
- C11D1/00—Detergent compositions based essentially on surface-active compounds; Use of these compounds as a detergent
- C11D1/66—Non-ionic 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
- C11D11/0088—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 the liquefied ingredients being sprayed or adsorbed onto solid particles
-
- C—CHEMISTRY; METALLURGY
- C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
- C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
- C11D17/00—Detergent materials or soaps characterised by their shape or physical properties
- C11D17/0034—Fixed on a solid conventional detergent ingredient
-
- C—CHEMISTRY; METALLURGY
- C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
- C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
- C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
- C11D3/02—Inorganic compounds ; Elemental compounds
- C11D3/12—Water-insoluble compounds
- C11D3/124—Silicon containing, e.g. silica, silex, quartz or glass beads
- C11D3/1246—Silicates, e.g. diatomaceous earth
- C11D3/128—Aluminium silicates, e.g. zeolites
Landscapes
- Chemical & Material Sciences (AREA)
- Life Sciences & Earth Sciences (AREA)
- Engineering & Computer Science (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Oil, Petroleum & Natural Gas (AREA)
- Wood Science & Technology (AREA)
- Organic Chemistry (AREA)
- Inorganic Chemistry (AREA)
- Detergent Compositions (AREA)
Abstract
ABSTRACT OF THE DISCLOSURE
Pourable washing agent compositions comprising essentially a premix powder component and optionally a second powder component obtained by hot drying of an aqueous composi-tion containing conventional heat-insensitive components, consisting essentially of (1) from 30% to 100% by weight of a premix consisting essen-tially of (A) finely-dispersed, water-insoluble silicate compounds having a calcium-binding power of at least 50 mg CaO/gm of anhydrous active substance and having the formula, combined water not shown, of (M2/nO)x ? Me2O3 ? (SiO2)y where M is a cation of the valence n, exchangeable with calcium, x is a number of from 0.7 to 1.5, Me is a member selected from aluminum and boron and y is a number of from 0.8 to 6, which silicate com-pounds optionally are partly replaced by highly dispersed silica in amounts of not more than 4% by weight, based on the weight of the premix;
(B) optionally bleaching components selected from the group consisting of inorganic peroxyhydrate com-pounds capable of supplying H2O2 in water, activators for percompounds, for percompounds and mixtures thereof;
- A -(C) non-ionic surface-active compounds finely distri-buted on and throughout component (A) or the mixture of components (A) and (B);
where the mixture of component (A) to component (C) is in the ratio of 10:1 to 1:3; and (2) from 0 to 70% by weight of a powdery component obtained by hot drying of an aqueous composition containing conventional heat-insensitive washing components; as well as a process for the production of said pourable washing compositions.
- B -
Pourable washing agent compositions comprising essentially a premix powder component and optionally a second powder component obtained by hot drying of an aqueous composi-tion containing conventional heat-insensitive components, consisting essentially of (1) from 30% to 100% by weight of a premix consisting essen-tially of (A) finely-dispersed, water-insoluble silicate compounds having a calcium-binding power of at least 50 mg CaO/gm of anhydrous active substance and having the formula, combined water not shown, of (M2/nO)x ? Me2O3 ? (SiO2)y where M is a cation of the valence n, exchangeable with calcium, x is a number of from 0.7 to 1.5, Me is a member selected from aluminum and boron and y is a number of from 0.8 to 6, which silicate com-pounds optionally are partly replaced by highly dispersed silica in amounts of not more than 4% by weight, based on the weight of the premix;
(B) optionally bleaching components selected from the group consisting of inorganic peroxyhydrate com-pounds capable of supplying H2O2 in water, activators for percompounds, for percompounds and mixtures thereof;
- A -(C) non-ionic surface-active compounds finely distri-buted on and throughout component (A) or the mixture of components (A) and (B);
where the mixture of component (A) to component (C) is in the ratio of 10:1 to 1:3; and (2) from 0 to 70% by weight of a powdery component obtained by hot drying of an aqueous composition containing conventional heat-insensitive washing components; as well as a process for the production of said pourable washing compositions.
- B -
Description
~039608 In the production of powdered washlng and clean~lng agent composltions, non-lonic ~urface-~ctive compounds (~on-ionlc~) are ~requently u~ed in addition to or instead of the anionic surface-active compounds. Accordlng to a technically preferr~d productlon method, the aqueous mixture o~ the co~-po~ents of the pr~paration 1~ trans~ormed lnto a pourable powder by hot drying, partlcularly by atomization in a hot gas. Since the Non-lonlcs are ~tea~-volatile~ a part thereo~
18 108t in the above hot dryin~. Thi~ 1~ undesirable for economical ~nd ecological rea~ons. In order to a~oid tbese lo~es, it i~ desirable to lncorporate the No~-ionlcs into a preli~lnary m$xture by spray~ng them on powdered sub~trates, ~hich represent themselves conventlonal component~ Or solid ~ashing and cleanlng a6ent compo~itions, such a~ ~odium ~ri-polypho~phate, sodium perborate or ~odlum sulfate. The~e preliminary mlxture~ can then be admlxed wlth the remslnder . ., o~ the co~po~ente. However, the premixes obtained in this :
- m~nner have un~atis~actory po~der qualltie~ the Non-ionics portlon in the pre~x e~ceeds 10% by weight of the total premix. Iher~iore, wlth a premlx portion o~ about 50% by weight in the total deterg¢nts, which 1~ conventional, only 5% by weight of Non-lonlcs can be l~corporated 1R the end product.
It 18 also known to ~mprove the powder quallty of the~e premixe~ by tbe addition o~ other 3ubstrates wlth a large active surrace area, such a~ hlghly dlsper~ed slllca, but in this matter, wash-lnactlve ball~t materlals ar~
;: introduced lnto the wa~hlng compo~ltion. In addition, sodlum trlphosphate as a ~olid sub~trate ~h~uld be avoldsd, llkeNlse ior ecologlcal rea~on~.
, ............................................................ . . .
.
,: . . . . ... . . ... .
`` ~039608 In cope~ding, commonly asslgned Canadlan Patent Application Serial No. 197,628, filed April 16, 1974, an improvement in the process of washing and ble.aching textiles is described wherein the soiled textiles are immer~ed in an aqueous solltion containing a water softening agent for a time sufficient to disperse or dis-solve the soil from said soiled textiles into said aqueous solu-tion, separating said aqueous solution and recovering said tex-: tlles substantially soil-free. This improvement consists of using at least one finely-dispersed water-insoluble silicate com-10 pound containing at least some combined water and having a cal-. cium binding power of at least 50 mg CaO/gm of anhydrous active substance and the formula on the anhydrous basis (M2jn)X Me23 (SiO2)y . where M is a cation of the valence n, exchangeable with calcium .
. x is a member of from 0.7 to 1.5, Me is a member selected from the group consisting of aluminum and boron, and y is a number from 0.8 to 6, as said water softening agent.
The calcium binding power of the silicate compounds can be as high as 200 mg CaOlgm of anhydrous active substance (AS) ~:
. 20 and preferably is in the range of 100 to 200 mg CaO/gm AS.
.: The cation ~ employed is preferably sodium. However, the same can also be totally or partially replaced by other cations :` exchangeable with calcium, such as hydrogen, lithium, potassium, ammonium or magnesium, as well as by the cations of water-soluble organic bases, for example, by those of primary, secondary or ter-tiary alkylamines or alkylolamines with not more than 2 carbon a~oms per alkyl radical, or not more than 3 carbon atoms per alkylol radical.
18 108t in the above hot dryin~. Thi~ 1~ undesirable for economical ~nd ecological rea~ons. In order to a~oid tbese lo~es, it i~ desirable to lncorporate the No~-ionlcs into a preli~lnary m$xture by spray~ng them on powdered sub~trates, ~hich represent themselves conventlonal component~ Or solid ~ashing and cleanlng a6ent compo~itions, such a~ ~odium ~ri-polypho~phate, sodium perborate or ~odlum sulfate. The~e preliminary mlxture~ can then be admlxed wlth the remslnder . ., o~ the co~po~ente. However, the premixes obtained in this :
- m~nner have un~atis~actory po~der qualltie~ the Non-ionics portlon in the pre~x e~ceeds 10% by weight of the total premix. Iher~iore, wlth a premlx portion o~ about 50% by weight in the total deterg¢nts, which 1~ conventional, only 5% by weight of Non-lonlcs can be l~corporated 1R the end product.
It 18 also known to ~mprove the powder quallty of the~e premixe~ by tbe addition o~ other 3ubstrates wlth a large active surrace area, such a~ hlghly dlsper~ed slllca, but in this matter, wash-lnactlve ball~t materlals ar~
;: introduced lnto the wa~hlng compo~ltion. In addition, sodlum trlphosphate as a ~olid sub~trate ~h~uld be avoldsd, llkeNlse ior ecologlcal rea~on~.
, ............................................................ . . .
.
,: . . . . ... . . ... .
`` ~039608 In cope~ding, commonly asslgned Canadlan Patent Application Serial No. 197,628, filed April 16, 1974, an improvement in the process of washing and ble.aching textiles is described wherein the soiled textiles are immer~ed in an aqueous solltion containing a water softening agent for a time sufficient to disperse or dis-solve the soil from said soiled textiles into said aqueous solu-tion, separating said aqueous solution and recovering said tex-: tlles substantially soil-free. This improvement consists of using at least one finely-dispersed water-insoluble silicate com-10 pound containing at least some combined water and having a cal-. cium binding power of at least 50 mg CaO/gm of anhydrous active substance and the formula on the anhydrous basis (M2jn)X Me23 (SiO2)y . where M is a cation of the valence n, exchangeable with calcium .
. x is a member of from 0.7 to 1.5, Me is a member selected from the group consisting of aluminum and boron, and y is a number from 0.8 to 6, as said water softening agent.
The calcium binding power of the silicate compounds can be as high as 200 mg CaOlgm of anhydrous active substance (AS) ~:
. 20 and preferably is in the range of 100 to 200 mg CaO/gm AS.
.: The cation ~ employed is preferably sodium. However, the same can also be totally or partially replaced by other cations :` exchangeable with calcium, such as hydrogen, lithium, potassium, ammonium or magnesium, as well as by the cations of water-soluble organic bases, for example, by those of primary, secondary or ter-tiary alkylamines or alkylolamines with not more than 2 carbon a~oms per alkyl radical, or not more than 3 carbon atoms per alkylol radical.
2 :
.
;`
:
: db/n'~>, ~039608 An ob~ect of the present invention is to develop - a preferably phosphate-free or low-pho~phats pourable deter-gent containing non-ionl~ surface-active compounds, which do not have the above-described disadvantages and where a 1088 o~ Non-ionics 1R avo~ded in the production.
Another bb~ect of the present inventlon i8 the d~elop~ent o~ a pourable washing agent composltlon compri8ing a premix powder component and optionally a ~econd powder -:
component obtained by hot drylng of an aqueous composltlon containlng conventional heat-i~sen~itive washing agent - component~, conslsting essentially Or .~' (1) from 30~ to lO0~ by wsight o~ a prem~x powder component con~ist~ng es~entially of (A) at lea~t one rinely-dispersed, ~ater-in~olubl~ 8ill-- cate compound containing at l~ast some comblned ; ~ater and ha~lng a calclum bindlng pow~ of ~t least ~; 50 mg cao/gm of anhydrous active substa~ce and the r~rmul~ o~ the anhydrQua ba~s - (M2~)X ~e203 (S102)y where M i~ a catlon of the val~nce n, exchangeable with calcium, x ~ a number of from 0.7 to 1.5, 18 a ~ember ~elected from the group con~istl~g Or alumi~um and boron, and y i~ a number from 0.8 to ,6., which sllicate compou~d can optional~y be :'. ' partly replac~d with hi~hly disper~ed ~ilica in an amount Or not more than ~% by weight of the ~eight of t}~e premix, (B) from 0 to 80% by weight oi the premix Or bleaching oomponent~ ~elected :ero~ the eroup cQnsistlng of inorganic peroxyhydrate co~pound~ eapable ~ ~upplylng , ~
.
;`
:
: db/n'~>, ~039608 An ob~ect of the present invention is to develop - a preferably phosphate-free or low-pho~phats pourable deter-gent containing non-ionl~ surface-active compounds, which do not have the above-described disadvantages and where a 1088 o~ Non-ionics 1R avo~ded in the production.
Another bb~ect of the present inventlon i8 the d~elop~ent o~ a pourable washing agent composltlon compri8ing a premix powder component and optionally a ~econd powder -:
component obtained by hot drylng of an aqueous composltlon containlng conventional heat-i~sen~itive washing agent - component~, conslsting essentially Or .~' (1) from 30~ to lO0~ by wsight o~ a prem~x powder component con~ist~ng es~entially of (A) at lea~t one rinely-dispersed, ~ater-in~olubl~ 8ill-- cate compound containing at l~ast some comblned ; ~ater and ha~lng a calclum bindlng pow~ of ~t least ~; 50 mg cao/gm of anhydrous active substa~ce and the r~rmul~ o~ the anhydrQua ba~s - (M2~)X ~e203 (S102)y where M i~ a catlon of the val~nce n, exchangeable with calcium, x ~ a number of from 0.7 to 1.5, 18 a ~ember ~elected from the group con~istl~g Or alumi~um and boron, and y i~ a number from 0.8 to ,6., which sllicate compou~d can optional~y be :'. ' partly replac~d with hi~hly disper~ed ~ilica in an amount Or not more than ~% by weight of the ~eight of t}~e premix, (B) from 0 to 80% by weight oi the premix Or bleaching oomponent~ ~elected :ero~ the eroup cQnsistlng of inorganic peroxyhydrate co~pound~ eapable ~ ~upplylng , ~
- 3 -' ! ' , .
' ' " . ' ' .
22 in water, ~ 6Pc~ ated activators ~or per-compounds, powdery stabil~zers for percompounds and mlxtures thereof;~
(C) non-ionic surface-active compounds f~nely dlstrlbuted . on and throughout component (A) or the mlxture o~ :
. components (A) and (B);
where ~,he mix ratlo of component (A) to component (C) " i8 in the ratio of lO:l to 1:3 and at least 20~
: of said premix are component~ (A) and ~C) together, the final mix ratio of the components being selected whereby the premix i~ a pourable powder; and (2) from O to 70% by weight of a ~econd powdery component obtained by hot drying of an agueous composition eontaln-ing conventional heat-~nsensltive washing agent component~.
~ Another ob~ect o~ the present invention i~ the .- development of a pourable premix po~dery component for ad-: m~xture in washlng agent compo~itions consisting essentially of (A) at least one finely-dispersed, ~ater-insoluble 8il~-. cate compound containing at least some combined water and having a calcium bindlng power of ~t least 50 Lg CaO/gm of anhydrou~ active ~u~stance and the formula on the anhydrous ba~is (M2/n)x M~203 (si2)y ~: where M is a cation o~ the valence n, exchangeable wlth calcium, x $8 a number of from 0.7 to 1.5, ., - .
M~ i~ a member selected from the group consistlng . . o~ alum~r~um and boron, and y i~ a number from 0.8 to 6, whlch ~ilicate comp~und can optionally be 3 partly replaced with highly disper~ed siLica in an . .
~` ~1039608 amount Or no~ more than ~ by weight of the ~elght the premix;
(B) rrom 0 to 80% ~y weight o~ the premlx o~ bleaching :
components selected from the group consisting of inorganlc peroxyhydrate compounds capable of supplylng . .
H202 in ~ater, powdery acylated actlvators for per-compounds, powdery stabil~zers ~or perc~mpounds and ;~ ~xture~ thereo~;
(C) non-ioDlc surface-active compounds finely distrlbuted on and throughout component (A) or the mlxture o~
. components (A) and (B3;
where ~,he mix rat1o of component (A) to component (C) ~ -; 1~ in the ratio of 10:1 to 1:3 and at le~st 20%
; o~ ssid premix are components (A) and (C) together, : the ~inal ~ ratio o~ the component~ being selected :
. whereby the premix iB a pourable powder.
m ese and other ob~ects of the lnventlon will ~ . becom~ more apparent as the descriptlon thereo~ proceeds.
::: The above drawback~ have been overcome and the above ob~ects hav~ been achieved by the pre~ent pourable ~a~hing agent compositions. The pourable .washing and clean-.. iDg agent~ accordlng to the invention conslst Or ~rom 30% to 100% by w~ight o~ a prem~x composed of:
~A) Rt least one finely-dispersed, water-insolub~e silicate compound contain$ng combined water in the given case, .~ havlng a calcium blnding power o~ at least 50 mg CaO~gm .
oi' anhydrous acti-ve substance and the general for~ula (on the anhydrou~ basig) (M2/n)x Me2~3 (si2)y ... .
w~nere M i8 a catio~ o~ the valence n, exchangeable wlth ~ ~
.,'' , .
~ ,. ' -: ' '-' ' '" ~039608 calcium, x i~ a number from 0.7 to 1.5, pre~er~bly rom 0.7 to 1.1, ~e i8 aluminum or boron, and y i8 a number from 0.8 to 6, prererably ~ro~ 1.3 to 4, whore . these compound~ can likewi~e be substituted partly by highly d~sperEed silica ln amounts of not more tha~ 4%
by weight based on the entire premix;
(B) optionally, a bleachlng compollent o~ lnorganic percom-:~ pounas whlch supply H22 in water, and/or activator~ for the~e percompound~
~- 10 (C) Non-ionlc~ finely distrlbuted ~ver the component accord- -lng to (A) or over the mixture o~ components (A) and (B);
ana from 0 to 70% by weight o~ a powder cQmponent obta~n~d by hot drying of an aqueou~ co~po~ition with ~onventional heat-insensltive components Or washlng and cleanin8 agents.
e premi~o~ mu~t, therefore, al~eady be con~idered a8 wa~hlng and cleaning agent compQsltlon~ in the sen~e of the inv~ntion.
The quantitative ratlo Or the cation-exchan~lng 20 component (A) and o~ the ~on-ionic~ (C) in the above-aerined ~ premix can b~ ln the range Or 10:1 to 3sl, ~epending o~
: ~hether the subetrates o~ co~po~ent (B) are alao pre~ent, ~hereby tne cation exchanging compoun~ accordln~ to (A) and : the Non-ionics (C) r~present at lea~t 10% by ~eight o~ the ;. premlx.
