CA1253769A - Detergency builder system - Google Patents
Detergency builder systemInfo
- Publication number
- CA1253769A CA1253769A CA000501968A CA501968A CA1253769A CA 1253769 A CA1253769 A CA 1253769A CA 000501968 A CA000501968 A CA 000501968A CA 501968 A CA501968 A CA 501968A CA 1253769 A CA1253769 A CA 1253769A
- Authority
- CA
- Canada
- Prior art keywords
- weight
- ethoxylated
- dispersing
- moiety
- agent
- 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
- 239000003599 detergent Substances 0.000 claims abstract description 82
- -1 ether carboxylate Chemical class 0.000 claims abstract description 74
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 62
- 150000001412 amines Chemical class 0.000 claims abstract description 54
- 239000000463 material Substances 0.000 claims abstract description 52
- RTZKZFJDLAIYFH-UHFFFAOYSA-N ether Substances CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 claims abstract description 46
- 229920000642 polymer Polymers 0.000 claims abstract description 41
- 239000000654 additive Substances 0.000 claims abstract description 40
- 230000000996 additive effect Effects 0.000 claims abstract description 39
- 150000003839 salts Chemical class 0.000 claims abstract description 34
- 239000003352 sequestering agent Substances 0.000 claims abstract description 23
- 229920001577 copolymer Polymers 0.000 claims abstract description 14
- CFPOJWPDQWJEMO-UHFFFAOYSA-N 2-(1,2-dicarboxyethoxy)butanedioic acid Chemical compound OC(=O)CC(C(O)=O)OC(C(O)=O)CC(O)=O CFPOJWPDQWJEMO-UHFFFAOYSA-N 0.000 claims abstract description 10
- 239000000203 mixture Substances 0.000 claims description 154
- 239000000306 component Substances 0.000 claims description 36
- 239000004094 surface-active agent Substances 0.000 claims description 29
- 239000007844 bleaching agent Substances 0.000 claims description 27
- 239000002253 acid Substances 0.000 claims description 25
- 125000002947 alkylene group Chemical group 0.000 claims description 22
- 229920005646 polycarboxylate Polymers 0.000 claims description 21
- 238000007046 ethoxylation reaction Methods 0.000 claims description 20
- 229920002873 Polyethylenimine Polymers 0.000 claims description 19
- 229910052783 alkali metal Inorganic materials 0.000 claims description 18
- 150000001340 alkali metals Chemical group 0.000 claims description 18
- 125000000129 anionic group Chemical group 0.000 claims description 18
- 125000005702 oxyalkylene group Chemical group 0.000 claims description 18
- 239000002689 soil Substances 0.000 claims description 18
- 125000004450 alkenylene group Chemical group 0.000 claims description 17
- 229920000768 polyamine Polymers 0.000 claims description 16
- 150000004985 diamines Chemical class 0.000 claims description 14
- 239000001257 hydrogen Substances 0.000 claims description 14
- 229910052739 hydrogen Inorganic materials 0.000 claims description 14
- 239000002738 chelating agent Substances 0.000 claims description 13
- 125000002768 hydroxyalkyl group Chemical group 0.000 claims description 13
- 150000001768 cations Chemical class 0.000 claims description 12
- 239000004744 fabric Substances 0.000 claims description 12
- 239000002243 precursor Substances 0.000 claims description 11
- 229920002125 Sokalan® Polymers 0.000 claims description 9
- 125000003118 aryl group Chemical group 0.000 claims description 9
- 239000004584 polyacrylic acid Substances 0.000 claims description 9
- 125000004178 (C1-C4) alkyl group Chemical group 0.000 claims description 8
- 102000004190 Enzymes Human genes 0.000 claims description 8
- 108090000790 Enzymes Proteins 0.000 claims description 8
- 125000003342 alkenyl group Chemical group 0.000 claims description 8
- 125000000732 arylene group Chemical group 0.000 claims description 8
- 125000004435 hydrogen atom Chemical class [H]* 0.000 claims description 8
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims description 7
- 239000002904 solvent Substances 0.000 claims description 7
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 claims description 6
- 239000002304 perfume Substances 0.000 claims description 6
- 229920000058 polyacrylate Polymers 0.000 claims description 6