, .
More particul~rly~ the present inve~tion res~de~
ln a pourable washing agent co~positlon co~prlsing a premix . po~d~r compone~t and optionally a ~econd powder component ~' obtained by hot drylng o~ an aqueous composition containing cQave~tional h~at-lnsensltlve wa~hlng age~t component~, con~lsti~g es~ntlally of , .
.
` 1039608 ~` (1) from 30% to 100% by weight of a premix powder component consisting essentially of (A) at lea~t one finely-dispersed, ~ater-insoluble sili-cate compound containlng at least some combined water and bavlng a calclum binding power-of at least 50 mg Cao/gm of anhydrous active substance and the formula on the anhydrou~ ba~i~
(M2/n)x ~ Me203 . (S102)y where M is a cation of the valence n, exchangeable ~
wlth calcium, x is a number of from 0.7 to 1.5, -:
Me i8 a member selected from the group consistlng of aluminum and boron, and y is a number from 0.8 to 6, which silicate compound can optionally be partly replaced with hi8hly dispersed ~llica in an amount of not more than ~% by ~Jeight of the weight . of the premix;
. (B) from 0 to 80% by wei8ht of the premix of bleaching components selected from the group con3i~ting of inorganic peroxyhydrate compounds capable of ~upplying 20 H202 1n wster, powdery ac~lated activators for per-compound6, powaery stabi~;zers ~or percompound~ and ~ixtures thereof;
;~ (C~ non-loDlc sur~ace-active compound~ ~inely distributed . on and throughout component (A) or the mlxture o~
components (A) and (B);
: where ~he mix ratlo of component (A) to component (C) i~ ln the ratio of 10:1 to 1:3 and at least 20~
o~ ~aid premix are components (A) and (C) together, the fi~al mix ratlo of the component~ being selected 3 whereby the premix iB a pourable powder; and ,-.
(2~ from 0 to 70~ by wei~lt of a second powdery component obtained by hot dry~ng of ~n aqueou~ composltlon contaln-lng conventional heat-lnsens1ti~e wsshing agent components.
Therefore, the invention also resides in a pourable prealx po~dery component for admi~ture in washlng a~ent composltions conslsting essentlally of (A) at least one finely-dispersed, water-insoluble 8ili-. cate compound containing at least some combined - water and having a calcium bindlng power of at lea~t 50 mg CaO/gm of anhydrous active substance and the formula on the anhydrous basi~
(M2/n)x M~03 (sio2~y where M is a cation of the valence n, exchangeable with calcium, x is a number of from 0.7 to 1.5~
:~ Me i~ a member selected from the group consisting ~ of aluminum and boron, and y is a number from 0.8 ; to 6, which silicate compound can optionally be : partly replaced wlth highly dispersed silica in a~
amount o~ not more than ~ by weight o~ the ~elght Or the premix, (B) from 0 to 80% by welght of the premlx of bleachlng component~ ~elected from the group consisting of ::~ inorganic peroxyhydrate compounds capable o~ ~upplylng H202 ln ~ater, powdery acylated acti~ators for per-compounds5 powdery stabi~1zers ror percompounds and m1 xture~ thereo~;
(C) non-lonic surface-active compounds ~nely distrlbuted on and throughout component (A) or the mixture of components (A) and (~);
~L0396Q8 ~here the mix ratlo of co~ponent (A) to comp-gnent (C) i8 in the ratio of 10:1 to 1:3 and at least 20%
o~ ~aid premix are co~ponent~ (A) and (C) together, ~; -the flnal mix ratio of the comp~nent~ being ~electe~
~hereby the premix i8 a pourable po~der.
The synthet~c water-ln~oluble ~ilicate compoun~
~efined as component (A) will her~after b~ called "alumino-silicates" iorsi~plicity'~ ~ake. Their Galcium bin~n~ :
.: power can attain ~alues ci 200 mg Cao/gm Or aDhydrous acti~e substa~ce (AS) and i8 pre~erably in the range o~ 1~0 to 200 mg CaO/g~ AS.
Sodium ~ preferably used as a ~ation, but it can al~o be replacea by hydroge~, lithiu~, potasffium~ ammoniu~ or m~gne~um, a~ ~ell as by the c~tion~ o$ water-~oluble organlc : ba~es, ~or exa~ple, by those Or pri~ry, seconaary or tertiary .. alkylamines or alkylola~i~es Nith not more t~an two c~rbon atoms per alkyl or not ~ore than three car~on atom~ per - j alkylol. s ~,.. j ~th particular ad~antage alumino~ilicates are u~ed . . 20 which CO~Bil3t of` at lea~t 80% by ~e~ght of p~rticles o~ a ~lz~
. . .
' ~ro~ 10 to 0~01 ~, pr~ferably ir~m 8 to 0.1 ~. The~ alu~ino~
. .
sllieate~ ~ontain pre~erably no prlmary or ~ecaldary parki~le~ : -of a ~ize above 40,~.
m~ non-lo~lc ~urface-actlve co~pound~ (No~ lcs) tG be utt-lized accordi~g to the lnventlon are the products o~ addition o~ 8 to 20 mc~ls of ethylone oxlde to 1 ~ol of a co~pound ha~ from 10 to 20 carbon ato~ d a labile hydrog~n ato~ ~uch a~ ~atty alcdQls, alkklphenol~, ratty aclas, ~atty amine~, fatty ac~d a~ide~ or alkan~ onamlaes.
E~pecially important are the purely aliphatic non-lonlc~
. . ~
,, .
` 1039608 derlved~ for example, from coconut or tallow ~atty alcohols, fro~ oleyl alcohol or from secondary alkanol~-with 12 to 18 carbon atom~.
In addltion to the~e practically water-so~uble Non-lonic~, the ~ater-lnsoluble or not readlly ~ater-soluble ethoxylation product~ with 2 to 6 mol~ of ethylene oxide to 1 ~ol of the above compounds haring from 10 to 20 carbon atoms and a labile bydrogen atom are Or i~ere~t becau~e of thelr fat-di~solving and greying-inhibi~lng propertie~
these are used together wlth the water-~oluble Non-lonics and/or other ~urfactants, a good cleanlag sifect i8 achie~ed, partlcularly with hydrophobic 80il, ~f the quantitatiYe ratio ln th~ iinisbed d~tergent iormulas of the low-etho~ylated : Non-lonic~ to the hlgher ethoxylated Non-ionic~ 18 in the range of 1:3 to 2:1, particularly 1:2 to 1:1.
Partlcularly preferred, be~ause of their good cleaning actlon in co~bination wlth a ~ood biodegradability, are the ethoxylatlo~ product~ of th~ prlmary, straight-cha~ned C12 to C18 alkanols or alkenol~ ~ith an average degree o~ ethoxylation ~f 3 to 5 or 10 to 15, respecti~ely, in the .
above-indicated qua~tltati~e ratios.
,~ Al~o the product~ o~ additio~ o~ ethylene oxide to - terminal or ~on-terminal vicln~l alkanediols having from 10 .~ to 20 carbon ato~ can be used as no~-ionic surrace-active ¢ompounde, with 2 to 4 or respectively 8 to 1~ ethyleneglycol ether l~n~ts in the molecule being preferred.
Other ~uit~ble Non-lonlcs are those of the type of the acid amlde~ which are obtained by reacting fatty acids, ratty acid esters, fatty acid halides or alkane~ulfonic acid hallde~ wlth mono- or dieth~nol~lne or by further ethoxylatlon of the~e reaction products.
'' ` 3L0396()8 me invention thu~ concern~ substantlally the u~e o~ tbe finely divided, cation-exchanglng alumlnoslllcates according to (A) as solid ~ubstrates with good adsorptlon power for the NQn-ionics. Thi8 mahes i8 not only posslble to provide pourable ~ashlng and cle~ning agent eompo~ltions with a high No~-lonics content, but lt make~ it unnec~s~ary to a ~reat extent to use conventlonal water-soluble lnorganic or organic sequester agents for calcium-ion~, because o~ the excellent cation exchanger propertles of the alumino~illcate~. Pho8-phoru~-containl~g calclum sequeskering agents3 partlcularly sodium trlpolyphosphat~, can be completely eliminated ~rom the prem$x acoording to the invention and thu~ from the washing : and cleaDing age~ composttions made ~here~rom.
: The premixe~ suitable for the product~on of bleaehin~
: ~ashing agent compo~l~ions contaln a~ an additional solid ; sub~trate the bleaching component (B), ~hich con~i~ts o~ an .~ lnorganic percompound or peroxyhydrate compound supplyi~g H22 in water, partlcularly of sodlum perborate and/or a so~ia actiYator for the percompound as ~ell as a atabilizer fo~ the percompound, and ~hich can amount to ~rom 15% to 80% by weight .:
c. of the prem~x when th9 8a~e i8 pre~en~. But ~ompo~ent ~B) can also con~ist exclusively of the actlvatox for percompounda In the latter ca~e, three part~al mixtures are u~ed ~or the production of the bleaching preparations, namely, the aeti- -vator-containing premix, a hot-drled po~der, and the powdered perco~pound. Ih premixes rOr non-bleaching ~reparatlQns, such as prewashlng, fine wa~hing or ~ain wa~hing agent composltio~s, compon~nt (B) 1~ naturally ~i9~ing.
- Tho pre~ixe~ accordlng to the ln~ention caa also - 30 contain other co~v~ntl ~ 1 powdered comp~nents of washing and clea~sing agent compo~ition~. m e~e include as a po~lb~e :.
, .: .
, ` ~l039608 constltuent of component (A) a hlghly dispersed silica with a specl~ic ~ET-~urface of at least 250 m2/gm, wnl~h'should be contain, however, only up to 4% by wei~ht of the premlx be-cause Or its nature a~ a ballast sub~tance. The premixe~ con-tai ~ a bleaching component (B) can also contain additlonally a stabiLlzer, preferably ~agnesium ~ilicate to erih ~ce the bles.chlng action. Optlonall~, and ln addition, the preml~ces can contain the following water-soluble substrates: sodium eul~ate, the alkali ~etal carbona~es, bicarbonate~, ~ilicat*~
10 or borate~, known as wash alkalls, or the water-~oluble builder~ or se~uestering agent~ de3crlbed below; urea i~ also .., :~ ~u~table as a substrate.
Substances, such as enzymes, antl~lcrobial compounds or per~umes, which are not ~ub~ected to hot drying bec~use o~
their instablllty relative to water and/or heat~ or becauso of - their volatllity can al~o be added in ~mall Q~ounts to the pre~lxes.
Tbe compositl~n of a pre~ix c~ntainlng percompounds i8 generally llithin the follolring formula:
-. 20 10% to 60% by ~eight of the aluminosilicates according to (A), 20% to ~0% by weight o~ inor~anic percompound~ 8UpplylDg H22 in ~fater, particlllarly 80dium perborate, 10% to 30,~ by weight of Nor~-lonics, O to 4% by weight oi highly di~persed silica, O to 30% by lfeight Or ~ powdered activator ~d/or stabilizer ~or percompounds, Premixe~ without percompounds ca~ ha~re the ~ollowing comp~sltl0n:
60% to 90% by weight of the aluminosilicate~ aacordillg to (A), 10% to 40,~ by welght of llon-ionlcs, : O to 4% by weight of hlghly disper~ed sllica, o to 30~ by welght of a po-adered actlvator for-percompounds.
.: ' - 12 _ :lC~39608 The above-defined aluminosilicates can be produced syn-thetically in a known, s~mple manner, or example, by reacting wster-soluble s~licates with water-soluble aluminates in the presence of water. To this end aqueous solutions of the start-ing materials can be mixed with each other, or one component which is present in solid form can be reacted with another com-ponent which is present as an aqueous solution. The desired aluminosilicates can also be obtained by mixing both solid com-ponents in the presence of water. Aluminosilicates can also be produced from Al(OH)3, Al203 or SiO2 by reaction with alkali -metal silicate or alkali metal aluminate solutions. Finally, such substances are also formed from the melt, but this method seems of less economical interest because of the required high melting temperature and the necessity of transforming the melt ~-into finely-dispersed products. -The cation-exchanging aluminosilicates to be used accord-ing to the invention are only formed if special precipitation . ~ .
conditions are maintained, otherwise products are formed which have no, or an inadequate, calcium exchanging power. The cal-cium exchanging power of at least 50 mg CaO/gm of anhydrous ~-active substance (AS) is critical to the present process. If aluminosilicates are employed with belo~ the critical limit of calcium exchanging power, very little if any soil removal from the soiled textiles is effected in the absence of other types of calcium sequestering or precipitating agents. The production of -useable alumlnosilicates according to the invention is described in the experimental part.
The aluminosilicates in aqueous suspension produced by precipitation or by transformation in finely-dispersed form according tc other methods can be transformed from the :
~.
db ~
. . .. . -, - ~ . , . - -. .
amorphous into the aged or into the crystalline state by heating the suspension to temperatures oP 50 to 200C. However, there is hardly any difference between these two forms as far as the calcium binding power is concerned. Aslde from the drying con-dltions, the calcium binding power of the aluminosilicates is proportional to the amount of aluminum contained therein with reference to the amount of silicon.
The preferred calcium binding power, which is in the range of 100 to 200 mg CaO/gm AS, is found primarily in com-pounds of the composition:
0-7 to 1-1 Na2 A123 1-3 to 3-3 Si2 This summation formula comprises two types of different crystal structures (or their non-crystalline initial products) which also differ by their summation formulas.
* These are:
S a) 0-7 to 1~ a2O . A1203 . 1.3 to 2.4 SiO2 . , b) 0.7 to 1.1 Na2 A123 >2-4 to 3-3 Si2 The different crystal structures can be seen in the X-ray ~ diffraction diagram. In X-ray amorphous products, the crystal ; 20 structure can mostly still be recognized in an electron dif-fraction diagram.
A representative of type (A) above is ~he compound I of the composition:
0.9 Na20 . A12O3 . 2.04 SiO2 ~ 4'3 ~2 (I) A representative of type (B) above is compound II of the composition:
0.8 Na2O . 1 A12O3 . 2.65 SiO2 . 5.2 ~2 (II) The water content of compounds I and II was determined after drying for 24 hours at 100C.
The amorphous or crystalline aluminosilicate contained ln the aqueous suspension can be separated by filtration from . , .,, ' , .
tb / ~
l03a60s the remaining aqueous Aolution and be drled at temperatures of 50C to 800C, for example. Depending on the-drying conditions, the product contains more or less combined water. Anhydrous pro-ducts are obtained by drying at 800~C. If we want to remove the water completely, this can be done by heating for 1 hour to 800C.
This is the way the AS contents of the aluminosilicates are also tetermined.
:; .
Such high drying temperatures are not recommended for the aluminosilicates to be used according to the invention, pre-ferably the temperature should not exceed 400C. It is of par-: ticular advantage that even products dried at substantially - lower temperatures of 80 to 200C, for example, until the ad-.... .. .
hering liquid water is removed, can be used for the purposes of the invention. The aluminosilicates thus produced, ~hich con-tain varying amounts of combined water, are obtained after the ~ -disintegration of the dried filter cake, as fine powders whose ~
primary particle size does not exceed 0.1 mm, but is mostly lower - -and ranges down to dust fineness, for example, to 0.1 ~. It must be kept in mind that the primary particles can be agglomerated to larger structures. In some production methods primary particle sizes ranging from 50 to 1 ~ are obtained.
Of particular advantage are aluminosilicates having at -least 80% by weight of particles of 10 to 0.01 ~, preferably 8 to 0.1 ~. These aluminosilicates preferably contain no primary or secondary particles above 40 ~. As far as the products are crystalline, they are "micro-crystalline."
~ ! ' The formation of smaller particle sizes can already be enhanced by the precipitation contitions. For these smaller particle sizes, the intermixed aluminate and silicate solutions, . , .
, ~ .
db/~ ~
: - . . ~ - : : , . . . -, - , . ~ . - ...
10;~96~)8 wnich can also be introduced ~lmultaneously into the reaction vessel, are sub~ected to great shearlng forces. If crystalline aluminum silicates are produced, which are preferred according to the invention, the formation of larger or inter-penetrating crystals is prevented by slowly stirring the orystallizing mass.
Nevertheless, undesired agglomeration of crystal particles can occur during the drying, so that it is advisable to remove these secondary particles in a suitable manner, for example, by air sifting. Aluminosilicates obtained in coarser form, which are ground to the desired particle size, can also be used.
Suitable for this purpose are, for example, mills and/or air sifters or combinations thereof. The latter are described, for example, in Ullmann, "Enzyklopadie der technischen Chemie" vol. 1, 1951, p. 632 to 634.
Prom the sodium aluminosilicates, aluminosilicates of other cations, for example, those of potassium, magnesium or water-soluble organic bases can be produced in 2 simple manner by the exchange of bases.
In order to produce aluminosilicates I and II, the following conditions are employed.
PROCESS CONDITIONS
The aluminate ~olution, diluted with deioni~ed water was mixed in a vessel of 15 liter capacity, under vigorous stirring with the silicate solution. Both solutions were at room tempera-; ture. An X-ray amorphous sodium aluminosilicate was formed in the exothermic reaction as a primary precipitation product.
After stirring for 10 minutes, the suspension of the precipita-tion product was either separated as an amorphous product or trans-ferred to a crystallization vessel where it remained for some time at the elevated temperature given .;' '' ' db/ ~
, :, :
1~39S08 to crystalllze. A~ter draining off the liquor from the cry~tals and washing with deionized water untll the outflowing wash water hat 8 pH-value of about 10, the fllter residue was dried. When there iR any deviation from this general production procedure, this is mentioned explicitly in the specific part. Thus, for example, in some cases for the practical tests, the homogenized uncrystallized suspension of the precipitation product or the crystal sludge was used. The water content was determined by ~-heating the product for one hour to 800C.
In the production of microcrystalline aluminosilicates, indicated by the suffix "m", the aluminate solution diluted with deionized water was mixet with the silicate solution and mixed in a high-speed intensive stirrer (10,000 rpm, "Ultraturrax~", made ;, .
by Janke & Kunkel IKA-Werk, Stauffen/Breisgau/Federal Republic ; of Germany). ~fter vigorous stirring for 10 minutes, the sus- -pension of the amorphous precipitation product was transferred to a crystallization vessel where the formation of large crystals was prevented by stirring the suspension. After draining off the liquor and wa~hing with deionized water until the outflowing `-20 water had a pH value of about 10, the filter residue was dried, then ground in a ball mill and separated in a centrifugal sifter ("MicroplexG~" air sifter, made by Alpine, Augsburg, Federal ~ Republic of Germany) into two fractions, of which the finer ., fraction contained no portions above 10 ~. The particle size distribution was determined by means of a sedimentation scale.
` The degree of crystallization of an aluminosilicate can be determined from the intensity of the interference lines of an ~-ray diffraction diagram of the re~pective product, compared to the correspond~ng diagrams of X-ray amorphous or fully crystal-lized products.
'-' ' . ' :
.
db/~
... .. . . . . . . . .
" -~ , . . . .
:. ~ . , ., , : ,. . .
All data in % are ln percent by welght.
The calcium binding power of the aluminosilicates or borosilicates was determined in the following manner. 1 liter of an aqueous solution, containing 0.594 gm of CaCl2 (- 300 mg CaO/1 = 30dH) and ad~usted to a pH of 10 with diluted NaOH, was - mixed with 1 gm of the aluminosilicate or borosilicate (on the anhydrous basis, AS). Then the suspension was stirred vigorously for 15 minutes at a temperature of 22C (+ 2C). After filtering off the aluminosilicate, the residual hardness x of the filtrate was determined. From it, the calcium binding power was calculated in mg CaO/gm. As according to the formula:
(30 - x) . 10 ` If calcium binding power is determined at higher tempera-ture, for example, at 60C, better values are obtained than at 22C. This fact distinguishes the aluminosilicates from most of the soluble sequestering agents that have been suggested so far for use in detergents and represents a particular technical pro-gress in their use.
Production conditions for aluminosilicate I:
Precipitation: 2.985 kg of an aluminate solution of the composi-tion 17-7% Na20, 15-8% Al203, 66.6% H20 0.15 kg of sodium hydroxide 9.420 kg of water 2.445 kg of a 25.8% sodium silicate solution of the composition 1 Na20. 6.0 SiO2, prepared freshly from commercial waterglass and easily alkali-soluble silica .~
Cry8tallization: 24 hours at 80C
Drying: 24 hours at 100C
~ , :
. - ' :
db¦~ -- :. ~ : . . ~ .
` ` lC~39608 Composition: 0.9 Na20 . 1 A12O3 . 2.04 SiO2 . 4.3 H20 (e2 l ~ 6% H20 ) ' Degree of cry6tsl-llzation: Fully crystalline Calclum binding power: 150 mg CaO/gm AS.
If the product obtained ~as dried for 1 hour at 400C, an aluminum silicate Ia was obtained of the composition: ~ ;
0.9 Na20 . 1 A1203 . 2.04 SiO2. 2.0 H2O t= 11-4% H2O) which is likewise suitable for the purposes of the invention.
Product conditions for aluminosilicate II:
Precipitation: 2.115 kg of an aluminate solution of the composition: 17.7% Na2O 15.8% A12O3, 66.5% H20 0.585 kg of sodium hydroxide 9.615 kg of water ;. 2.685 kg of a 25.8% sodium silicate solution of the composition: l Na20. 6 SiO2 (pre-- pared as under I) " 20 Crystallization: 24 hours at 80C
Drying: 24 hours at 100C and 20 torr.
Composition: 0.8 Na2O. 1 Al2O3. 2.655 SiO2. 5.2 H20 Degree of crystal-lization: Fully crystalline , :`
.~ Calcium binding ' power: 120 mg CaO/gm AS.
r ~ ' `
. ~ 9 ~
:: .
: ~ .
tb/~i!~
The aluminosl1icates I and II show in the x-ray dif-fraction diagram the following interference lines.
d- values, recorded with Cu-K~- radiation in A
I II
_ 14.4 12.4 - 8.8 8.6 . 7.0 ~ 4-4 (+)
' ' " . ' ' .
22 in water, ~ 6Pc~ ated activators ~or per-compounds, powdery stabil~zers for percompounds and mlxtures thereof;~
(C) non-ionic surface-active compounds f~nely dlstrlbuted . on and throughout component (A) or the mlxture o~ :
. components (A) and (B);
where ~,he mix ratlo of component (A) to component (C) " i8 in the ratio of lO:l to 1:3 and at least 20~
: of said premix are component~ (A) and ~C) together, the final mix ratio of the components being selected whereby the premix i~ a pourable powder; and (2) from O to 70% by weight of a ~econd powdery component obtained by hot drying of an agueous composition eontaln-ing conventional heat-~nsensltive washing agent component~.
~ Another ob~ect o~ the present invention i~ the .- development of a pourable premix po~dery component for ad-: m~xture in washlng agent compo~itions consisting essentially of (A) at least one finely-dispersed, ~ater-insoluble 8il~-. cate compound containing at least some combined water and having a calcium bindlng power of ~t least 50 Lg CaO/gm of anhydrou~ active ~u~stance and the formula on the anhydrous ba~is (M2/n)x M~203 (si2)y ~: where M is a cation o~ the valence n, exchangeable wlth calcium, x $8 a number of from 0.7 to 1.5, ., - .
M~ i~ a member selected from the group consistlng . . o~ alum~r~um and boron, and y i~ a number from 0.8 to 6, whlch ~ilicate comp~und can optionally be 3 partly replaced with highly disper~ed siLica in an . .
~` ~1039608 amount Or no~ more than ~ by weight of the ~elght the premix;
(B) rrom 0 to 80% ~y weight o~ the premlx o~ bleaching :
components selected from the group consisting of inorganlc peroxyhydrate compounds capable of supplylng . .
H202 in ~ater, powdery acylated actlvators for per-compounds, powdery stabil~zers ~or perc~mpounds and ;~ ~xture~ thereo~;
(C) non-ioDlc surface-active compounds finely distrlbuted on and throughout component (A) or the mlxture o~
. components (A) and (B3;
where ~,he mix rat1o of component (A) to component (C) ~ -; 1~ in the ratio of 10:1 to 1:3 and at le~st 20%
; o~ ssid premix are components (A) and (C) together, : the ~inal ~ ratio o~ the component~ being selected :
. whereby the premix iB a pourable powder.
m ese and other ob~ects of the lnventlon will ~ . becom~ more apparent as the descriptlon thereo~ proceeds.
::: The above drawback~ have been overcome and the above ob~ects hav~ been achieved by the pre~ent pourable ~a~hing agent compositions. The pourable .washing and clean-.. iDg agent~ accordlng to the invention conslst Or ~rom 30% to 100% by w~ight o~ a prem~x composed of:
~A) Rt least one finely-dispersed, water-insolub~e silicate compound contain$ng combined water in the given case, .~ havlng a calcium blnding power o~ at least 50 mg CaO~gm .
oi' anhydrous acti-ve substance and the general for~ula (on the anhydrou~ basig) (M2/n)x Me2~3 (si2)y ... .
w~nere M i8 a catio~ o~ the valence n, exchangeable wlth ~ ~
.,'' , .
~ ,. ' -: ' '-' ' '" ~039608 calcium, x i~ a number from 0.7 to 1.5, pre~er~bly rom 0.7 to 1.1, ~e i8 aluminum or boron, and y i8 a number from 0.8 to 6, prererably ~ro~ 1.3 to 4, whore . these compound~ can likewi~e be substituted partly by highly d~sperEed silica ln amounts of not more tha~ 4%
by weight based on the entire premix;
(B) optionally, a bleachlng compollent o~ lnorganic percom-:~ pounas whlch supply H22 in water, and/or activator~ for the~e percompound~
~- 10 (C) Non-ionlc~ finely distrlbuted ~ver the component accord- -lng to (A) or over the mixture o~ components (A) and (B);
ana from 0 to 70% by weight o~ a powder cQmponent obta~n~d by hot drying of an aqueou~ co~po~ition with ~onventional heat-insensltive components Or washlng and cleanin8 agents.
e premi~o~ mu~t, therefore, al~eady be con~idered a8 wa~hlng and cleaning agent compQsltlon~ in the sen~e of the inv~ntion.
The quantitative ratlo Or the cation-exchan~lng 20 component (A) and o~ the ~on-ionic~ (C) in the above-aerined ~ premix can b~ ln the range Or 10:1 to 3sl, ~epending o~
: ~hether the subetrates o~ co~po~ent (B) are alao pre~ent, ~hereby tne cation exchanging compoun~ accordln~ to (A) and : the Non-ionics (C) r~present at lea~t 10% by ~eight o~ the ;. premlx.
, .
More particul~rly~ the present inve~tion res~de~
ln a pourable washing agent co~positlon co~prlsing a premix . po~d~r compone~t and optionally a ~econd powder component ~' obtained by hot drylng o~ an aqueous composition containing cQave~tional h~at-lnsensltlve wa~hlng age~t component~, con~lsti~g es~ntlally of , .
.
` 1039608 ~` (1) from 30% to 100% by weight of a premix powder component consisting essentially of (A) at lea~t one finely-dispersed, ~ater-insoluble sili-cate compound containlng at least some combined water and bavlng a calclum binding power-of at least 50 mg Cao/gm of anhydrous active substance and the formula on the anhydrou~ ba~i~
(M2/n)x ~ Me203 . (S102)y where M is a cation of the valence n, exchangeable ~
wlth calcium, x is a number of from 0.7 to 1.5, -:
Me i8 a member selected from the group consistlng of aluminum and boron, and y is a number from 0.8 to 6, which silicate compound can optionally be partly replaced with hi8hly dispersed ~llica in an amount of not more than ~% by ~Jeight of the weight . of the premix;
. (B) from 0 to 80% by wei8ht of the premix of bleaching components selected from the group con3i~ting of inorganic peroxyhydrate compounds capable of ~upplying 20 H202 1n wster, powdery ac~lated activators for per-compound6, powaery stabi~;zers ~or percompound~ and ~ixtures thereof;
;~ (C~ non-loDlc sur~ace-active compound~ ~inely distributed . on and throughout component (A) or the mlxture o~
components (A) and (B);
: where ~he mix ratlo of component (A) to component (C) i~ ln the ratio of 10:1 to 1:3 and at least 20~
o~ ~aid premix are components (A) and (C) together, the fi~al mix ratlo of the component~ being selected 3 whereby the premix iB a pourable powder; and ,-.
(2~ from 0 to 70~ by wei~lt of a second powdery component obtained by hot dry~ng of ~n aqueou~ composltlon contaln-lng conventional heat-lnsens1ti~e wsshing agent components.
Therefore, the invention also resides in a pourable prealx po~dery component for admi~ture in washlng a~ent composltions conslsting essentlally of (A) at least one finely-dispersed, water-insoluble 8ili-. cate compound containing at least some combined - water and having a calcium bindlng power of at lea~t 50 mg CaO/gm of anhydrous active substance and the formula on the anhydrous basi~
(M2/n)x M~03 (sio2~y where M is a cation of the valence n, exchangeable with calcium, x is a number of from 0.7 to 1.5~
:~ Me i~ a member selected from the group consisting ~ of aluminum and boron, and y is a number from 0.8 ; to 6, which silicate compound can optionally be : partly replaced wlth highly dispersed silica in a~
amount o~ not more than ~ by weight o~ the ~elght Or the premix, (B) from 0 to 80% by welght of the premlx of bleachlng component~ ~elected from the group consisting of ::~ inorganic peroxyhydrate compounds capable o~ ~upplylng H202 ln ~ater, powdery acylated acti~ators for per-compounds5 powdery stabi~1zers ror percompounds and m1 xture~ thereo~;
(C) non-lonic surface-active compounds ~nely distrlbuted on and throughout component (A) or the mixture of components (A) and (~);
~L0396Q8 ~here the mix ratlo of co~ponent (A) to comp-gnent (C) i8 in the ratio of 10:1 to 1:3 and at least 20%
o~ ~aid premix are co~ponent~ (A) and (C) together, ~; -the flnal mix ratio of the comp~nent~ being ~electe~
~hereby the premix i8 a pourable po~der.
The synthet~c water-ln~oluble ~ilicate compoun~
~efined as component (A) will her~after b~ called "alumino-silicates" iorsi~plicity'~ ~ake. Their Galcium bin~n~ :
.: power can attain ~alues ci 200 mg Cao/gm Or aDhydrous acti~e substa~ce (AS) and i8 pre~erably in the range o~ 1~0 to 200 mg CaO/g~ AS.
Sodium ~ preferably used as a ~ation, but it can al~o be replacea by hydroge~, lithiu~, potasffium~ ammoniu~ or m~gne~um, a~ ~ell as by the c~tion~ o$ water-~oluble organlc : ba~es, ~or exa~ple, by those Or pri~ry, seconaary or tertiary .. alkylamines or alkylola~i~es Nith not more t~an two c~rbon atoms per alkyl or not ~ore than three car~on atom~ per - j alkylol. s ~,.. j ~th particular ad~antage alumino~ilicates are u~ed . . 20 which CO~Bil3t of` at lea~t 80% by ~e~ght of p~rticles o~ a ~lz~
. . .
' ~ro~ 10 to 0~01 ~, pr~ferably ir~m 8 to 0.1 ~. The~ alu~ino~
. .
sllieate~ ~ontain pre~erably no prlmary or ~ecaldary parki~le~ : -of a ~ize above 40,~.
m~ non-lo~lc ~urface-actlve co~pound~ (No~ lcs) tG be utt-lized accordi~g to the lnventlon are the products o~ addition o~ 8 to 20 mc~ls of ethylone oxlde to 1 ~ol of a co~pound ha~ from 10 to 20 carbon ato~ d a labile hydrog~n ato~ ~uch a~ ~atty alcdQls, alkklphenol~, ratty aclas, ~atty amine~, fatty ac~d a~ide~ or alkan~ onamlaes.
E~pecially important are the purely aliphatic non-lonlc~
. . ~
,, .
` 1039608 derlved~ for example, from coconut or tallow ~atty alcohols, fro~ oleyl alcohol or from secondary alkanol~-with 12 to 18 carbon atom~.
In addltion to the~e practically water-so~uble Non-lonic~, the ~ater-lnsoluble or not readlly ~ater-soluble ethoxylation product~ with 2 to 6 mol~ of ethylene oxide to 1 ~ol of the above compounds haring from 10 to 20 carbon atoms and a labile bydrogen atom are Or i~ere~t becau~e of thelr fat-di~solving and greying-inhibi~lng propertie~
these are used together wlth the water-~oluble Non-lonics and/or other ~urfactants, a good cleanlag sifect i8 achie~ed, partlcularly with hydrophobic 80il, ~f the quantitatiYe ratio ln th~ iinisbed d~tergent iormulas of the low-etho~ylated : Non-lonic~ to the hlgher ethoxylated Non-ionic~ 18 in the range of 1:3 to 2:1, particularly 1:2 to 1:1.
Partlcularly preferred, be~ause of their good cleaning actlon in co~bination wlth a ~ood biodegradability, are the ethoxylatlo~ product~ of th~ prlmary, straight-cha~ned C12 to C18 alkanols or alkenol~ ~ith an average degree o~ ethoxylation ~f 3 to 5 or 10 to 15, respecti~ely, in the .
above-indicated qua~tltati~e ratios.
,~ Al~o the product~ o~ additio~ o~ ethylene oxide to - terminal or ~on-terminal vicln~l alkanediols having from 10 .~ to 20 carbon ato~ can be used as no~-ionic surrace-active ¢ompounde, with 2 to 4 or respectively 8 to 1~ ethyleneglycol ether l~n~ts in the molecule being preferred.
Other ~uit~ble Non-lonlcs are those of the type of the acid amlde~ which are obtained by reacting fatty acids, ratty acid esters, fatty acid halides or alkane~ulfonic acid hallde~ wlth mono- or dieth~nol~lne or by further ethoxylatlon of the~e reaction products.
'' ` 3L0396()8 me invention thu~ concern~ substantlally the u~e o~ tbe finely divided, cation-exchanglng alumlnoslllcates according to (A) as solid ~ubstrates with good adsorptlon power for the NQn-ionics. Thi8 mahes i8 not only posslble to provide pourable ~ashlng and cle~ning agent eompo~ltions with a high No~-lonics content, but lt make~ it unnec~s~ary to a ~reat extent to use conventlonal water-soluble lnorganic or organic sequester agents for calcium-ion~, because o~ the excellent cation exchanger propertles of the alumino~illcate~. Pho8-phoru~-containl~g calclum sequeskering agents3 partlcularly sodium trlpolyphosphat~, can be completely eliminated ~rom the prem$x acoording to the invention and thu~ from the washing : and cleaDing age~ composttions made ~here~rom.
: The premixe~ suitable for the product~on of bleaehin~
: ~ashing agent compo~l~ions contaln a~ an additional solid ; sub~trate the bleaching component (B), ~hich con~i~ts o~ an .~ lnorganic percompound or peroxyhydrate compound supplyi~g H22 in water, partlcularly of sodlum perborate and/or a so~ia actiYator for the percompound as ~ell as a atabilizer fo~ the percompound, and ~hich can amount to ~rom 15% to 80% by weight .:
c. of the prem~x when th9 8a~e i8 pre~en~. But ~ompo~ent ~B) can also con~ist exclusively of the actlvatox for percompounda In the latter ca~e, three part~al mixtures are u~ed ~or the production of the bleaching preparations, namely, the aeti- -vator-containing premix, a hot-drled po~der, and the powdered perco~pound. Ih premixes rOr non-bleaching ~reparatlQns, such as prewashlng, fine wa~hing or ~ain wa~hing agent composltio~s, compon~nt (B) 1~ naturally ~i9~ing.
- Tho pre~ixe~ accordlng to the ln~ention caa also - 30 contain other co~v~ntl ~ 1 powdered comp~nents of washing and clea~sing agent compo~ition~. m e~e include as a po~lb~e :.
, .: .