- 125000002877 alkyl aryl group Chemical group 0.000 claims description 5
- 239000003752 hydrotrope Substances 0.000 claims description 5
- 239000003605 opacifier Substances 0.000 claims description 5
- 239000004902 Softening Agent Substances 0.000 claims description 4
- 239000006172 buffering agent Substances 0.000 claims description 4
- 229920001495 poly(sodium acrylate) polymer Polymers 0.000 claims description 4
- NNMHYFLPFNGQFZ-UHFFFAOYSA-M sodium polyacrylate Chemical compound [Na+].[O-]C(=O)C=C NNMHYFLPFNGQFZ-UHFFFAOYSA-M 0.000 claims description 4
- KXDHJXZQYSOELW-UHFFFAOYSA-N Carbamic acid Chemical class NC(O)=O KXDHJXZQYSOELW-UHFFFAOYSA-N 0.000 claims description 3
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 claims description 2
- XGMYMWYPSYIPQB-UHFFFAOYSA-J tetrasodium;2-(1,2-dicarboxylatoethoxy)butanedioate Chemical compound [Na+].[Na+].[Na+].[Na+].[O-]C(=O)CC(C([O-])=O)OC(C([O-])=O)CC([O-])=O XGMYMWYPSYIPQB-UHFFFAOYSA-J 0.000 claims description 2
- 125000004029 hydroxymethyl group Chemical group [H]OC([H])([H])* 0.000 claims 3
- 238000006467 substitution reaction Methods 0.000 claims 3
- 229940000425 combination drug Drugs 0.000 claims 1
- QPCDCPDFJACHGM-UHFFFAOYSA-K pentetate(3-) Chemical group OC(=O)CN(CC([O-])=O)CCN(CC([O-])=O)CCN(CC(O)=O)CC([O-])=O QPCDCPDFJACHGM-UHFFFAOYSA-K 0.000 claims 1
- NIXOWILDQLNWCW-UHFFFAOYSA-N 2-Propenoic acid Natural products OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 abstract description 10
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical class COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 abstract description 7
- 150000007942 carboxylates Chemical class 0.000 abstract description 7
- 125000000217 alkyl group Chemical group 0.000 description 24
- 125000004432 carbon atom Chemical group C* 0.000 description 24
- 150000001875 compounds Chemical class 0.000 description 23
- IAYPIBMASNFSPL-UHFFFAOYSA-N Ethylene oxide Chemical compound C1CO1 IAYPIBMASNFSPL-UHFFFAOYSA-N 0.000 description 21
- 239000011734 sodium Substances 0.000 description 21
- 229910052708 sodium Inorganic materials 0.000 description 21
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 19
- 229910000323 aluminium silicate Inorganic materials 0.000 description 19
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 17
- HNPSIPDUKPIQMN-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Al]O[Al]=O HNPSIPDUKPIQMN-UHFFFAOYSA-N 0.000 description 17
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 17
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 16
- 229940117927 ethylene oxide Drugs 0.000 description 15
- 238000005342 ion exchange Methods 0.000 description 15
- 229910019142 PO4 Inorganic materials 0.000 description 13
- 235000021317 phosphate Nutrition 0.000 description 12
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 description 11
- 239000003945 anionic surfactant Substances 0.000 description 11
- 229920001601 polyetherimide Polymers 0.000 description 11
- 235000014113 dietary fatty acids Nutrition 0.000 description 10
- 239000000194 fatty acid Substances 0.000 description 10
- 229930195729 fatty acid Natural products 0.000 description 10
- 239000000344 soap Substances 0.000 description 10
- 150000004665 fatty acids Chemical class 0.000 description 9
- 239000002736 nonionic surfactant Substances 0.000 description 9
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 description 9
- 239000010452 phosphate Substances 0.000 description 9
- 239000000243 solution Substances 0.000 description 9
- VZCYOOQTPOCHFL-UHFFFAOYSA-N trans-butenedioic acid Natural products OC(=O)C=CC(O)=O VZCYOOQTPOCHFL-UHFFFAOYSA-N 0.000 description 9
- 229940123150 Chelating agent Drugs 0.000 description 8
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 8
- 150000003863 ammonium salts Chemical class 0.000 description 8
- 239000002245 particle Substances 0.000 description 8
- 229910052698 phosphorus Inorganic materials 0.000 description 8
- 239000011574 phosphorus Substances 0.000 description 8
- 239000000047 product Substances 0.000 description 8
- 239000000377 silicon dioxide Substances 0.000 description 8