, ` ~l039608 constltuent of component (A) a hlghly dispersed silica with a specl~ic ~ET-~urface of at least 250 m2/gm, wnl~h'should be contain, however, only up to 4% by wei~ht of the premlx be-cause Or its nature a~ a ballast sub~tance. The premixe~ con-tai ~ a bleaching component (B) can also contain additlonally a stabiLlzer, preferably ~agnesium ~ilicate to erih ~ce the bles.chlng action. Optlonall~, and ln addition, the preml~ces can contain the following water-soluble substrates: sodium eul~ate, the alkali ~etal carbona~es, bicarbonate~, ~ilicat*~
10 or borate~, known as wash alkalls, or the water-~oluble builder~ or se~uestering agent~ de3crlbed below; urea i~ also .., :~ ~u~table as a substrate.
Substances, such as enzymes, antl~lcrobial compounds or per~umes, which are not ~ub~ected to hot drying bec~use o~
their instablllty relative to water and/or heat~ or becauso of - their volatllity can al~o be added in ~mall Q~ounts to the pre~lxes.
Tbe compositl~n of a pre~ix c~ntainlng percompounds i8 generally llithin the follolring formula:
-. 20 10% to 60% by ~eight of the aluminosilicates according to (A), 20% to ~0% by weight o~ inor~anic percompound~ 8UpplylDg H22 in ~fater, particlllarly 80dium perborate, 10% to 30,~ by weight of Nor~-lonics, O to 4% by weight oi highly di~persed silica, O to 30% by lfeight Or ~ powdered activator ~d/or stabilizer ~or percompounds, Premixe~ without percompounds ca~ ha~re the ~ollowing comp~sltl0n:
60% to 90% by weight of the aluminosilicate~ aacordillg to (A), 10% to 40,~ by welght of llon-ionlcs, : O to 4% by weight of hlghly disper~ed sllica, o to 30~ by welght of a po-adered actlvator for-percompounds.
.: ' - 12 _ :lC~39608 The above-defined aluminosilicates can be produced syn-thetically in a known, s~mple manner, or example, by reacting wster-soluble s~licates with water-soluble aluminates in the presence of water. To this end aqueous solutions of the start-ing materials can be mixed with each other, or one component which is present in solid form can be reacted with another com-ponent which is present as an aqueous solution. The desired aluminosilicates can also be obtained by mixing both solid com-ponents in the presence of water. Aluminosilicates can also be produced from Al(OH)3, Al203 or SiO2 by reaction with alkali -metal silicate or alkali metal aluminate solutions. Finally, such substances are also formed from the melt, but this method seems of less economical interest because of the required high melting temperature and the necessity of transforming the melt ~-into finely-dispersed products. -The cation-exchanging aluminosilicates to be used accord-ing to the invention are only formed if special precipitation . ~ .
conditions are maintained, otherwise products are formed which have no, or an inadequate, calcium exchanging power. The cal-cium exchanging power of at least 50 mg CaO/gm of anhydrous ~-active substance (AS) is critical to the present process. If aluminosilicates are employed with belo~ the critical limit of calcium exchanging power, very little if any soil removal from the soiled textiles is effected in the absence of other types of calcium sequestering or precipitating agents. The production of -useable alumlnosilicates according to the invention is described in the experimental part.
The aluminosilicates in aqueous suspension produced by precipitation or by transformation in finely-dispersed form according tc other methods can be transformed from the :
~.
db ~
. . .. . -, - ~ . , . - -. .
amorphous into the aged or into the crystalline state by heating the suspension to temperatures oP 50 to 200C. However, there is hardly any difference between these two forms as far as the calcium binding power is concerned. Aslde from the drying con-dltions, the calcium binding power of the aluminosilicates is proportional to the amount of aluminum contained therein with reference to the amount of silicon.
The preferred calcium binding power, which is in the range of 100 to 200 mg CaO/gm AS, is found primarily in com-pounds of the composition:
0-7 to 1-1 Na2 A123 1-3 to 3-3 Si2 This summation formula comprises two types of different crystal structures (or their non-crystalline initial products) which also differ by their summation formulas.
* These are:
S a) 0-7 to 1~ a2O . A1203 . 1.3 to 2.4 SiO2 . , b) 0.7 to 1.1 Na2 A123 >2-4 to 3-3 Si2 The different crystal structures can be seen in the X-ray ~ diffraction diagram. In X-ray amorphous products, the crystal ; 20 structure can mostly still be recognized in an electron dif-fraction diagram.
A representative of type (A) above is ~he compound I of the composition:
0.9 Na20 . A12O3 . 2.04 SiO2 ~ 4'3 ~2 (I) A representative of type (B) above is compound II of the composition:
0.8 Na2O . 1 A12O3 . 2.65 SiO2 . 5.2 ~2 (II) The water content of compounds I and II was determined after drying for 24 hours at 100C.
The amorphous or crystalline aluminosilicate contained ln the aqueous suspension can be separated by filtration from . , .,, ' , .
tb / ~
l03a60s the remaining aqueous Aolution and be drled at temperatures of 50C to 800C, for example. Depending on the-drying conditions, the product contains more or less combined water. Anhydrous pro-ducts are obtained by drying at 800~C. If we want to remove the water completely, this can be done by heating for 1 hour to 800C.
This is the way the AS contents of the aluminosilicates are also tetermined.
:; .
Such high drying temperatures are not recommended for the aluminosilicates to be used according to the invention, pre-ferably the temperature should not exceed 400C. It is of par-: ticular advantage that even products dried at substantially - lower temperatures of 80 to 200C, for example, until the ad-.... .. .
hering liquid water is removed, can be used for the purposes of the invention. The aluminosilicates thus produced, ~hich con-tain varying amounts of combined water, are obtained after the ~ -disintegration of the dried filter cake, as fine powders whose ~
primary particle size does not exceed 0.1 mm, but is mostly lower - -and ranges down to dust fineness, for example, to 0.1 ~. It must be kept in mind that the primary particles can be agglomerated to larger structures. In some production methods primary particle sizes ranging from 50 to 1 ~ are obtained.
Of particular advantage are aluminosilicates having at -least 80% by weight of particles of 10 to 0.01 ~, preferably 8 to 0.1 ~. These aluminosilicates preferably contain no primary or secondary particles above 40 ~. As far as the products are crystalline, they are "micro-crystalline."
~ ! ' The formation of smaller particle sizes can already be enhanced by the precipitation contitions. For these smaller particle sizes, the intermixed aluminate and silicate solutions, . , .
, ~ .
db/~ ~
: - . . ~ - : : , . . . -, - , . ~ . - ...
10;~96~)8 wnich can also be introduced ~lmultaneously into the reaction vessel, are sub~ected to great shearlng forces. If crystalline aluminum silicates are produced, which are preferred according to the invention, the formation of larger or inter-penetrating crystals is prevented by slowly stirring the orystallizing mass.
Nevertheless, undesired agglomeration of crystal particles can occur during the drying, so that it is advisable to remove these secondary particles in a suitable manner, for example, by air sifting. Aluminosilicates obtained in coarser form, which are ground to the desired particle size, can also be used.
Suitable for this purpose are, for example, mills and/or air sifters or combinations thereof. The latter are described, for example, in Ullmann, "Enzyklopadie der technischen Chemie" vol. 1, 1951, p. 632 to 634.
Prom the sodium aluminosilicates, aluminosilicates of other cations, for example, those of potassium, magnesium or water-soluble organic bases can be produced in 2 simple manner by the exchange of bases.
In order to produce aluminosilicates I and II, the following conditions are employed.
PROCESS CONDITIONS
The aluminate ~olution, diluted with deioni~ed water was mixed in a vessel of 15 liter capacity, under vigorous stirring with the silicate solution. Both solutions were at room tempera-; ture. An X-ray amorphous sodium aluminosilicate was formed in the exothermic reaction as a primary precipitation product.
After stirring for 10 minutes, the suspension of the precipita-tion product was either separated as an amorphous product or trans-ferred to a crystallization vessel where it remained for some time at the elevated temperature given .;' '' ' db/ ~
, :, :
1~39S08 to crystalllze. A~ter draining off the liquor from the cry~tals and washing with deionized water untll the outflowing wash water hat 8 pH-value of about 10, the fllter residue was dried. When there iR any deviation from this general production procedure, this is mentioned explicitly in the specific part. Thus, for example, in some cases for the practical tests, the homogenized uncrystallized suspension of the precipitation product or the crystal sludge was used. The water content was determined by ~-heating the product for one hour to 800C.
In the production of microcrystalline aluminosilicates, indicated by the suffix "m", the aluminate solution diluted with deionized water was mixet with the silicate solution and mixed in a high-speed intensive stirrer (10,000 rpm, "Ultraturrax~", made ;, .
by Janke & Kunkel IKA-Werk, Stauffen/Breisgau/Federal Republic ; of Germany). ~fter vigorous stirring for 10 minutes, the sus- -pension of the amorphous precipitation product was transferred to a crystallization vessel where the formation of large crystals was prevented by stirring the suspension. After draining off the liquor and wa~hing with deionized water until the outflowing `-20 water had a pH value of about 10, the filter residue was dried, then ground in a ball mill and separated in a centrifugal sifter ("MicroplexG~" air sifter, made by Alpine, Augsburg, Federal ~ Republic of Germany) into two fractions, of which the finer ., fraction contained no portions above 10 ~. The particle size distribution was determined by means of a sedimentation scale.
` The degree of crystallization of an aluminosilicate can be determined from the intensity of the interference lines of an ~-ray diffraction diagram of the re~pective product, compared to the correspond~ng diagrams of X-ray amorphous or fully crystal-lized products.
'-' ' . ' :
.
db/~
... .. . . . . . . . .
" -~ , . . . .
:. ~ . , ., , : ,. . .
All data in % are ln percent by welght.
The calcium binding power of the aluminosilicates or borosilicates was determined in the following manner. 1 liter of an aqueous solution, containing 0.594 gm of CaCl2 (- 300 mg CaO/1 = 30dH) and ad~usted to a pH of 10 with diluted NaOH, was - mixed with 1 gm of the aluminosilicate or borosilicate (on the anhydrous basis, AS). Then the suspension was stirred vigorously for 15 minutes at a temperature of 22C (+ 2C). After filtering off the aluminosilicate, the residual hardness x of the filtrate was determined. From it, the calcium binding power was calculated in mg CaO/gm. As according to the formula:
(30 - x) . 10 ` If calcium binding power is determined at higher tempera-ture, for example, at 60C, better values are obtained than at 22C. This fact distinguishes the aluminosilicates from most of the soluble sequestering agents that have been suggested so far for use in detergents and represents a particular technical pro-gress in their use.
Production conditions for aluminosilicate I:
Precipitation: 2.985 kg of an aluminate solution of the composi-tion 17-7% Na20, 15-8% Al203, 66.6% H20 0.15 kg of sodium hydroxide 9.420 kg of water 2.445 kg of a 25.8% sodium silicate solution of the composition 1 Na20. 6.0 SiO2, prepared freshly from commercial waterglass and easily alkali-soluble silica .~
Cry8tallization: 24 hours at 80C
Drying: 24 hours at 100C
~ , :
. - ' :
db¦~ -- :. ~ : . . ~ .
` ` lC~39608 Composition: 0.9 Na20 . 1 A12O3 . 2.04 SiO2 . 4.3 H20 (e2 l ~ 6% H20 ) ' Degree of cry6tsl-llzation: Fully crystalline Calclum binding power: 150 mg CaO/gm AS.
If the product obtained ~as dried for 1 hour at 400C, an aluminum silicate Ia was obtained of the composition: ~ ;
0.9 Na20 . 1 A1203 . 2.04 SiO2. 2.0 H2O t= 11-4% H2O) which is likewise suitable for the purposes of the invention.
Product conditions for aluminosilicate II:
Precipitation: 2.115 kg of an aluminate solution of the composition: 17.7% Na2O 15.8% A12O3, 66.5% H20 0.585 kg of sodium hydroxide 9.615 kg of water ;. 2.685 kg of a 25.8% sodium silicate solution of the composition: l Na20. 6 SiO2 (pre-- pared as under I) " 20 Crystallization: 24 hours at 80C
Drying: 24 hours at 100C and 20 torr.
Composition: 0.8 Na2O. 1 Al2O3. 2.655 SiO2. 5.2 H20 Degree of crystal-lization: Fully crystalline , :`
.~ Calcium binding ' power: 120 mg CaO/gm AS.
r ~ ' `
. ~ 9 ~
:: .
: ~ .
tb/~i!~
The aluminosl1icates I and II show in the x-ray dif-fraction diagram the following interference lines.
d- values, recorded with Cu-K~- radiation in A
I II
_ 14.4 12.4 - 8.8 8.6 . 7.0 ~ 4-4 (+)
4.1 (+) - 3.8 (+) 3.68 ~+) : 3.38 (+) 3.26 (+) - 2.96 (+) ~ 2.88 (+) .. ,~ .
~ 2.79 (+) . 2.73 (+) ~,, .
:. 20 - 2.66 (+) 2.60 (+) It is quite possible that not all these interference .~lines will appear in the X-ray diffraction diagram, particularly if the aluminosilicates are not futly crystallized. For this ~ .
. . .
:.~ reason, the d-v.alues which are the most important for the char-aeterization of these types are identi$ied by a "~+)".
,':
s ,, . .-."'' ~'.
O ~:
';.' :~' ., ~ .
. .
db~
. , . ., ~
The catldR-exchanglng aluml~oelllcates can partly or complotely replace the phosphorus-containlng inorganic or organlc cal¢iu~ sequèstering agenta Or the Nashlng and cleans-lng agent compositlon~ especially aodlu~ trlpolypho~phate, 80 that tbe phosphoru~ concentratio~ in the sewage i~ con-siderably redueed by U81ng the preparation according to the lnventlon in~tead o~ the kno~n preparatlon~ wlth a hlgh sod~u~
: tripolypho~phate content.
Among the percompounds servine as bleaGhlng agentB
and releaslng H22 in ~a~er, sodlum perborate tetrahydrate (NaB02 H2~ 3 H20) a~d the monohydrate (~aB02 ~22) are o~ partlcular i~portance, but also other H202-releasing borates can al~o be used, euch as p~rborax ~a2B4 ~ 4 H202.
The~ ¢ompounde can be roplaced partly or co~pletely by other c~rrier~ of actl~e oxygen, particularly by peroxyhydrates, ~uch a~ poroxycarbo~tes, (Na2C ~ 1.5 H202) or peroxypyro-pho~phate~.
It i8 reco~ended to incorpo~ate water-in~olubl~
. stabili3ers ~or the percompounds to~ether with the latter.
.. 20 Water-insoluble stabilizer~ are, ~r example, ~a~nesiu~ ~ilicatc , . .
havlng a NgO:SiO2 ratio of 4:1 to 1:4, preferably 2:1 to 1:2, : and particularly 1~ hlch are mostly obtained by precipita-tlon from aqueou~ solutlon~. In thelr plaee, othsr alkallne --e~rth mctal, cadmlu~ or tin sillcate~ o~ corresponding com-position~ are also w able. A130 hydrous oxldo~ of tln are `~ ~ultable a~ otabllizer~. The water-insoluble ~tablllzer~
and partlcularly m~gneslu~ sillcate can be i~corporated in the wa~hing agent composition both in the pre~ix accordin~ -: to the lnv~ntlon and in the atomlzation-drled powder~, addlng lt ln such amounts that the portlon Or the ~ini~hod ~ashi~e agent compositlonm 18 fro~ 1% to 4% by weight.
.
.. . ..
.
~1039608 In order to obtaln a satls~actory bleaching effect wlth the washing agent composltlons eontaining pereompounds at temperatures belo~ 80C, partieularly in th~ range of 40 to 60C, actlvator~ for the perco~pound~, particularly for perborate, can be lneorporated in the preparatlon~ in the pre~ix accordl~g to the i~vontlon. Preferred acti~ators are those of the type of the N-acyl compounds whieh have a ~elting : polnt Or at lea3t 70C, preferably at lOO~C~ for exa~ple, the co~pounds N,N,N'~N'-tetraac~tylethylenediamlne, tetraa¢etyl-glycoluril and tetrapropionylglycoluril. Particularly pre-erred as an acylated aetlvator for percompounds i~ tetra-aeetylglycolurll, melting point 233 to 240C, which 1~ al~o suitabl~ as a ~olid substrate and whlch has a gOoa activatin~
efiect i~ amounts of 0.1 to 1 mol p~r ~ atom o~ activated oxygen oi the p¢rcompound~. The premlxes according to the inventlon can contaln pre~erably rrO~ 15% to 25% by welght .. ~ of an activa~or a~ part of com~onent (B).
The inventlon also eoncerns a method for the pro-ductlon Or the above-de~lned pre~i~es, whieh iB charaeterize~
i~ that the liguid ~o~-ionic~ are applied on a ~oving powder the ~bove~defined eomponent~ according to (A) or on a ~; po~der ~ixture o~ the c~fflponent8 (A) and (B), a~d that the `~ premix product 1~ mlxed likewi~e with a powder in the pourable stat~, obtained by hot-drying of an aqueou co~po~ition con-81~ting of heat-inaen~itive co~pon~nts Or ~shing and elean~lDg ~ a~e~t co~po~ition8.
~ Preferably the ll~uid Non-lo~lcs, ~r those llque-fied by heati~g, are sprayed on the powder mlxture, ~hich 1~ done possibly in a closed ~essel. However, ~luld bed method~ can also be used.
''' .
_ 22 -.
... ..
1~39608 Apart from the components of the premix, the ~inished wa~hine and cleanslng agent composltions can al80 contaln the follo~ing co~ponents: anionic and/or non-ionic surface-actlv~ compound~ or tenslde~, ~urface-active or non-sur~ace-actlve ~oam stabllizers or foam l~hibltors, textile ~o~tening agents, neutral or alkallne reactlng builder co~-pounds, as well as auxiliary sub~bancea and additives ~hlch sre pre~ent in s~all a~ouAt~, such as eorros1on lnhlbitor~, -8011 8U8pen810n agent~, optical brlght~ners, dyes, etc.
The co~posltion Or a typlcal te~tlle ~ashlng agent co~pQsltlo~ to be usQd in the washing temperature ranup o~
30~:C to 100C i8 ~lthln the follo~ng formula:
:: 5~ to 30~ by ~ight Or anionic and/or non-ionic or amphoterlc ~ur~ace-actl~e eo~pounds;
~ 2.79 (+) . 2.73 (+) ~,, .
:. 20 - 2.66 (+) 2.60 (+) It is quite possible that not all these interference .~lines will appear in the X-ray diffraction diagram, particularly if the aluminosilicates are not futly crystallized. For this ~ .
. . .
:.~ reason, the d-v.alues which are the most important for the char-aeterization of these types are identi$ied by a "~+)".
,':
s ,, . .-."'' ~'.
O ~:
';.' :~' ., ~ .
. .
db~
. , . ., ~
The catldR-exchanglng aluml~oelllcates can partly or complotely replace the phosphorus-containlng inorganic or organlc cal¢iu~ sequèstering agenta Or the Nashlng and cleans-lng agent compositlon~ especially aodlu~ trlpolypho~phate, 80 that tbe phosphoru~ concentratio~ in the sewage i~ con-siderably redueed by U81ng the preparation according to the lnventlon in~tead o~ the kno~n preparatlon~ wlth a hlgh sod~u~
: tripolypho~phate content.
Among the percompounds servine as bleaGhlng agentB
and releaslng H22 in ~a~er, sodlum perborate tetrahydrate (NaB02 H2~ 3 H20) a~d the monohydrate (~aB02 ~22) are o~ partlcular i~portance, but also other H202-releasing borates can al~o be used, euch as p~rborax ~a2B4 ~ 4 H202.
The~ ¢ompounde can be roplaced partly or co~pletely by other c~rrier~ of actl~e oxygen, particularly by peroxyhydrates, ~uch a~ poroxycarbo~tes, (Na2C ~ 1.5 H202) or peroxypyro-pho~phate~.
It i8 reco~ended to incorpo~ate water-in~olubl~
. stabili3ers ~or the percompounds to~ether with the latter.
.. 20 Water-insoluble stabilizer~ are, ~r example, ~a~nesiu~ ~ilicatc , . .
havlng a NgO:SiO2 ratio of 4:1 to 1:4, preferably 2:1 to 1:2, : and particularly 1~ hlch are mostly obtained by precipita-tlon from aqueou~ solutlon~. In thelr plaee, othsr alkallne --e~rth mctal, cadmlu~ or tin sillcate~ o~ corresponding com-position~ are also w able. A130 hydrous oxldo~ of tln are `~ ~ultable a~ otabllizer~. The water-insoluble ~tablllzer~
and partlcularly m~gneslu~ sillcate can be i~corporated in the wa~hing agent composition both in the pre~ix accordin~ -: to the lnv~ntlon and in the atomlzation-drled powder~, addlng lt ln such amounts that the portlon Or the ~ini~hod ~ashi~e agent compositlonm 18 fro~ 1% to 4% by weight.
.
.. . ..
.
~1039608 In order to obtaln a satls~actory bleaching effect wlth the washing agent composltlons eontaining pereompounds at temperatures belo~ 80C, partieularly in th~ range of 40 to 60C, actlvator~ for the perco~pound~, particularly for perborate, can be lneorporated in the preparatlon~ in the pre~ix accordl~g to the i~vontlon. Preferred acti~ators are those of the type of the N-acyl compounds whieh have a ~elting : polnt Or at lea3t 70C, preferably at lOO~C~ for exa~ple, the co~pounds N,N,N'~N'-tetraac~tylethylenediamlne, tetraa¢etyl-glycoluril and tetrapropionylglycoluril. Particularly pre-erred as an acylated aetlvator for percompounds i~ tetra-aeetylglycolurll, melting point 233 to 240C, which 1~ al~o suitabl~ as a ~olid substrate and whlch has a gOoa activatin~
efiect i~ amounts of 0.1 to 1 mol p~r ~ atom o~ activated oxygen oi the p¢rcompound~. The premlxes according to the inventlon can contaln pre~erably rrO~ 15% to 25% by welght .. ~ of an activa~or a~ part of com~onent (B).
The inventlon also eoncerns a method for the pro-ductlon Or the above-de~lned pre~i~es, whieh iB charaeterize~
i~ that the liguid ~o~-ionic~ are applied on a ~oving powder the ~bove~defined eomponent~ according to (A) or on a ~; po~der ~ixture o~ the c~fflponent8 (A) and (B), a~d that the `~ premix product 1~ mlxed likewi~e with a powder in the pourable stat~, obtained by hot-drying of an aqueou co~po~ition con-81~ting of heat-inaen~itive co~pon~nts Or ~shing and elean~lDg ~ a~e~t co~po~ition8.
~ Preferably the ll~uid Non-lo~lcs, ~r those llque-fied by heati~g, are sprayed on the powder mlxture, ~hich 1~ done possibly in a closed ~essel. However, ~luld bed method~ can also be used.
''' .
_ 22 -.
... ..
1~39608 Apart from the components of the premix, the ~inished wa~hine and cleanslng agent composltions can al80 contaln the follo~ing co~ponents: anionic and/or non-ionic surface-actlv~ compound~ or tenslde~, ~urface-active or non-sur~ace-actlve ~oam stabllizers or foam l~hibltors, textile ~o~tening agents, neutral or alkallne reactlng builder co~-pounds, as well as auxiliary sub~bancea and additives ~hlch sre pre~ent in s~all a~ouAt~, such as eorros1on lnhlbitor~, -8011 8U8pen810n agent~, optical brlght~ners, dyes, etc.
The co~posltion Or a typlcal te~tlle ~ashlng agent co~pQsltlo~ to be usQd in the washing temperature ranup o~
30~:C to 100C i8 ~lthln the follo~ng formula:
:: 5~ to 30~ by ~ight Or anionic and/or non-ionic or amphoterlc ~ur~ace-actl~e eo~pounds;
5% to 70% by welght of water-insoluble, but water_containing, : ~ ~ ooili~ate~ of the defi~itiQn indieated under (A);
2% to 45% by ~ei~ht o~ water-soluble s-questering ~gent~ for calcium 10~8;
O t~ 50% by ~lght o~ builder co~pound~ not capable of se~u~toring calclu~ ions, particulaxly alkaline builder ~alt~;
O to 40~ by welght Or A-bleachln~ co~ponent cQn~istln~ Or percompou~ds, particul~rly 80diu~ p~rborate, and, optlonally, ~tabilizers and/or activators;
O to 10~ by weight of other additlve~, which ar~ ~oatly present in 8~11 a~ount~ in textile wa~hlng compositions.
~ The pre-washlng and maln wa~hin~ agent co~po~itlon~
of this ~ormula contain no percompound~ tho full range wa~hing agent compo~ition~ u~ed pre~rably at hlgh or co~klng _ 23 -~ 1~39608 temperature~, the content o~ the ~leachlng compo~ent 18 10%
to 40% by ~eight.
The quantitative data refer to the entire for~ula, dlsregarding the fact. that lt con~ of both a premix and a hot-dried poNder in ad~ixture. Indi~idual component~, particularly the alumlnosllicate~, c~n be present both in the premlxes and the hot-dried co~ponent.
The washing and clean~ing ~gent compo3itions obtained accordlng to the invsntlon are used pre~erably ~or 10 wa~hing textiles, but they ca~ al~o be w ed ~or cle~ning the ~urface~ Or non-textile obJect~, particularly ~arlous household appliances.
Here follow~ a list o~ co~pound3 in ~ach of the abov~ classlilcatlo~ ~hich are sultable ror u~ in the pre-parQtions accoraing to the inventlon.
Tho anlonic or a~photerlc ~urface-acti~e compounds or ten~lde~ contain ln the mol~cule at lea~t one hydrophobic - organic molety and on~-water-~olubillzing, anionic or ampho-~ terlc group. The hydrophobic molety i8 mo~tly an aliphatic -~ 20 hydrocarbon radical ~ith 8 to 26, pre~erably 10 to 22 ana particul~rly 12 to 18,carbon atoms or an alkyl aro~atic radlcal, such as alkylphenyl, wlth 6 to 18, preferably 8 t0 16, aliphatic c~rbon atom~.
Among the anionic sur~ace-active compounda are, ~or exaE~le, 80~p8 of natural or synthetlc, pre~erably - saturated, fatty aclds, optlonally al~o, ~oaps of reslnic or n~phthonlc acid~. Suitablo 8ynthetic anionlc tenaides are those of the type of the sulfonate~, 9ul~ate8 and synthetic carboxylates~
_ 24 -"` :10396Q8 Sultable anlon~c tensldes of the sulfonate type are alkyl-benzene sulfonates (Cg 15 alkyl) mixtures of alkenesulfonates and hydroxyalkanesulfonates, as well as alkanedisulfonates, as the~J
are obtained, for example, from monoolefins with terminal or non-terminal double bonds by sulfonation with gaseous sulfur tri-oxide and subsequent alkaline or acid hydrolysis of the sulfona-: tion products. Also suitable are alkanesulfonates which are obtained from alkanes by sulfochlorination or sulfoxidation and subsequent hydrolysis or neutralization or by bisulfite addition to olefins. Other suitable tensides of the sulfonate type arethe esters of ~-sulfofatty acids, for example, the ~-sulfonic ` acids of hydrogenated methyl or ethyl esters of coconut, palm-kernel or tallow fatty acids.
` Suitable tensides of the sulfate type are the sulfuric ;
acid monoesters of primary alcohols (e.g. from coconut fatty al-cohols, tallow fatty alcohols or oleyl alcohol) and those of ~` secondary alcohols. Also suitable are sulfated fatty acid -alkanolamides, sulfated fatty acid monoglycerides or sulfated resction products of 1 to 4 mols of ethylene oxide with primary ; 20 or secondary fatty alcohols or alkylphenols.
Other suitable anionic tensides are the fatty acid esters or amides of hydroxy- or amino-carboxylic acids or sulfonic acids, . .r .
such as the fatty acid sarcosides, fatty acid glycolates, fatty .; acid lactates, fatty acid taurides or fatty acid isoethionates.
.,"~,, .
~ The anionic tensides can be present in the form of their ",,. ~
~ alkali metal salts, ~uch as the sodium or potassium salts, the ~ . ~
ammonium salts, as well as soluble salts of organic bases, such as the lower alkylolamines, for example, mono-, di- or triethanol am~ne.
2 ~ ~
~ ,.
tb/~
.~ .. . . .
, . .. .
The foamlng power of the tenside can be lncreased or reduced by combination of suitable tenside types. A reduction can also be achieved by additions of non-surface-active organic substances.
A reduced foaming power, that is desirable ~or the use in washing machines, is often attained by combination of different tenside types, such as of sulfates and/or sulfonates with the - nonionics, and/or with soaps. In soaps, the foam inhibition in-creases with the degree of saturation and the number of carbons in the fatty acid residue. Soaps derived from saturated C20 24 fatty acids have been proven good as foam inhibitors.
The amphoteric surface-active compounds or tensides which can be employed are particularly betaines containing a quadruple substituted, that is, quaternary ammonium group and a covalently-bound acid group, whose positive and negative charges are ba-lanced intramolecularly. The betaines have on the nitrogen at ~
most two, but generally only one higher-molecular-weight ali- ~ -phatic hydrocarbon radical of a hydrophobic nature, and at least one, but gene~ally two, lower alkyl radicals with 1 to 3 carbon a~oms, which can be substituted by hydroxyl groups or connected with each other directly or over a hetero atom. The anionic, water-solubilizing acid group is connected with the ammonium nitrogen over the fourth substituent, which consists mostly of . . . - ::.
a short-chained aliphatic radical having, optionally, a double bond or a hydroxyl group, such as an alkylene, hydroxyalkylene or alkenylene, all having from 1 to 3 carbon atoms. Typical re-presentatives are, for example, the compounds:
3-(N-hexadecyl-N,N-dimethylammonio~-propane sulfonates, .' '. , 2 B :
.
:
.:
db/~
- : . ,, ~039608 3-(N-tallow-alXyl-N,N-dimethyl~mmonio)-2-hydroxypropane 8~ onate3, : 3-(N-hexadecyl-N,N-bis-~2-hydroxyethyl3-ammonio)-2-hydroxy-- pro wl sulfate, and N-tetradecyl-N,N-di~ethyl-a~onio-acetate.
Compound~ can al30 be used for the purpo e3 of the inventi~n es seq~eeterlng agent~ ~or calcium with such a se~uester~ng capacity that they were not considered heretofore aæ typical ~eque~tering age~ts for calclum, but ~uch eompounds . 10 are frequently capable of delaying the precipitation of cal-: cium carbonate from aqueou~ solutlon.
Amon8 the ~e~uestcrlng agents are thos~ of an inorganlc nature, such a~ the alkali ~etal pyrophosphate~, tripolyphosph~tes, hlgher polypho~phate~ and ~taphosphat~.
Org~nlc co~pounds which are u~ed as ~equestering agents are found, as known, among the polycarboxylic acid~, hydroxyearboxylic acids, amlnoearboxyl~e acids, ~arboxyalkyl ether~, poly~n~ onie polym0r~, and particularly the polymeric ~ earboxylic acids a~d the phosphonic a¢ids, these coalpound~ ~
:~ 20 being u~ed mo~tly in the form o~ their water-~oluble salts~
.~ ~uch as their aIkali metal ~alts.
W~akly acid, ~Rutral or alkaline-reacting i~organic - or organic salt~ ca~ b~ used a~ bullder -3alt8 as ladicated above.
Sultable ~akly acid, neutral or alkaline-reacting ~alts ~or use according to the inventio~ are, for exa~ple, the bicarbonate~, carbo~t~, bora~s or silicatea of thc alkali ~etal~, alkali metal sul~ates, as well a~ the alkali metal ~alts or organic, non~urf~ce-actlve ~ul~onic acids, carboxylic acld~ and ~ulfocarboxylic acid~ c~ntaining from - 27 _ ,. .
. -.. , . ~ . .. .
r ~ ~L039608 to 9 carbon atoms. The~e include, ~or example, water-soluble salts of benzenesulfonic acid, toluene~ulfonic acit or xylene-sulfonic acid, water-soluble salt6 of sulfoacetic acld, sulfo-benzoic acid or of sulfodicarboxylic acids, as well as the salts of acetic acid, lactlc acid, citric acid and tartaric acid.
The preparations according to the invention can further-more contain soil suspension agents or dirt carriers, which keep the dirt released from the fibers in suspension in the liquor and so prevent graying. Suitable compounds are water-soluble ~`
colloids, mostly of an organic nature, such as the water-soluble salts of polymeric carboxylic acids, glue, gelatin, salts of ether carboxylic acids or ether sulfonic acids of starch or cellu-; lose, or salts of acid sulfuric acid esters of cellulose or starch. Water-soluble polyamides containing acid groups are also suitable for this purpose. ~urthermore, soluble starch prepara-tions and other than the above-mentioned starch products can be ~;
` used, for example, degraded starches aldehyde starches etc.
Polyvinyl pyrrolidone can also be used. `~
The enzyme preparations to be used are mostly a mixture of enzymes with different effects, such as proteases, carbo-hydrases, esterases, lipases, oxidoreductases, catalases, pero-xidases, ureases, isomerases, lyases, transferases, desmolases, or nucleases. Of particular interest are the enzymes, obtained :.
from bacteria strains or from fungi, such as Bacillus subtilis or Streptomyces griseus, particularly proteases and amylases, which are relatively stable towards alkalis, percompounds, and anionic tensides and are still effective at temperatures up to 70C.
~:
, ~:
: 28 ~ ~:
- , :' . :~ `
... ~.~ ':``
db/~
.
. ::
' Enzyme preparations are marketed by the manufacturers ..
mostly as aqueous solutions of the actlve substances or as powders, granulates or as cold-sprayed products. They frequently contain sodium sulfate, sodium chloride, alkali metal ortho-, pyro- and polyphosphates, particularly tripolyphosphate, as fillers. Dust-:..
free preparations are particularly valued. These are obtainedin a known manner by incorporating of oily or pasty nonionics or by granulation with the aid of melts of water-of-crystallization-containing salts in their own water-of-crystallization.
Enzymes may be incorporated which are specific for certain types of soil, for example, proteases or amylases or lipases.
Preferably, combinations of enzymes with different effects are used, particularly combinations of proteases and amylases.
The washing agents can contain optical brighteners such as those for cotton, particularly derivatives of diaminostilbene-disulfonic acid or its alkali metal salts. Suitable are, for example, salts of'4,4'-bis-(2-anilino-4-morpholino-1,3,5-triazin-
2% to 45% by ~ei~ht o~ water-soluble s-questering ~gent~ for calcium 10~8;
O t~ 50% by ~lght o~ builder co~pound~ not capable of se~u~toring calclu~ ions, particulaxly alkaline builder ~alt~;
O to 40~ by welght Or A-bleachln~ co~ponent cQn~istln~ Or percompou~ds, particul~rly 80diu~ p~rborate, and, optlonally, ~tabilizers and/or activators;
O to 10~ by weight of other additlve~, which ar~ ~oatly present in 8~11 a~ount~ in textile wa~hlng compositions.
~ The pre-washlng and maln wa~hin~ agent co~po~itlon~
of this ~ormula contain no percompound~ tho full range wa~hing agent compo~ition~ u~ed pre~rably at hlgh or co~klng _ 23 -~ 1~39608 temperature~, the content o~ the ~leachlng compo~ent 18 10%
to 40% by ~eight.
The quantitative data refer to the entire for~ula, dlsregarding the fact. that lt con~ of both a premix and a hot-dried poNder in ad~ixture. Indi~idual component~, particularly the alumlnosllicate~, c~n be present both in the premlxes and the hot-dried co~ponent.
The washing and clean~ing ~gent compo3itions obtained accordlng to the invsntlon are used pre~erably ~or 10 wa~hing textiles, but they ca~ al~o be w ed ~or cle~ning the ~urface~ Or non-textile obJect~, particularly ~arlous household appliances.
Here follow~ a list o~ co~pound3 in ~ach of the abov~ classlilcatlo~ ~hich are sultable ror u~ in the pre-parQtions accoraing to the inventlon.