- 239000003760 tallow Substances 0.000 description 8
- HZAXFHJVJLSVMW-UHFFFAOYSA-N 2-Aminoethan-1-ol Chemical compound NCCO HZAXFHJVJLSVMW-UHFFFAOYSA-N 0.000 description 7
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 description 7
- GSEJCLTVZPLZKY-UHFFFAOYSA-N Triethanolamine Chemical compound OCCN(CCO)CCO GSEJCLTVZPLZKY-UHFFFAOYSA-N 0.000 description 7
- 239000012190 activator Substances 0.000 description 7
- 239000003093 cationic surfactant Substances 0.000 description 7
- 238000004140 cleaning Methods 0.000 description 7
- 229910052700 potassium Inorganic materials 0.000 description 7
- 239000011591 potassium Substances 0.000 description 7
- 238000002360 preparation method Methods 0.000 description 7
- 235000012239 silicon dioxide Nutrition 0.000 description 7
- 239000007787 solid Substances 0.000 description 7
- FAGUFWYHJQFNRV-UHFFFAOYSA-N tetraethylenepentamine Chemical compound NCCNCCNCCNCCN FAGUFWYHJQFNRV-UHFFFAOYSA-N 0.000 description 7
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 description 6
- 239000005977 Ethylene Substances 0.000 description 6
- BPQQTUXANYXVAA-UHFFFAOYSA-N Orthosilicate Chemical compound [O-][Si]([O-])([O-])[O-] BPQQTUXANYXVAA-UHFFFAOYSA-N 0.000 description 6
- OFOBLEOULBTSOW-UHFFFAOYSA-N Propanedioic acid Natural products OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 0.000 description 6
- 150000001298 alcohols Chemical class 0.000 description 6
- 229910052681 coesite Inorganic materials 0.000 description 6
- 229910052906 cristobalite Inorganic materials 0.000 description 6
- 229940093470 ethylene Drugs 0.000 description 6
- 150000002500 ions Chemical class 0.000 description 6
- 235000019832 sodium triphosphate Nutrition 0.000 description 6
- 229910052682 stishovite Inorganic materials 0.000 description 6
- 229910052905 tridymite Inorganic materials 0.000 description 6
- 238000005406 washing Methods 0.000 description 6
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 description 5
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 5
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 5
- 239000004115 Sodium Silicate Substances 0.000 description 5
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 description 5
- 239000011230 binding agent Substances 0.000 description 5
- 239000011575 calcium Substances 0.000 description 5
- 229910001424 calcium ion Inorganic materials 0.000 description 5
- 238000006243 chemical reaction Methods 0.000 description 5
- 239000003240 coconut oil Substances 0.000 description 5
- 235000019864 coconut oil Nutrition 0.000 description 5
- 239000007788 liquid Substances 0.000 description 5
- 239000011777 magnesium Substances 0.000 description 5
- VZCYOOQTPOCHFL-UPHRSURJSA-N maleic acid Chemical compound OC(=O)\C=C/C(O)=O VZCYOOQTPOCHFL-UPHRSURJSA-N 0.000 description 5
- 125000004805 propylene group Chemical group [H]C([H])([H])C([H])([*:1])C([H])([H])[*:2] 0.000 description 5
- NTHWMYGWWRZVTN-UHFFFAOYSA-N sodium silicate Chemical compound [Na+].[Na+].[O-][Si]([O-])=O NTHWMYGWWRZVTN-UHFFFAOYSA-N 0.000 description 5
- 229910052911 sodium silicate Inorganic materials 0.000 description 5
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 4
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 description 4
- BHPQYMZQTOCNFJ-UHFFFAOYSA-N Calcium cation Chemical group [Ca+2] BHPQYMZQTOCNFJ-UHFFFAOYSA-N 0.000 description 4
- KCXVZYZYPLLWCC-UHFFFAOYSA-N EDTA Chemical class OC(=O)CN(CC(O)=O)CCN(CC(O)=O)CC(O)=O KCXVZYZYPLLWCC-UHFFFAOYSA-N 0.000 description 4
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 4
- DNIAPMSPPWPWGF-UHFFFAOYSA-N Propylene glycol Chemical compound CC(O)CO DNIAPMSPPWPWGF-UHFFFAOYSA-N 0.000 description 4
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 4
- BGRWYDHXPHLNKA-UHFFFAOYSA-N Tetraacetylethylenediamine Chemical compound CC(=O)N(C(C)=O)CCN(C(C)=O)C(C)=O BGRWYDHXPHLNKA-UHFFFAOYSA-N 0.000 description 4
- 150000007513 acids Chemical class 0.000 description 4
- 239000002671 adjuvant Substances 0.000 description 4
- 229910052910 alkali metal silicate Inorganic materials 0.000 description 4
- 239000002585 base Substances 0.000 description 4