Tho anlonic or a~photerlc ~urface-acti~e compounds or ten~lde~ contain ln the mol~cule at lea~t one hydrophobic - organic molety and on~-water-~olubillzing, anionic or ampho-~ terlc group. The hydrophobic molety i8 mo~tly an aliphatic -~ 20 hydrocarbon radical ~ith 8 to 26, pre~erably 10 to 22 ana particul~rly 12 to 18,carbon atoms or an alkyl aro~atic radlcal, such as alkylphenyl, wlth 6 to 18, preferably 8 t0 16, aliphatic c~rbon atom~.
Among the anionic sur~ace-active compounda are, ~or exaE~le, 80~p8 of natural or synthetlc, pre~erably - saturated, fatty aclds, optlonally al~o, ~oaps of reslnic or n~phthonlc acid~. Suitablo 8ynthetic anionlc tenaides are those of the type of the sulfonate~, 9ul~ate8 and synthetic carboxylates~
_ 24 -"` :10396Q8 Sultable anlon~c tensldes of the sulfonate type are alkyl-benzene sulfonates (Cg 15 alkyl) mixtures of alkenesulfonates and hydroxyalkanesulfonates, as well as alkanedisulfonates, as the~J
are obtained, for example, from monoolefins with terminal or non-terminal double bonds by sulfonation with gaseous sulfur tri-oxide and subsequent alkaline or acid hydrolysis of the sulfona-: tion products. Also suitable are alkanesulfonates which are obtained from alkanes by sulfochlorination or sulfoxidation and subsequent hydrolysis or neutralization or by bisulfite addition to olefins. Other suitable tensides of the sulfonate type arethe esters of ~-sulfofatty acids, for example, the ~-sulfonic ` acids of hydrogenated methyl or ethyl esters of coconut, palm-kernel or tallow fatty acids.
` Suitable tensides of the sulfate type are the sulfuric ;
acid monoesters of primary alcohols (e.g. from coconut fatty al-cohols, tallow fatty alcohols or oleyl alcohol) and those of ~` secondary alcohols. Also suitable are sulfated fatty acid -alkanolamides, sulfated fatty acid monoglycerides or sulfated resction products of 1 to 4 mols of ethylene oxide with primary ; 20 or secondary fatty alcohols or alkylphenols.
Other suitable anionic tensides are the fatty acid esters or amides of hydroxy- or amino-carboxylic acids or sulfonic acids, . .r .
such as the fatty acid sarcosides, fatty acid glycolates, fatty .; acid lactates, fatty acid taurides or fatty acid isoethionates.
.,"~,, .
~ The anionic tensides can be present in the form of their ",,. ~
~ alkali metal salts, ~uch as the sodium or potassium salts, the ~ . ~
ammonium salts, as well as soluble salts of organic bases, such as the lower alkylolamines, for example, mono-, di- or triethanol am~ne.
2 ~ ~
~ ,.
tb/~
.~ .. . . .
, . .. .
The foamlng power of the tenside can be lncreased or reduced by combination of suitable tenside types. A reduction can also be achieved by additions of non-surface-active organic substances.
A reduced foaming power, that is desirable ~or the use in washing machines, is often attained by combination of different tenside types, such as of sulfates and/or sulfonates with the - nonionics, and/or with soaps. In soaps, the foam inhibition in-creases with the degree of saturation and the number of carbons in the fatty acid residue. Soaps derived from saturated C20 24 fatty acids have been proven good as foam inhibitors.
The amphoteric surface-active compounds or tensides which can be employed are particularly betaines containing a quadruple substituted, that is, quaternary ammonium group and a covalently-bound acid group, whose positive and negative charges are ba-lanced intramolecularly. The betaines have on the nitrogen at ~
most two, but generally only one higher-molecular-weight ali- ~ -phatic hydrocarbon radical of a hydrophobic nature, and at least one, but gene~ally two, lower alkyl radicals with 1 to 3 carbon a~oms, which can be substituted by hydroxyl groups or connected with each other directly or over a hetero atom. The anionic, water-solubilizing acid group is connected with the ammonium nitrogen over the fourth substituent, which consists mostly of . . . - ::.
a short-chained aliphatic radical having, optionally, a double bond or a hydroxyl group, such as an alkylene, hydroxyalkylene or alkenylene, all having from 1 to 3 carbon atoms. Typical re-presentatives are, for example, the compounds:
3-(N-hexadecyl-N,N-dimethylammonio~-propane sulfonates, .' '. , 2 B :
.
:
.:
db/~
- : . ,, ~039608 3-(N-tallow-alXyl-N,N-dimethyl~mmonio)-2-hydroxypropane 8~ onate3, : 3-(N-hexadecyl-N,N-bis-~2-hydroxyethyl3-ammonio)-2-hydroxy-- pro wl sulfate, and N-tetradecyl-N,N-di~ethyl-a~onio-acetate.
Compound~ can al30 be used for the purpo e3 of the inventi~n es seq~eeterlng agent~ ~or calcium with such a se~uester~ng capacity that they were not considered heretofore aæ typical ~eque~tering age~ts for calclum, but ~uch eompounds . 10 are frequently capable of delaying the precipitation of cal-: cium carbonate from aqueou~ solutlon.
Amon8 the ~e~uestcrlng agents are thos~ of an inorganlc nature, such a~ the alkali ~etal pyrophosphate~, tripolyphosph~tes, hlgher polypho~phate~ and ~taphosphat~.
Org~nlc co~pounds which are u~ed as ~equestering agents are found, as known, among the polycarboxylic acid~, hydroxyearboxylic acids, amlnoearboxyl~e acids, ~arboxyalkyl ether~, poly~n~ onie polym0r~, and particularly the polymeric ~ earboxylic acids a~d the phosphonic a¢ids, these coalpound~ ~
:~ 20 being u~ed mo~tly in the form o~ their water-~oluble salts~
.~ ~uch as their aIkali metal ~alts.
W~akly acid, ~Rutral or alkaline-reacting i~organic - or organic salt~ ca~ b~ used a~ bullder -3alt8 as ladicated above.
Sultable ~akly acid, neutral or alkaline-reacting ~alts ~or use according to the inventio~ are, for exa~ple, the bicarbonate~, carbo~t~, bora~s or silicatea of thc alkali ~etal~, alkali metal sul~ates, as well a~ the alkali metal ~alts or organic, non~urf~ce-actlve ~ul~onic acids, carboxylic acld~ and ~ulfocarboxylic acid~ c~ntaining from - 27 _ ,. .
. -.. , . ~ . .. .
r ~ ~L039608 to 9 carbon atoms. The~e include, ~or example, water-soluble salts of benzenesulfonic acid, toluene~ulfonic acit or xylene-sulfonic acid, water-soluble salt6 of sulfoacetic acld, sulfo-benzoic acid or of sulfodicarboxylic acids, as well as the salts of acetic acid, lactlc acid, citric acid and tartaric acid.
The preparations according to the invention can further-more contain soil suspension agents or dirt carriers, which keep the dirt released from the fibers in suspension in the liquor and so prevent graying. Suitable compounds are water-soluble ~`
colloids, mostly of an organic nature, such as the water-soluble salts of polymeric carboxylic acids, glue, gelatin, salts of ether carboxylic acids or ether sulfonic acids of starch or cellu-; lose, or salts of acid sulfuric acid esters of cellulose or starch. Water-soluble polyamides containing acid groups are also suitable for this purpose. ~urthermore, soluble starch prepara-tions and other than the above-mentioned starch products can be ~;
` used, for example, degraded starches aldehyde starches etc.
Polyvinyl pyrrolidone can also be used. `~
The enzyme preparations to be used are mostly a mixture of enzymes with different effects, such as proteases, carbo-hydrases, esterases, lipases, oxidoreductases, catalases, pero-xidases, ureases, isomerases, lyases, transferases, desmolases, or nucleases. Of particular interest are the enzymes, obtained :.
from bacteria strains or from fungi, such as Bacillus subtilis or Streptomyces griseus, particularly proteases and amylases, which are relatively stable towards alkalis, percompounds, and anionic tensides and are still effective at temperatures up to 70C.
~:
, ~:
: 28 ~ ~:
- , :' . :~ `
... ~.~ ':``
db/~
.
. ::
' Enzyme preparations are marketed by the manufacturers ..
mostly as aqueous solutions of the actlve substances or as powders, granulates or as cold-sprayed products. They frequently contain sodium sulfate, sodium chloride, alkali metal ortho-, pyro- and polyphosphates, particularly tripolyphosphate, as fillers. Dust-:..
free preparations are particularly valued. These are obtainedin a known manner by incorporating of oily or pasty nonionics or by granulation with the aid of melts of water-of-crystallization-containing salts in their own water-of-crystallization.
Enzymes may be incorporated which are specific for certain types of soil, for example, proteases or amylases or lipases.
Preferably, combinations of enzymes with different effects are used, particularly combinations of proteases and amylases.
The washing agents can contain optical brighteners such as those for cotton, particularly derivatives of diaminostilbene-disulfonic acid or its alkali metal salts. Suitable are, for example, salts of'4,4'-bis-(2-anilino-4-morpholino-1,3,5-triazin-
6-yl-amino)-stilbene-2,2'-disulfonic acid or similarly compounds which have instead of the morpholino group, a diethanolamino group, a methylamino group or a 2-methoxy-ethylamino group. ~righteners for polyamide fibers which can be used are those of the type of the 1,3-diaryl-2-pyrazolines, for example, the compound l-(p-sulfamoylphenyl)-3-(p-chlorophenyl)-2-pyrazoline, as well as com-pounds of similar composition which have instead of the sulfamoyl group, for example, the methoxycarbonyl group, the 2-methoxy-ethoxycarbonyl group, the acetylamino group or the vinylsulfonyl group. Suitable polyamide brighteners are also the substituted aminocumarins, for example, 4-methyl-7-dimethylamino-cumarin or 4-methyl-.
~ 29 "
-~ :
.
db/Sj~
~ , .
, . ~ , . ~
~ 29 "
-~ :
.
db/Sj~
~ , .
, . ~ , . ~
7-dlethylaminocumarin. Furthermore, the compound~ 1-(2-benzimidazolyl)-2-(1-hydroxyethyl-2-benzimidazolyl)-ethylene and l-ethyl-3-pheny1-7-dlethylamino-carbo~tyril can al~o be used as polyamide brightener~. Brighteners for polyester and polyamide ~ibers which can be u~ed are the compounds 2,5-dl-(2-benzoxazolyl)-thiophene,2-(2-benzoxazolyl)-naphtho-[2,3-b~-thiophene and 1,2-di-(5-methyl-2-benzoxazolyl)-ethylene.
Furthermoro, brighteners Or the type of the substituted 4,4'-distyryl-diphenyl~ can be utilize~, for examplo, the compound 4,4'-bl~-(4-chloro-3-sul~ostyryl)-diphengl. ~ix~ure~ of the above-mentio~ed brlghtener~ can likewi3e be u~ed.
The rollowlng speclflc embodi~ent~ aro ill~stratlve Or the inventlon without being li~ltatlv~ in any r~s~ect.
E X A M P L E S
The alumin~silicate u~ed in the example~ has the folloNing composltion:
O.9 Na20 A1203 2.0 SiO2 4 ~2 a~d a calclum bind~ng power o~ 165 mæ CaO/g~ AS. The partlclo 8iz~ distrlbutiQ~ wa8 within the ~ollowlng range:
~ 40Ju ~ 0% by wolght Maxi~um rang~ o~ the particle 30~u ~ 100% by weight ~ize diatributi0~ curve at < 10Jl = 90% ~y ~eight 1 to 5)u.
The ~ was a commercial product of the approxim~te com~o~ition:
~aB2 ~22 3 H~O, bulk d~nsity 830 gm/l.
: "TA + 5 ~0", "TA + 14 EO", "OC~ + 10 EO" are the additlon products of 5, 14 and 10 mols of ethylene oxlde ~EO) to 1 mol of tallow ~atty alcohol (TA) (lodine number = 0.5) and oleyl/cotyl al~ohol (lodine nu~ber - 50).
...
. .
,' . . . ~ . : .
` 1039608 Th~ ~'sllica~ o~ the premixe~ was a highly disper~ed slllcon dlQxlde wlth a partlcle size r~Dge of 1 to 12 ~, a llter weight of 90 to 100 gm/l, and a BET-sur~acs area of 300 m2/gm.
The follewlng Table I conta~ns the formulas of some premixos ~hich had been produce~ ln a closod mixor by spraylng the liquid Non-ioDlcs on the moving powd~r mlxture.
.. 'i .
. . .
- .
. .
,~
-' .
. .
.
: ;
~03960~9 ' _ o oo ~. .:
.,.................. ~ ' ~ ' ~,, ' ,, ., ~ o~ o ~ o U~ o ,. ~
~ ~ i ~:
. ~ 0 o o o ~ ~.
,,` Y~ ~
: ~ ~ ~ ~ t H P- ~ ~ ~1 ~: ~
or~ ~o I I ~
~1 ~ ~ ,, o ~
~.
~ ~ ~
~ ~' ~' ~ ~ ~ U~ C~ O ':
"/ ~ o O
~. ~ ~ l ~ ' . `.
r~1 O O ,.~
; ~ I U~ I I I ,~ I : ' L~ ~ ~ a d~l .. ~ O ~'aD
,`
~"'.
_ 32 - ~
`. . ..
e following examples give formulas oi ~ashing agent compo~ltion~ which contain the pre~ixes according to - Examples V l to V lO.
Ths salt constituent~ contained in the de*ertents of the examples, such as sur~actant~ ln ~alt forL, other : organic salts, as well as inorg~nic ~alts, Nere present as sodium salt, unless explicit~ ~tated otherwise.
"ABS" - the salt o~ alkglbenzenesulfonic acld ~lth ~0 to 15, pre~erably ll to 13, carbon atoma ~n the alkyl chain obtained by co~d~nsation of ~traight-chain ole~ wlth benzene and ~ulfonation Or the alkylbenzene thu~ o~tained.
nOlefinsulfonat~" - a sulfonate obtained from a-ole~in ~l~tures having 12 to 18 carbon ato~s by sulronatlng wlth S03 and hydrolyzing the ~ul~onatlon product wlth sodlu~ hydroxide 801utio~, conslstlng essentlally o~ alken~ sulfonat~ and hydroxyalkan sulfonate, but also containing sm~ll amounts o~
alkanedisulronate 8 .
: "~s-ester ~ulfonate" - a ~ulfonate obtained by ~ul-.- fonat~6 hydrogenated palm ker~el fatty aci~ methyl ester -.` 20 with S03.
: nAl~anesulfonate" - a 8ul~0nate obtainsd by 8ulfo~1-datio~ Or para~fin~ haviag 12 to 18 carbon atoms.
nSoap" - the gatty acld co~pone~t of a hardened ~ixture o~ equal part8 ~y ~eight of tallo~ and ra~ oil ~atty acid~ (Cl~-C~2, iodine ~umber ~ l).
'~ A" - the salt Or ethylenedia~lnotetraacetic ~cid.
CMCn - the ~alt ~r carboxymethyl cellulose.
. , .
1039~08 The follo~ing cQ~talns ~ormulations of some ~a~hing agent compositions according to the ln~entlon. These compo~
~lons were obtained ~rom the premixe~ according to Examples . Vl to V 10 by mlxing with a powder produced by hot ato~ization of an aqueou~ solutlon containing the listed lngred~ent~.
Both the premlxes and the finl~hed washlng agent composition~
~ ~howed good powder properties. They were easily pourable, : despite their content o~ oily or pasty Non-lonlc~.
' E ~ W 1 Low-phosphate ~ull ran~e washing a~ent compo~ition The pr~parA~lon ~as obtained by mixlng 59 part~ by -~ weight Qf pro~ix V 3 with 41 part~ by welght of.a powder obtained by hot atomixation (Tower Powd~r No. 1) of th~
following compo~ition:
~ By Welght : ~BS 19.6 Soap 9.5 :: EDTA o.9 odiu~ tripolyphosphate 28.0 Watergla~s (1:3.3) 14.0 . Sodi~m sulfate 1.4 : Magnesium slllcate 5.S
- CMC 4.2 :
;:~ Balance (water, perfu~e, optical brighteners) 16.8 The fin~l full range ~a~hing age~t compo~ition cp~ained the following~
~ ~ , , 10396Q8 %13y Wei~ht ABS ~ 8.03 TA + 5 E0 3-7 TA + 14 E0 7.08 Soap 3.89 Sodium trlpolyphosphate 11.49 Aluminosilicate 20.36 P~rborato 28 . 50 ME~gne~ium æillcate 2.29 Water~lass 5.74 Sodium ~ul~ate o.57 CMC 1. 72 Balance (water, perrume, optical brlghteners ) 6 . 89 ELU~E W 2 osphato-rree full ra~e ~a~hing aç~ent compo~itioQ
.~ The prsp~ration wa# obtalne~ by ~ g 57 part~ of th~ prer~ V 4 with 43 part8 by ~eight oi a powder obtaln~d by 20 hot ato~ization o~ the ~ollow~g ~ompc~ition (~ower P~wder ~o.2):
% By Wei~ht Fs-ester 8ul~0nate 7.0 ~ ~DTA o . 6 Sodium cltrate 20.0 Alulaino~illcate 25.3 Waterglaes (1:3.3) 10.2 Sodium sul~ate 13.8 Magn s~um ~ilic~te 4.8 CMC 3 . 9 ~alanc~ (~rater, perruEIle~ optical br~ ~htener) 14 .4 - 35 ~
. ~ .
~039608 The preparation contalns 28.5% by ~elght ef ~odium perborate. Ihe water-insoluble calcium-blnding aluminosllicate Wa8 incorporRted ln the preparation both through the premix and through the Tower Powder in a total amount of 29.2% by ~alght.
EXAMP~ W 3 Low-pho~phat~ pre~a~hing a~ent compo~itlon The prepar~tlon was obtained by ml~in~ 50 parts by ~eight Or pr mix ~ 1 and 50 parts by ~eight o~ Tower Powder No. 1 indicated ln Example ~
~XAMPIE W 4 Phos~hate-iree main ~ashln~iagent compo~ition .