- 229940077388 benzenesulfonate Drugs 0.000 description 4
- 150000002148 esters Chemical class 0.000 description 4
- 239000011976 maleic acid Substances 0.000 description 4
- 238000000034 method Methods 0.000 description 4
- 125000001570 methylene group Chemical group [H]C([H])([*:1])[*:2] 0.000 description 4
- 238000002156 mixing Methods 0.000 description 4
- 229910052757 nitrogen Inorganic materials 0.000 description 4
- 238000001556 precipitation Methods 0.000 description 4
- 159000000000 sodium salts Chemical group 0.000 description 4
- 229960004418 trolamine Drugs 0.000 description 4
- 239000010457 zeolite Substances 0.000 description 4
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 3
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 3
- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 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
- JLVVSXFLKOJNIY-UHFFFAOYSA-N Magnesium ion Chemical group [Mg+2] JLVVSXFLKOJNIY-UHFFFAOYSA-N 0.000 description 3
- BCXBKOQDEOJNRH-UHFFFAOYSA-N NOP(O)=O Chemical class NOP(O)=O BCXBKOQDEOJNRH-UHFFFAOYSA-N 0.000 description 3
- 229920000388 Polyphosphate Polymers 0.000 description 3
- GOOHAUXETOMSMM-UHFFFAOYSA-N Propylene oxide Chemical compound CC1CO1 GOOHAUXETOMSMM-UHFFFAOYSA-N 0.000 description 3
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- 229910021536 Zeolite Inorganic materials 0.000 description 3
- 125000001931 aliphatic group Chemical group 0.000 description 3
- 229910000288 alkali metal carbonate Inorganic materials 0.000 description 3
- 229910000272 alkali metal oxide Inorganic materials 0.000 description 3
- 230000033228 biological regulation Effects 0.000 description 3
- 229910052791 calcium Inorganic materials 0.000 description 3
- 229910000019 calcium carbonate Inorganic materials 0.000 description 3
- 229910002092 carbon dioxide Inorganic materials 0.000 description 3
- 239000003054 catalyst Substances 0.000 description 3
- 239000004927 clay Substances 0.000 description 3
- 239000003086 colorant Substances 0.000 description 3
- 239000007859 condensation product Substances 0.000 description 3
- 125000004122 cyclic group Chemical group 0.000 description 3
- NFDRPXJGHKJRLJ-UHFFFAOYSA-N edtmp Chemical compound OP(O)(=O)CN(CP(O)(O)=O)CCN(CP(O)(O)=O)CP(O)(O)=O NFDRPXJGHKJRLJ-UHFFFAOYSA-N 0.000 description 3
- 150000002431 hydrogen Chemical group 0.000 description 3
- 230000002209 hydrophobic effect Effects 0.000 description 3
- 229910052749 magnesium Inorganic materials 0.000 description 3
- FPYJFEHAWHCUMM-UHFFFAOYSA-N maleic anhydride Chemical compound O=C1OC(=O)C=C1 FPYJFEHAWHCUMM-UHFFFAOYSA-N 0.000 description 3
- IJGRMHOSHXDMSA-UHFFFAOYSA-N nitrogen Substances N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 3
- 125000004433 nitrogen atom Chemical group N* 0.000 description 3
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 description 3
- 150000003013 phosphoric acid derivatives Chemical class 0.000 description 3
- 239000001205 polyphosphate Substances 0.000 description 3
- 235000011176 polyphosphates Nutrition 0.000 description 3
- 239000000843 powder Substances 0.000 description 3
- 239000011541 reaction mixture Substances 0.000 description 3
- 239000002002 slurry Substances 0.000 description 3
- 229910000029 sodium carbonate Inorganic materials 0.000 description 3
- 230000003381 solubilizing effect Effects 0.000 description 3
- 238000003756 stirring Methods 0.000 description 3
- BDHFUVZGWQCTTF-UHFFFAOYSA-M sulfonate Chemical compound [O-]S(=O)=O BDHFUVZGWQCTTF-UHFFFAOYSA-M 0.000 description 3
- 150000003467 sulfuric acid derivatives Chemical class 0.000 description 3
- 239000002888 zwitterionic surfactant Substances 0.000 description 3
- VILCJCGEZXAXTO-UHFFFAOYSA-N 2,2,2-tetramine Chemical compound NCCNCCNCCN VILCJCGEZXAXTO-UHFFFAOYSA-N 0.000 description 2
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical group N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 2
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 2
- 244000060011 Cocos nucifera Species 0.000 description 2
- 235000013162 Cocos nucifera Nutrition 0.000 description 2
- 229940120146 EDTMP Drugs 0.000 description 2
- VZCYOOQTPOCHFL-OWOJBTEDSA-N Fumaric acid Chemical compound OC(=O)\C=C\C(O)=O VZCYOOQTPOCHFL-OWOJBTEDSA-N 0.000 description 2
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 2
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 description 2
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 2
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 2
- 229910000503 Na-aluminosilicate Inorganic materials 0.000 description 2
- KFSLWBXXFJQRDL-UHFFFAOYSA-N Peracetic acid Chemical compound CC(=O)OO KFSLWBXXFJQRDL-UHFFFAOYSA-N 0.000 description 2
- 229920003171 Poly (ethylene oxide) Polymers 0.000 description 2
- QQONPFPTGQHPMA-UHFFFAOYSA-N Propene Chemical compound CC=C QQONPFPTGQHPMA-UHFFFAOYSA-N 0.000 description 2
- PMZURENOXWZQFD-UHFFFAOYSA-L Sodium Sulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=O PMZURENOXWZQFD-UHFFFAOYSA-L 0.000 description 2
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 description 2
- 238000007792 addition Methods 0.000 description 2
- 239000003513 alkali Substances 0.000 description 2
- 150000008041 alkali metal carbonates Chemical class 0.000 description 2
- 229910052784 alkaline earth metal Inorganic materials 0.000 description 2
- 150000001342 alkaline earth metals Chemical class 0.000 description 2
- 150000004996 alkyl benzenes Chemical class 0.000 description 2
- 150000008051 alkyl sulfates Chemical class 0.000 description 2
- 150000001450 anions Chemical class 0.000 description 2
- 229910052786 argon Inorganic materials 0.000 description 2
- 239000000872 buffer Substances 0.000 description 2
- 229910052799 carbon Inorganic materials 0.000 description 2
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 2
- 239000007795 chemical reaction product Substances 0.000 description 2
- 238000009833 condensation Methods 0.000 description 2
- 230000005494 condensation Effects 0.000 description 2
- 230000002950 deficient Effects 0.000 description 2
- 235000011180 diphosphates Nutrition 0.000 description 2
- 238000004851 dishwashing Methods 0.000 description 2
- 125000000816 ethylene group Chemical group [H]C([H])([*:1])C([H])([H])[*:2] 0.000 description 2
- 239000008187 granular material Substances 0.000 description 2
- 150000004820 halides Chemical class 0.000 description 2
- 125000001165 hydrophobic group Chemical group 0.000 description 2
- 229910052816 inorganic phosphate Inorganic materials 0.000 description 2
- 239000002563 ionic surfactant Substances 0.000 description 2
- 229910052742 iron Inorganic materials 0.000 description 2
- SUMDYPCJJOFFON-UHFFFAOYSA-N isethionic acid Chemical compound OCCS(O)(=O)=O SUMDYPCJJOFFON-UHFFFAOYSA-N 0.000 description 2
- 229910052744 lithium Inorganic materials 0.000 description 2
- 229910001425 magnesium ion Inorganic materials 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 229910052751 metal Inorganic materials 0.000 description 2
- 239000002184 metal Substances 0.000 description 2
- JZMJDSHXVKJFKW-UHFFFAOYSA-M methyl sulfate(1-) Chemical compound COS([O-])(=O)=O JZMJDSHXVKJFKW-UHFFFAOYSA-M 0.000 description 2
- 150000004967 organic peroxy acids Chemical class 0.000 description 2
- 125000000864 peroxy group Chemical group O(O*)* 0.000 description 2
- 229920000728 polyester Polymers 0.000 description 2
- 229920000573 polyethylene Polymers 0.000 description 2
- 229920001223 polyethylene glycol Polymers 0.000 description 2
- 230000000379 polymerizing effect Effects 0.000 description 2
- 229920005862 polyol Polymers 0.000 description 2
- 150000003077 polyols Chemical class 0.000 description 2
- 229920001296 polysiloxane Polymers 0.000 description 2
- 150000003138 primary alcohols Chemical class 0.000 description 2
- 235000013772 propylene glycol Nutrition 0.000 description 2
- 229920005989 resin Polymers 0.000 description 2
- 239000011347 resin Substances 0.000 description 2
- 150000004760 silicates Chemical class 0.000 description 2
- 235000012217 sodium aluminium silicate Nutrition 0.000 description 2
- QSKQNALVHFTOQX-UHFFFAOYSA-M sodium nonanoyloxybenzenesulfonate Chemical compound [Na+].CCCCCCCCC(=O)OC1=CC=CC=C1S([O-])(=O)=O QSKQNALVHFTOQX-UHFFFAOYSA-M 0.000 description 2