. The prepnratlon wae obta~aed by mixi~g 60 part~ by ~:
~E weieht Or premix V 2 wlth 40 par~ by ~oight o~ Tower Powder ` No. 2 indicated ~ Example W 2.
,, EXA ~ W 5 The preparation W~B ob~ained by ~ixlng 40 p~rt~ by weight of premix V 8 ~ith 60 parts by weight Or a Tower powder ~-. obtalned by hot atomizati~a of the following compo~ition: :
Tower Po~der No. 3 ~ By Weight Alkane~7~onate 8.Q
: Soap 5 0 TA + 14 ~0 5.0 .~ Sodium tripolyphosphata 30.0 Waterglas~ 3.3) a.o Sodlum carbonate 8.0 CMC 3.o : Sodiu~ sulrate 20.0 `
Balanee (water, perfume, optical bri~htener) 12.5 ~: ' .: .
. . . ~ . , . ~
_ osphate-~ree prewashlng agent compositlon m e preparatlon wa8 obtained by mixing 50 parts by ~elght o~ pre~lx V 1 and 50 par~s..by weight Or a Tower pow~er obtalned by hot atomization of the roll~wing compo~ltlon:
Tower Powder No. 4 % ~ Wei~ht . .
Ole~insulfo~ate 6.0 TA + 5 EO 4.o Waterglas~ 3.3) 10.0 :. 10 CMG 3.0 Sodium citrate 8.0 Sodlum sul~Ate 58.5 Balance (water, p~rfu~e, optlca~
brigh~ener) 1~.5 . ~XA~PIæ W 7 .. Low-phosphate bleaching washin~gent co~posi~ion : ~or 60C ~ashi~
~ 4 m e praparatlon ~a8 obtained by mixing 40 part~ by . .
watght of premix V 9 and 60 part~ by weight of a T~wer po~der obtainea by hot atomizatlon of the followlng composltlon:
Tow~r Po~dor No. 5 ~ By Nei~ht Toluene sul~onat~ 2.5 Soap ~.2 ~DTA o.5 Sodium trlpolypho~ph~to 25.0 ~atergla~3 (1:3.3) 8.3 - C~C 3.o Alumino~llicate 16.7 Magne~lum Billeate 3.o Balance (~odium ~ulfate~ optical brl~hte~or) 31.0 : ~.
10396(~8 The preparation cont~lns 10.4% by ~elght Or ~odlum perborate and 9.6% by weight of tetraacetyl glycoluril a~ a perborat~ activator. The w~ter-in~olubl~ calclu~ bindlng alu~inosillcate ~as incorporated ln the preparatlon through both the pre~ix and the Tower poNder in a total a~ount of 22.6% by weieht.
: BxAMPLæ W 8 ~- Lo~-phosphate bleaching ~a~hing agent compositlon ~or washin~ at 60C
- 10 The prep~ration W~5 obtained by mixing 50 parts by welght of premlx V 10, 40 parts by welght o~ Tower Powd~r No. ~ -1 a~d 10 part~ ~y w~ight of sodium perborate.
If it i~ deslred to reduce the ~oaming p~er of the ~ashlng age~t co~po~itlon~, known fo~m inhibltors are work0d in. miB iB partlcularly tr~o for preparatio~ wh1ch contai~ no 80ap.
m~ non-tensiae foam iDhibitor~ included N-alkylated a~inotriazines, QptiQnally conta~nlng chlorine, wh~ch are : obtainod by ~he reaction of 1 ~ol o~ cy~nuric acld Ghloride :.
~ith 2 to 3 mols of a mono- a~d/or dialkylamine with 6 to 20, preferably a to 18, carbon atoms in the alkyl radieal~. SiQi-larly ef~ctlve are propoxyl~tad and/or but0xylated amin -triazine~, such as products that are obtalned by tbe a~ditlon . ~ Or ~rom 5 to 10 mol~ o~ propylene oxiae to 1 mol Or ~elamine -:
: and fur~her additlon Or from 10 to 50 mol~ o~ butylene oxlde to tbi8 propyle~e-oxide d~rivative.
Lik~wise suitable as non-t~ide *oam inhibitbr~
are water-~n~oluble organic compound~, like paraffin~, or halogenated p~rar~ins w~th melti~g point~ below 100C, aliph~tic G18 to C40 keton~, a~ well ~8 aliphatic carboxylic .; .
` ~039f~08 acid esters whlch contain in the acid or alcohol resldue, optionally, also in both of theso resi~ues, at least 18 carbon atoms (such as triglycerides or fatty acid/fatty alcohol esters). These compound~ can ~e used to reduce ~oaming, particularly in combination~ of tensides of the ~ulfate and/or sulfonate type with soaps. Also alkali-~table silicones ~ay be incorporated as non-ten~ide foam t~hibitors.
The precedl~g specific embodiments are illu~tratlYe oi the practice of the in~entio~. It ls to be understooa, 10 however, that other expedients hno~n to tho~e skllled ln the art or disclosed herein, may be employed without departing from the spirit of the in~ention or the scope of the appended claims.
.
Furthermoro, brighteners Or the type of the substituted 4,4'-distyryl-diphenyl~ can be utilize~, for examplo, the compound 4,4'-bl~-(4-chloro-3-sul~ostyryl)-diphengl. ~ix~ure~ of the above-mentio~ed brlghtener~ can likewi3e be u~ed.
The rollowlng speclflc embodi~ent~ aro ill~stratlve Or the inventlon without being li~ltatlv~ in any r~s~ect.
E X A M P L E S
The alumin~silicate u~ed in the example~ has the folloNing composltion:
O.9 Na20 A1203 2.0 SiO2 4 ~2 a~d a calclum bind~ng power o~ 165 mæ CaO/g~ AS. The partlclo 8iz~ distrlbutiQ~ wa8 within the ~ollowlng range:
~ 40Ju ~ 0% by wolght Maxi~um rang~ o~ the particle 30~u ~ 100% by weight ~ize diatributi0~ curve at < 10Jl = 90% ~y ~eight 1 to 5)u.
The ~ was a commercial product of the approxim~te com~o~ition:
~aB2 ~22 3 H~O, bulk d~nsity 830 gm/l.
: "TA + 5 ~0", "TA + 14 EO", "OC~ + 10 EO" are the additlon products of 5, 14 and 10 mols of ethylene oxlde ~EO) to 1 mol of tallow ~atty alcohol (TA) (lodine number = 0.5) and oleyl/cotyl al~ohol (lodine nu~ber - 50).
...
. .
,' . . . ~ . : .
` 1039608 Th~ ~'sllica~ o~ the premixe~ was a highly disper~ed slllcon dlQxlde wlth a partlcle size r~Dge of 1 to 12 ~, a llter weight of 90 to 100 gm/l, and a BET-sur~acs area of 300 m2/gm.
The follewlng Table I conta~ns the formulas of some premixos ~hich had been produce~ ln a closod mixor by spraylng the liquid Non-ioDlcs on the moving powd~r mlxture.
.. 'i .
. . .
- .
. .
,~
-' .
. .
.
: ;
~03960~9 ' _ o oo ~. .:
.,.................. ~ ' ~ ' ~,, ' ,, ., ~ o~ o ~ o U~ o ,. ~
~ ~ i ~:
. ~ 0 o o o ~ ~.
,,` Y~ ~
: ~ ~ ~ ~ t H P- ~ ~ ~1 ~: ~
or~ ~o I I ~
~1 ~ ~ ,, o ~
~.
~ ~ ~
~ ~' ~' ~ ~ ~ U~ C~ O ':
"/ ~ o O
~. ~ ~ l ~ ' . `.
r~1 O O ,.~
; ~ I U~ I I I ,~ I : ' L~ ~ ~ a d~l .. ~ O ~'aD
,`
~"'.
_ 32 - ~
`. . ..
e following examples give formulas oi ~ashing agent compo~ltion~ which contain the pre~ixes according to - Examples V l to V lO.
Ths salt constituent~ contained in the de*ertents of the examples, such as sur~actant~ ln ~alt forL, other : organic salts, as well as inorg~nic ~alts, Nere present as sodium salt, unless explicit~ ~tated otherwise.
"ABS" - the salt o~ alkglbenzenesulfonic acld ~lth ~0 to 15, pre~erably ll to 13, carbon atoma ~n the alkyl chain obtained by co~d~nsation of ~traight-chain ole~ wlth benzene and ~ulfonation Or the alkylbenzene thu~ o~tained.
nOlefinsulfonat~" - a sulfonate obtained from a-ole~in ~l~tures having 12 to 18 carbon ato~s by sulronatlng wlth S03 and hydrolyzing the ~ul~onatlon product wlth sodlu~ hydroxide 801utio~, conslstlng essentlally o~ alken~ sulfonat~ and hydroxyalkan sulfonate, but also containing sm~ll amounts o~
alkanedisulronate 8 .
: "~s-ester ~ulfonate" - a ~ulfonate obtained by ~ul-.- fonat~6 hydrogenated palm ker~el fatty aci~ methyl ester -.` 20 with S03.
: nAl~anesulfonate" - a 8ul~0nate obtainsd by 8ulfo~1-datio~ Or para~fin~ haviag 12 to 18 carbon atoms.
nSoap" - the gatty acld co~pone~t of a hardened ~ixture o~ equal part8 ~y ~eight of tallo~ and ra~ oil ~atty acid~ (Cl~-C~2, iodine ~umber ~ l).
'~ A" - the salt Or ethylenedia~lnotetraacetic ~cid.
CMCn - the ~alt ~r carboxymethyl cellulose.
. , .
1039~08 The follo~ing cQ~talns ~ormulations of some ~a~hing agent compositions according to the ln~entlon. These compo~
~lons were obtained ~rom the premixe~ according to Examples . Vl to V 10 by mlxing with a powder produced by hot ato~ization of an aqueou~ solutlon containing the listed lngred~ent~.
Both the premlxes and the finl~hed washlng agent composition~
~ ~howed good powder properties. They were easily pourable, : despite their content o~ oily or pasty Non-lonlc~.
' E ~ W 1 Low-phosphate ~ull ran~e washing a~ent compo~ition The pr~parA~lon ~as obtained by mixlng 59 part~ by -~ weight Qf pro~ix V 3 with 41 part~ by welght of.a powder obtained by hot atomixation (Tower Powd~r No. 1) of th~
following compo~ition:
~ By Welght : ~BS 19.6 Soap 9.5 :: EDTA o.9 odiu~ tripolyphosphate 28.0 Watergla~s (1:3.3) 14.0 . Sodi~m sulfate 1.4 : Magnesium slllcate 5.S
- CMC 4.2 :
;:~ Balance (water, perfu~e, optical brighteners) 16.8 The fin~l full range ~a~hing age~t compo~ition cp~ained the following~
~ ~ , , 10396Q8 %13y Wei~ht ABS ~ 8.03 TA + 5 E0 3-7 TA + 14 E0 7.08 Soap 3.89 Sodium trlpolyphosphate 11.49 Aluminosilicate 20.36 P~rborato 28 . 50 ME~gne~ium æillcate 2.29 Water~lass 5.74 Sodium ~ul~ate o.57 CMC 1. 72 Balance (water, perrume, optical brlghteners ) 6 . 89 ELU~E W 2 osphato-rree full ra~e ~a~hing aç~ent compo~itioQ
.~ The prsp~ration wa# obtalne~ by ~ g 57 part~ of th~ prer~ V 4 with 43 part8 by ~eight oi a powder obtaln~d by 20 hot ato~ization o~ the ~ollow~g ~ompc~ition (~ower P~wder ~o.2):
% By Wei~ht Fs-ester 8ul~0nate 7.0 ~ ~DTA o . 6 Sodium cltrate 20.0 Alulaino~illcate 25.3 Waterglaes (1:3.3) 10.2 Sodium sul~ate 13.8 Magn s~um ~ilic~te 4.8 CMC 3 . 9 ~alanc~ (~rater, perruEIle~ optical br~ ~htener) 14 .4 - 35 ~
. ~ .
~039608 The preparation contalns 28.5% by ~elght ef ~odium perborate. Ihe water-insoluble calcium-blnding aluminosllicate Wa8 incorporRted ln the preparation both through the premix and through the Tower Powder in a total amount of 29.2% by ~alght.
EXAMP~ W 3 Low-pho~phat~ pre~a~hing a~ent compo~itlon The prepar~tlon was obtained by ml~in~ 50 parts by ~eight Or pr mix ~ 1 and 50 parts by ~eight o~ Tower Powder No. 1 indicated ln Example ~
~XAMPIE W 4 Phos~hate-iree main ~ashln~iagent compo~ition .
. The prepnratlon wae obta~aed by mixi~g 60 part~ by ~:
~E weieht Or premix V 2 wlth 40 par~ by ~oight o~ Tower Powder ` No. 2 indicated ~ Example W 2.
,, EXA ~ W 5 The preparation W~B ob~ained by ~ixlng 40 p~rt~ by weight of premix V 8 ~ith 60 parts by weight Or a Tower powder ~-. obtalned by hot atomizati~a of the following compo~ition: :
Tower Po~der No. 3 ~ By Weight Alkane~7~onate 8.Q
: Soap 5 0 TA + 14 ~0 5.0 .~ Sodium tripolyphosphata 30.0 Waterglas~ 3.3) a.o Sodlum carbonate 8.0 CMC 3.o : Sodiu~ sulrate 20.0 `
Balanee (water, perfume, optical bri~htener) 12.5 ~: ' .: .
. . . ~ . , . ~
_ osphate-~ree prewashlng agent compositlon m e preparatlon wa8 obtained by mixing 50 parts by ~elght o~ pre~lx V 1 and 50 par~s..by weight Or a Tower pow~er obtalned by hot atomization of the roll~wing compo~ltlon:
Tower Powder No. 4 % ~ Wei~ht . .
Ole~insulfo~ate 6.0 TA + 5 EO 4.o Waterglas~ 3.3) 10.0 :. 10 CMG 3.0 Sodium citrate 8.0 Sodlum sul~Ate 58.5 Balance (water, p~rfu~e, optlca~
brigh~ener) 1~.5 . ~XA~PIæ W 7 .. Low-phosphate bleaching washin~gent co~posi~ion : ~or 60C ~ashi~
~ 4 m e praparatlon ~a8 obtained by mixing 40 part~ by . .
watght of premix V 9 and 60 part~ by weight of a T~wer po~der obtainea by hot atomizatlon of the followlng composltlon:
Tow~r Po~dor No. 5 ~ By Nei~ht Toluene sul~onat~ 2.5 Soap ~.2 ~DTA o.5 Sodium trlpolypho~ph~to 25.0 ~atergla~3 (1:3.3) 8.3 - C~C 3.o Alumino~llicate 16.7 Magne~lum Billeate 3.o Balance (~odium ~ulfate~ optical brl~hte~or) 31.0 : ~.
10396(~8 The preparation cont~lns 10.4% by ~elght Or ~odlum perborate and 9.6% by weight of tetraacetyl glycoluril a~ a perborat~ activator. The w~ter-in~olubl~ calclu~ bindlng alu~inosillcate ~as incorporated ln the preparatlon through both the pre~ix and the Tower poNder in a total a~ount of 22.6% by weieht.
: BxAMPLæ W 8 ~- Lo~-phosphate bleaching ~a~hing agent compositlon ~or washin~ at 60C
- 10 The prep~ration W~5 obtained by mixing 50 parts by welght of premlx V 10, 40 parts by welght o~ Tower Powd~r No. ~ -1 a~d 10 part~ ~y w~ight of sodium perborate.
If it i~ deslred to reduce the ~oaming p~er of the ~ashlng age~t co~po~itlon~, known fo~m inhibltors are work0d in. miB iB partlcularly tr~o for preparatio~ wh1ch contai~ no 80ap.
m~ non-tensiae foam iDhibitor~ included N-alkylated a~inotriazines, QptiQnally conta~nlng chlorine, wh~ch are : obtainod by ~he reaction of 1 ~ol o~ cy~nuric acld Ghloride :.
~ith 2 to 3 mols of a mono- a~d/or dialkylamine with 6 to 20, preferably a to 18, carbon atoms in the alkyl radieal~. SiQi-larly ef~ctlve are propoxyl~tad and/or but0xylated amin -triazine~, such as products that are obtalned by tbe a~ditlon . ~ Or ~rom 5 to 10 mol~ o~ propylene oxiae to 1 mol Or ~elamine -:
: and fur~her additlon Or from 10 to 50 mol~ o~ butylene oxlde to tbi8 propyle~e-oxide d~rivative.
Lik~wise suitable as non-t~ide *oam inhibitbr~
are water-~n~oluble organic compound~, like paraffin~, or halogenated p~rar~ins w~th melti~g point~ below 100C, aliph~tic G18 to C40 keton~, a~ well ~8 aliphatic carboxylic .; .
` ~039f~08 acid esters whlch contain in the acid or alcohol resldue, optionally, also in both of theso resi~ues, at least 18 carbon atoms (such as triglycerides or fatty acid/fatty alcohol esters). These compound~ can ~e used to reduce ~oaming, particularly in combination~ of tensides of the ~ulfate and/or sulfonate type with soaps. Also alkali-~table silicones ~ay be incorporated as non-ten~ide foam t~hibitors.
The precedl~g specific embodiments are illu~tratlYe oi the practice of the in~entio~. It ls to be understooa, 10 however, that other expedients hno~n to tho~e skllled ln the art or disclosed herein, may be employed without departing from the spirit of the in~ention or the scope of the appended claims.
.