- RTVVXRKGQRRXFJ-UHFFFAOYSA-N sodium;2-sulfobutanedioic acid Chemical compound [Na].OC(=O)CC(C(O)=O)S(O)(=O)=O RTVVXRKGQRRXFJ-UHFFFAOYSA-N 0.000 description 2
- 239000007921 spray Substances 0.000 description 2
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- 235000011152 sodium sulphate Nutrition 0.000 description 1
- HJHVQCXHVMGZNC-JCJNLNMISA-M sodium;(2z)-2-[(3r,4s,5s,8s,9s,10s,11r,13r,14s,16s)-16-acetyloxy-3,11-dihydroxy-4,8,10,14-tetramethyl-2,3,4,5,6,7,9,11,12,13,15,16-dodecahydro-1h-cyclopenta[a]phenanthren-17-ylidene]-6-methylhept-5-enoate Chemical compound [Na+].O[C@@H]([C@@H]12)C[C@H]3\C(=C(/CCC=C(C)C)C([O-])=O)[C@@H](OC(C)=O)C[C@]3(C)[C@@]2(C)CC[C@@H]2[C@]1(C)CC[C@@H](O)[C@H]2C HJHVQCXHVMGZNC-JCJNLNMISA-M 0.000 description 1
- IBDSNZLUHYKHQP-UHFFFAOYSA-N sodium;3-oxidodioxaborirane;tetrahydrate Chemical compound O.O.O.O.[Na+].[O-]B1OO1 IBDSNZLUHYKHQP-UHFFFAOYSA-N 0.000 description 1
- KVCGISUBCHHTDD-UHFFFAOYSA-M sodium;4-methylbenzenesulfonate Chemical compound [Na+].CC1=CC=C(S([O-])(=O)=O)C=C1 KVCGISUBCHHTDD-UHFFFAOYSA-M 0.000 description 1
- YKLJGMBLPUQQOI-UHFFFAOYSA-M sodium;oxidooxy(oxo)borane Chemical compound [Na+].[O-]OB=O YKLJGMBLPUQQOI-UHFFFAOYSA-M 0.000 description 1
- SIXNTGDWLSRMIC-UHFFFAOYSA-N sodium;toluene Chemical compound [Na].CC1=CC=CC=C1 SIXNTGDWLSRMIC-UHFFFAOYSA-N 0.000 description 1
- 239000003549 soybean oil Substances 0.000 description 1
- 235000012424 soybean oil Nutrition 0.000 description 1
- 241000894007 species Species 0.000 description 1
- 238000001694 spray drying Methods 0.000 description 1
- 238000010186 staining Methods 0.000 description 1
- 238000010561 standard procedure Methods 0.000 description 1
- 125000004079 stearyl 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])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 125000003107 substituted aryl group Chemical group 0.000 description 1
- JDVPQXZIJDEHAN-UHFFFAOYSA-N succinamic acid Chemical class NC(=O)CCC(O)=O JDVPQXZIJDEHAN-UHFFFAOYSA-N 0.000 description 1
- 150000003871 sulfonates Chemical class 0.000 description 1
- 125000001273 sulfonato group Chemical group [O-]S(*)(=O)=O 0.000 description 1
- 239000000725 suspension Substances 0.000 description 1
- 239000003784 tall oil Substances 0.000 description 1
- KKEYFWRCBNTPAC-UHFFFAOYSA-L terephthalate(2-) Chemical compound [O-]C(=O)C1=CC=C(C([O-])=O)C=C1 KKEYFWRCBNTPAC-UHFFFAOYSA-L 0.000 description 1
- 150000003512 tertiary amines Chemical group 0.000 description 1
- 150000004685 tetrahydrates Chemical class 0.000 description 1
- 235000019818 tetrasodium diphosphate Nutrition 0.000 description 1
- 239000001577 tetrasodium phosphonato phosphate Substances 0.000 description 1
- GTZCVFVGUGFEME-UHFFFAOYSA-N trans-aconitic acid Natural products OC(=O)CC(C(O)=O)=CC(O)=O GTZCVFVGUGFEME-UHFFFAOYSA-N 0.000 description 1
- KHPCPRHQVVSZAH-UHFFFAOYSA-N trans-cinnamyl beta-D-glucopyranoside Natural products OC1C(O)C(O)C(CO)OC1OCC=CC1=CC=CC=C1 KHPCPRHQVVSZAH-UHFFFAOYSA-N 0.000 description 1
- GSEJCLTVZPLZKY-UHFFFAOYSA-O triethanolammonium Chemical compound OCC[NH+](CCO)CCO GSEJCLTVZPLZKY-UHFFFAOYSA-O 0.000 description 1
- AQLJVWUFPCUVLO-UHFFFAOYSA-N urea hydrogen peroxide Chemical compound OO.NC(N)=O AQLJVWUFPCUVLO-UHFFFAOYSA-N 0.000 description 1
- 239000008096 xylene Substances 0.000 description 1
- 229940071104 xylenesulfonate Drugs 0.000 description 1
Landscapes
- Detergent Compositions (AREA)
Abstract
DETERGENCY BUILDER SYSTEM
ABSTRACT OF THE DISCLOSURE
Disclosed is a highly effective detergency builder system comprising the combination of a particular ether carboxylate se-questering agent and particular types of dispersing/anti-rede-position agent. Such a selected ether carboxylate is oxydi-succinic acid or oxydisuccinate. Such particular dispers-ing/anti-redeposition agents can include salts of acrylic acid-based polymers and co-polymers or can include certain ethoxylated amine materials. This selected combination of a particular ether carboxylate sequestering agent and particular dispersing/anti-re-deposition agents provide an especially useful builder system for use in phosphorus-free detergent or laundry additive products.
ABSTRACT OF THE DISCLOSURE
Disclosed is a highly effective detergency builder system comprising the combination of a particular ether carboxylate se-questering agent and particular types of dispersing/anti-rede-position agent. Such a selected ether carboxylate is oxydi-succinic acid or oxydisuccinate. Such particular dispers-ing/anti-redeposition agents can include salts of acrylic acid-based polymers and co-polymers or can include certain ethoxylated amine materials. This selected combination of a particular ether carboxylate sequestering agent and particular dispersing/anti-re-deposition agents provide an especially useful builder system for use in phosphorus-free detergent or laundry additive products.
Description
iLZ~3 7~3 DETERGENCY BUILDER SYSTEM
TECHNICAL FIELD
The present invention relates to detergency builder systems useful in detergent compositions.
The term detergency builder can be applied to any component of a detergent composition which increases the ~etergent power of a surface active agent, hereinafter surfactant. Generally re-cognized functions of detergency builders include removal of 10alkaline earth~ e.g., calcium, and other undesirable metal ions from washing solutions by sequestration or precipitation, provid-ing alkalinity and buffer capacity, prevention of floculation, maintenance of ionic strength, protection of anionic surfactants from precipitation, extraction of metals from soils as an aid to 15their removal, soil suspension, and pep~ization and dispersion of soil. Polyphosphates such as tripolyphosphates and pyrophosphates are widely used as ingredlents in detergent compositions and are highly effective detergency builders. However, the effect of phosphorus on eutrophication of lakes and streams has been ques-20tioned and the use of phosphates in detergent compositions has been subject to government regulation or prohibition.
These circumstances have developed a need for highly effec-tive and efficient phosphorus-free detergency builders. Many materials and combinations o~ materials have been used or proposed 25as detergency builders, Carbonates and silicates are widely used in granular detergent compositions, but by themselves are deFi-cient as detergency builders in a number of respects. Alumino-silicates such as described in U.S. Patent 4,274,975, issued June 23, 1981, to Carkill et al., have also been used to replace 30polyphosphates. Aluminosilicates, however, have relatively low calcium and magnesium binding constants and can present solubility problems, particularly ln combination with sil~cates.
Very usePul phosphorus-Pree detergent builder materlals have been Found to include the ether polycarboxylates. A number oF
35ether carboxylate types have, ln fact, been dlsclosed in the ar~
for use as detergent builders. Many, but not all, ether ~A~
~25~76~
carboxylates are deficient in calcium binding power relative to inorganic polyphosphates. Some ether carboxylates, however~ such as oxydisuccinate as disclosed in Berg; U.S. Patent 3,128,287;
Issued April 7, 1964 and Lamberti et al; U.S. Patent 3,635,830;
Issued January 18, 1972, are quite effective in binding hardness ions such as calcium. These selected e~her carboxylates can therefore be utilized in detergent builder systems which are as effective as conventional phosphorus-type builders in enhancing cleaning performance of detergent products containing them.
Even though certain ether carboxylate compounds can be as effective in builder performance as phosphate materials, ether carboxylates tend to be relatively expensive materials. Accord-ingly, it would be desirable to formulate ether carboxylate-con-taining detergent compositions which provide builder performance that is superior to that of conventional phosphate builders. Such improved builder systems could then be utilized in somewhat lower concentrat~ons in detergent products or could be employed in detergent products which are superior in cleaning performance to conventional phosphate-containing formulations.
In view of the foregoing, it is an object of the present invention to provide ether carboxylate-containing builder composi-tions which, as a system, provide better builder performance than do conventional phosphate materials such as sodium tripolyphos-phate. It is a further object of the present invention to provide improved detergent and laundry additive compositions employing such ether carboxylate-containing builder systems.
SUMMARY OF THE INVENTION
.
The present invent~on provides detergent builder compositions which comprise a) from about 70~ to 99X by weight of an ether carboxylate sequestering agent having the general formula:
H-CH - CH - O - CH - CH-H
COOX COOX COOX COQX
wherein X is H or a salt-forming cation; and b) from about 1% to 30% by weight of a particular type of dispersing/anti-redeposition agent. Thls dispersing/antl-redeposltion agent can comprise e1ther a certain type of polycarboxylate material defined in ~ S 3~ 9 greater detail hereinafter (e.g., polyacrylates or acrylate/male-ate copolymers) or can comprise certain types of ethoxylated amine compounds also defined in greater detail hereinafter (e.g., ethoxylated polyethyleneamines and ethoxylated polyethylen~-imines~. Combinations of such polycarboxylates and ethoxylated amines may also be employed as the dispersing/anti-redeposition agent. The weight ratio of ether carboxylate to dispersingtanti-redeposition agent in such builder compositions ranges from about 99:1 to 70:30.