Claims (19)
1. A pourable washing agent composition comprising 2 premix powder component and optionally a second powder com-ponent obtained by hot drying of an aqueous composition contain-ing conventional heat-insensitive washing agent components, consisting essentially of (1) from 30% to 100% by weight of a premix powder component consisting essentially of (A) at least one finely-dispersed, water-insoluble, crystal-line silicate compound wherein at least 80% by weight of the crystalline particles of said silicate compound have a size from 10µ to 0.01µ and having a calcium bind-ing power of 100 to 200 mg CaO/gm of anhydrous active substance and the formula on the anhydrous basis (M2O)x ? Me2O3 (SiO2)y where M, is a cation selected from the group consisting of sodium and potassium, x is a number of from 0.7 to 1.5, Me is a member selected from the group consisting of aluminum and boron, and y is a number from 1.3 to 4, which silicate compound can optionally be partly replaced with highly dispersed silica with-a specific BET-surface of at least 250 m2/gm in an amount of not more than 4% by weight of the weight of the premix:
(B) from 0 to 80% by weight of the premix of bleaching com-ponents selected from the group consisting of inorganic peroxyhydrate compounds capable of supplying H2O2 in water, powdery acylated activators for percompounds, powdery stabilizers for percompounds and mixtures thereof;
(C) non-ionic surface-active compounds finely distributed on and throughout component (A) or the mixture of com-ponents (A) and (B); by applying the liquid form of component (C) thereon; where the mix ratio of component (A) to component (C) is in the ratio of 10:1 to 1:3 and at least 20% of said premix are components (A) and (C) together, the final mix ratio of the components being selected whereby the premix is a pourable powder; and (2) from 0 to 70% by weight of a second powdery component obtained by hot drying of an aqueous composition containing conven-tional heat-insensitive washing agent components.
(B) from 0 to 80% by weight of the premix of bleaching com-ponents selected from the group consisting of inorganic peroxyhydrate compounds capable of supplying H2O2 in water, powdery acylated activators for percompounds, powdery stabilizers for percompounds and mixtures thereof;
(C) non-ionic surface-active compounds finely distributed on and throughout component (A) or the mixture of com-ponents (A) and (B); by applying the liquid form of component (C) thereon; where the mix ratio of component (A) to component (C) is in the ratio of 10:1 to 1:3 and at least 20% of said premix are components (A) and (C) together, the final mix ratio of the components being selected whereby the premix is a pourable powder; and (2) from 0 to 70% by weight of a second powdery component obtained by hot drying of an aqueous composition containing conven-tional heat-insensitive washing agent components.
2. The composition of claim 1 wherein, in said formula for said silicate compound, x is a number from 0.7 to 1.1 and y is a number from 1.3 to 3.3.
3. The compositions of claim 1 wherein, in said formula for said silicate compounds M is sodium.
4. The composition of claim 1 wherein, said silicate com-pound has a crystal lattice with the following interference bands: -4.1 3.68 3.38 3.26 2.96 2.73 2.60.
5. The composition of claim 1 wherein, said silicate com-pound has a crystal lattice with the following interference bands:
4.4 3.8 2.88 2.79 2.66.
4.4 3.8 2.88 2.79 2.66.
6. The composition of claim 1 wherein, at least 80% by weight of the particles of said silicate compound have a size of from 8µ to 0.1µ.
7. The composition of claim 1 wherein, said silicate com-pound has no primary or secondary particles above 40µ.
8. The composition of claim wherein, component (B) is present in an amount of from 15% to 80% by weight in said premix powder component.
9. The composition of claim 1 wherein, said premix powder component consists of:
from 10% to 60% by weight of said silicate compound, from 0% to 4% by weight of said highly dispersed silica, from 20% to 80% by weight of said inorganic peroxyhydrate compounds, from 0% to 30% by weight of said activators for percompounds and said stabilizers for percompounds, and from 10% to 30% by weight of said non-ionic surface-active compounds.
from 10% to 60% by weight of said silicate compound, from 0% to 4% by weight of said highly dispersed silica, from 20% to 80% by weight of said inorganic peroxyhydrate compounds, from 0% to 30% by weight of said activators for percompounds and said stabilizers for percompounds, and from 10% to 30% by weight of said non-ionic surface-active compounds.
10. The composition of claim 1 wherein, said premix powder component consists of from 60% to 90% by weight of said silicate compound, from 0% to 30% by weight of said activator for percompounds, from 10% to 40% by weight of said non-ionic surface-active compounds, and from 0% to 4% by weight of highly dispersed silica.
11. The composition of claim 1 wherein, said premix powder component contains from 15% to 25% by weight of tetra-acetylglycoluril.
12. The composition of claim 1 wherein, said premix powder component is present in an amount of 100%.
13. The composition of claim 1 having an overall composition consisting of:
from 5% to 30% by weight of at least one surface-active compound selected from the group consisting of anionic surface-active compounds, non-ionic surface-active compounds, amphoteric surface-active compounds, and mixtures thereof, from 5% to 70% by weight of said at least one silicate compound, from 2% to 45% by weight of water-soluble sequestering agents capable of sequestering calcium ions, from 0% to 50% by weight of builder salts incapable of sequestering calcium ions, and from 0% to 40% by weight of said bleaching component.
from 5% to 30% by weight of at least one surface-active compound selected from the group consisting of anionic surface-active compounds, non-ionic surface-active compounds, amphoteric surface-active compounds, and mixtures thereof, from 5% to 70% by weight of said at least one silicate compound, from 2% to 45% by weight of water-soluble sequestering agents capable of sequestering calcium ions, from 0% to 50% by weight of builder salts incapable of sequestering calcium ions, and from 0% to 40% by weight of said bleaching component.
14. The composition of claim 13 wherein, said bleaching component is present in an amount of from 10% to 40% by weight.
15. The composition of claim 14 wherein, said bleaching component includes sodium perborate tetrahydrate.
16. The composition of claim 1 wherein, in said formula for said silicate compound, Me is aluminum.
17. The composition of claim 1 wherein, said silicate compound has the composition:
0.9 Na2O . Al2O3 . 2SiO2 , 4 H2O
and a calcium binding power of 165 mg CaO/gm AS.
0.9 Na2O . Al2O3 . 2SiO2 , 4 H2O
and a calcium binding power of 165 mg CaO/gm AS.
18. A pourable washing agent composition consisting (I) of 59 parts by weight of a premix containing 48.3% by weight of NaBO2 . H2O2 . 3 H2O, having a bulk density of 830 gm/l, 34.5%
by weight of an aluminosilicate of the composition:
0.9 Na2O . Al2O3 . 2SiO2 . 4H2O
a particle size distribution of 100% by weight below 30µ , 90% by weight below 10µ, the maximum range of the particle size distribu-tion curve at 1 to 5µ and a calcium binding power of 165 mg CaO/gm AS, as determined according to the calcium binding power test on page 18, lines 2 to 12, 5.2% by weight of the addition product of 5 mols of ethylene oxide to 1 mol of tallow fatty alcohol and 12.0% by weight of the addition product of 14 mols of ethylene oxide to 1 mol of tallow fatty alcohol, said premix being produced by spraying said addition products in liquid form onto the moving powder mixture of the remaining ingredients, and (II) 41 parts by weight of a spray-dried powder containing where the final washing agent composition after mixing said premix and said spray-dried powder was
by weight of an aluminosilicate of the composition:
0.9 Na2O . Al2O3 . 2SiO2 . 4H2O
a particle size distribution of 100% by weight below 30µ , 90% by weight below 10µ, the maximum range of the particle size distribu-tion curve at 1 to 5µ and a calcium binding power of 165 mg CaO/gm AS, as determined according to the calcium binding power test on page 18, lines 2 to 12, 5.2% by weight of the addition product of 5 mols of ethylene oxide to 1 mol of tallow fatty alcohol and 12.0% by weight of the addition product of 14 mols of ethylene oxide to 1 mol of tallow fatty alcohol, said premix being produced by spraying said addition products in liquid form onto the moving powder mixture of the remaining ingredients, and (II) 41 parts by weight of a spray-dried powder containing where the final washing agent composition after mixing said premix and said spray-dried powder was
19. A method for the production of the composition of claim 1 comprising applying the component (C) in liquid form from onto a moving powder of component (A) of components (A) and (B) to form said premix powder component, and optionally, mixing said premix powder component with a second powdery component obtained by hot drying of an aqueous composition containing conventional heat-insensitive washing agent components.
Applications Claiming Priority (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
AT0151474A AT373276B (en) | 1974-02-25 | 1974-02-25 | PROBLEABLE DETERGENTS CONTAINING NON-ionic surfactants |
Publications (1)
Publication Number | Publication Date |
---|---|
CA1039608A true CA1039608A (en) | 1978-10-03 |
Family
ID=3515324
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
CA220,615A Expired CA1039608A (en) | 1974-02-25 | 1975-02-24 | Pourable washing compositions containing aluminosilicates and non-ionics and method for their production |
Country Status (21)
Country | Link |
---|---|
JP (1) | JPS6052193B2 (en) |
AT (1) | AT373276B (en) |
BE (1) | BE825863A (en) |
BR (1) | BR7501095A (en) |
CA (1) | CA1039608A (en) |
CH (1) | CH625550A5 (en) |
CY (1) | CY1073A (en) |
DE (1) | DE2507926A1 (en) |
DK (1) | DK27475A (en) |
ES (1) | ES435028A1 (en) |
FI (1) | FI59419C (en) |
FR (1) | FR2262108B1 (en) |
GB (1) | GB1504211A (en) |
IE (1) | IE41133B1 (en) |
IT (1) | IT1030215B (en) |
LU (1) | LU71902A1 (en) |
NL (1) | NL174956C (en) |
NO (1) | NO750256L (en) |
SE (1) | SE425857B (en) |
TR (1) | TR18463A (en) |
ZA (1) | ZA751168B (en) |
Families Citing this family (23)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
ZA767170B (en) * | 1975-12-15 | 1978-07-26 | Colgate Palmolive Co | Detergent composition and method for use |
US4260651A (en) * | 1976-12-02 | 1981-04-07 | Colgate-Palmolive Company | Phosphate-free concentrated particulate heavy duty laundry detergent |
US4248911A (en) * | 1976-12-02 | 1981-02-03 | Colgate-Palmolive Company | Concentrated heavy duty particulate laundry detergent |
ZA776946B (en) * | 1976-12-02 | 1979-06-27 | Colgate Palmolive Co | Free flowing high bulk density particulate detergent softener |
US4666740A (en) * | 1976-12-02 | 1987-05-19 | The Colgate-Palmolive Co. | Phosphate-free concentrated particulate heavy duty laundry detergent |
US4663194A (en) * | 1976-12-02 | 1987-05-05 | The Colgate-Palmolive Co. | Phosphate-free concentrated particulate heavy duty laundry detergent |
US4347152A (en) * | 1976-12-02 | 1982-08-31 | Colgate-Palmolive Company | Phosphate-free concentrated particulate heavy duty laundry detergent |
JPS544908A (en) * | 1977-06-14 | 1979-01-16 | Kao Corp | Granular or powdery detergent composition with good fluidity |
NZ188469A (en) * | 1977-10-06 | 1980-12-19 | Colgate Palmolive Co | Detergent composition comprising a univalent cation-exchanging zeolite a nonionic detergent and builder salts |
DE2902236A1 (en) * | 1978-01-25 | 1979-07-26 | Kao Corp | BLEACHING AGENT |
DE2852285A1 (en) * | 1978-12-02 | 1980-06-12 | Henkel Kgaa | LOW-PHOSPHATE FRUIT SALT MIXTURE AND THEIR USE IN DETERGENT AND CLEANING AGENTS |
JPS5632321A (en) * | 1979-06-18 | 1981-04-01 | Pq Corp | Improved zeolite ion exchanging substance |
DE3066202D1 (en) | 1979-11-03 | 1984-02-23 | Procter & Gamble | Granular laundry compositions |
US4666738A (en) * | 1980-09-02 | 1987-05-19 | The Colgate-Palmolive Co. | Method for making a phosphate containing concentrated heavy duty particulate laundry detergent |
IE51848B1 (en) * | 1980-11-06 | 1987-04-15 | Procter & Gamble | Bleach activator compositions,preparation thereof and use in granular detergent compositions |
JPS5811597A (en) * | 1981-04-08 | 1983-01-22 | ザ・プロクタ−・エンド・ギヤンブル・カンパニ− | Detergent composition |
NZ201211A (en) * | 1981-07-15 | 1985-08-16 | Unilever Plc | Detergent additives and compositions |
DE3424987A1 (en) * | 1984-07-06 | 1986-02-06 | Unilever N.V., Rotterdam | METHOD FOR PRODUCING A POWDERED DETERGENT WITH INCREASED SHOULDER WEIGHT |
JPS6189300A (en) * | 1984-10-09 | 1986-05-07 | ライオン株式会社 | Production of granular detergent composition containing nonionic surfactant |
DE3621536A1 (en) * | 1986-06-27 | 1988-01-07 | Henkel Kgaa | LIQUID DETERGENT AND METHOD FOR THE PRODUCTION THEREOF |
DE3842007A1 (en) * | 1988-12-14 | 1990-06-21 | Henkel Kgaa | FLUID TO PASTOESES, BLEACHING DETERGENT |
DE69112970T2 (en) * | 1990-09-28 | 1996-03-21 | Kao Corp | Nonionic powder detergent composition. |
GB9113675D0 (en) * | 1991-06-25 | 1991-08-14 | Unilever Plc | Particulate detergent composition or component |
Family Cites Families (14)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
GB132511A (en) * | 1918-06-24 | 1900-01-01 | ||
GB339355A (en) * | 1929-09-07 | 1930-12-08 | Electric Smelting & Aluminum C | Improvements in and relating to detergents and method of preparing the same |
DE1038017B (en) * | 1953-12-24 | 1958-09-04 | Union Carbide Corp | Process for making crystalline zeolitic molecular sieves |
US3033641A (en) * | 1956-03-21 | 1962-05-08 | Union Carbide Corp | Process for cation separation using zeolitic materials |
US3206408A (en) * | 1961-04-07 | 1965-09-14 | American Cyanamid Co | Aqueous shampoo composition |
NL296018A (en) * | 1962-08-01 | |||
ZA670030B (en) * | 1966-03-09 | |||
US3650967A (en) * | 1969-09-15 | 1972-03-21 | Colgate Palmolive Co | Enzymatic granules |
FR2105475A5 (en) * | 1970-09-02 | 1972-04-28 | Sifrance | |
DE2055423A1 (en) * | 1970-11-11 | 1972-05-18 | Chemische Fabrik Budenheim, Rudolf A. Oetker, 6501 Budenheim | Washing compositions - containing water-insoluble crosslinked cation -exchange polymers especially crosslinked polystyrene,polyacrylic acid |
US3769222A (en) * | 1971-02-09 | 1973-10-30 | Colgate Palmolive Co | Free flowing nonionic surfactants |
AT330930B (en) * | 1973-04-13 | 1976-07-26 | Henkel & Cie Gmbh | PROCESS FOR THE PRODUCTION OF SOLID, SPILLABLE DETERGENTS OR CLEANING AGENTS WITH A CONTENT OF CALCIUM BINDING SUBSTANCES |
US4605509A (en) * | 1973-05-11 | 1986-08-12 | The Procter & Gamble Company | Detergent compositions containing sodium aluminosilicate builders |
JPS5838919B2 (en) | 1974-06-24 | 1983-08-26 | キヤノン株式会社 | Power supply circuit for flash device |
-
1974
- 1974-02-25 AT AT0151474A patent/AT373276B/en not_active IP Right Cessation
-
1975
- 1975-01-28 NL NLAANVRAGE7500980,A patent/NL174956C/en not_active IP Right Cessation
- 1975-01-28 DK DK27475*#A patent/DK27475A/da not_active Application Discontinuation
- 1975-01-28 SE SE7500901A patent/SE425857B/en not_active IP Right Cessation
- 1975-01-28 NO NO750256A patent/NO750256L/no unknown
- 1975-01-28 FI FI750212A patent/FI59419C/en not_active IP Right Cessation
- 1975-02-21 CY CY1073A patent/CY1073A/en unknown
- 1975-02-21 GB GB7278/75A patent/GB1504211A/en not_active Expired
- 1975-02-24 ES ES435028A patent/ES435028A1/en not_active Expired
- 1975-02-24 BE BE153635A patent/BE825863A/en not_active IP Right Cessation
- 1975-02-24 LU LU71902A patent/LU71902A1/xx unknown
- 1975-02-24 CA CA220,615A patent/CA1039608A/en not_active Expired
- 1975-02-24 CH CH224975A patent/CH625550A5/en not_active IP Right Cessation
- 1975-02-24 BR BR1095/75A patent/BR7501095A/en unknown
- 1975-02-24 DE DE19752507926 patent/DE2507926A1/en not_active Withdrawn
- 1975-02-25 ZA ZA00751168A patent/ZA751168B/en unknown
- 1975-02-25 IT IT67478/75A patent/IT1030215B/en active
- 1975-02-25 IE IE392/75A patent/IE41133B1/en unknown
- 1975-02-25 JP JP50023366A patent/JPS6052193B2/en not_active Expired
- 1975-02-25 FR FR7505855A patent/FR2262108B1/fr not_active Expired
- 1975-12-25 TR TR18463A patent/TR18463A/en unknown
Also Published As
Publication number | Publication date |
---|---|
NO750256L (en) | 1975-08-26 |
NL174956B (en) | 1984-04-02 |
NL174956C (en) | 1984-09-03 |
FI59419C (en) | 1981-08-10 |
JPS50119813A (en) | 1975-09-19 |
LU71902A1 (en) | 1975-12-09 |
IE41133L (en) | 1975-08-25 |
DE2507926B2 (en) | 1980-03-13 |
GB1504211A (en) | 1978-03-15 |
ATA151474A (en) | 1976-04-15 |
DE2507926A1 (en) | 1975-08-28 |
SE7500901L (en) | 1975-08-26 |
FR2262108B1 (en) | 1977-04-15 |
IT1030215B (en) | 1979-03-30 |
BE825863A (en) | 1975-08-25 |
CH625550A5 (en) | 1981-09-30 |
FR2262108A1 (en) | 1975-09-19 |
ZA751168B (en) | 1976-01-28 |
AT373276B (en) | 1984-01-10 |
ES435028A1 (en) | 1977-01-01 |
TR18463A (en) | 1977-02-18 |
NL7500980A (en) | 1975-08-27 |
DK27475A (en) | 1975-10-27 |
CY1073A (en) | 1980-10-24 |
FI59419B (en) | 1981-04-30 |
SE425857B (en) | 1982-11-15 |
BR7501095A (en) | 1975-12-02 |
JPS6052193B2 (en) | 1985-11-18 |
FI750212A (en) | 1975-08-26 |
IE41133B1 (en) | 1979-10-24 |
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