The present invention also provides detergent and laundry additive compositions containing the two-component, ether car-boxylate-based builder systems herein.
DETAILED DESCRIPTION OF THE INVENTION
The material of the general formula comprises oxydisuccinic acid and its water-soluble salts. This material, also known as 3-oxa-1,2,4,5-pentane-tetracarboxylic acid, in either its acid or water-soluble salt form, is hereinafter referred ~o as "ODS."
Preferred salt-forming cations for ODS include alkali metal (sodium, potassium, lithium), ammonium, C1-C4 substituted ammonium and C1-C4 alkanolamine.
ODS is a known mate~ial which can be prepared by reacting maleic anhydride, maleic acid and/or derivation thereof in the presence of an alkaline earth metal catalyst. ODS, its prepara-tion and its use as a detergent builder material are described more fully in Berg; U.S. Patent 3~128~287i Issued April 7~ 1964 and in Lamberti et al; U.S. Patent 3~635~830r Issued January 18, 1972.
The ODS ether carboxylate sequestering agent will generally comprise from about 70% to 99% by weight of the builder composi-tions. More preferably this ether carboxylate will comprise from about 80% to 95% by weight of the builder compositions. Most preferably, the ether carboxylate component will comprise from about 85% to 92% by weight of the bullder compositions herein.
The second essential component of the builder compositions herein comprlse~ one or more selected types of dispersing/anti-redepositinn ayents. These selected types of dispersin~/anti-~L2S37~
redeposition agents lnclude (1) certain types of polycarboxylate materials and (2) certain types of ethoxylated amine materials.
The polycarboxylate materials which can be employed as the dispersing/anti redeposition agent component herein are these polymers or copolymers which contain at least about 60% by weight o~ segments with the general formula _,( z_ -C_~_ I I
Y COOM n wherein X, Y, and Z are each selected from the group consisting of hydrogen~ methyl, carboxy9 carboxymethyl, hydroxy and hydroxy-lo methyl; a salt-forming cation and n is from about 30 to about 400.
Preferably, X is hydrogen or hydroxy, Y is hydrogen or carboxy, Z
is hydrogen and M is hydrogen, alkali metal, ammonia or substitut-ed ammonlum.
Polycarboxylate materials of this type can be prepared by polymerizing or copolymerizing suitable unsaturated monomers, preferably in their acid form. Unsaturated monomeric acids that can be polymerized to form suitable polymeric polycar~oxylates include acrylic acid, maleic acid (or maleic anhydride), fumaric acid~ itaconlc acid, aconitic acid, mesaconic acid, citracon~c acid and methylenemalonic acid. The presence in the polycarboxy-lates herein of monomeric segments, containing no carboxylate radicals such as vinylmethyl ether, styrene, ethylene, etc. is suitable provlded that such segments do not constitute more than about 40% by weight.
Particularly suitable polycarboxylates can be derived from acrylic acid. Such acrylic acld-based polymers which are useful herein are the water-soluble salts of polymerized acrylic acid.
The average molecular weight Q~ such polymers in the acid form ranges from about 4,000 tQ 10,000, more preferably from about 4000 ~0 to 7QOQ and most preferably from about 4QQO to 5QQO Water soluble salts o~ such acrylic acld polymers can lnclude, ~or example, the alkali metal, ammonium and substituted ammonium ~Z537~
salts. Soluble polymers of this type are known materials. Use of polyacrylates of this type in detergent compositions has been disclosed, for example, in Diehl; U.S. Patent 3,308,067; Issued March 7, 1967.
Acrylic/maleic-based copolymers may also be used as a pre-ferred component of the dispersing/anti-redeposition agent. Such materials include the water-soluble salts of copolymers of acrylic acid and maleic acid. The average molecular weight of such copolymers in the acid form ranges from about 5,000 to 20,~00, preferably from about 6000 to 15000~ more preferably from about 7000 to 12000. The ratio of acrylate to maleate segments in such copolymers will generally range from about 30:1 to about 1:1, more preferably from about 10:1 to 2:1. Water-soluble salts o~ such acrylic acid/maleic acid copolymers can include, for example~ the alkali metal, ammonium and substituted ammonium salts. ~oluble acrylate/maleate copolymers of this type are known materials which are described in European Patent Application No. 66915, published December 1~ 82.
Certain ethoxylated amine compounds may also be used as the dispersing/anti-redeposition component of the builder compositions herein. Such compounds are selected from the group consisting of:
(1) ethoxylated monoamines having the formula:
(X - L- )- N - (R2)2
TECHNICAL FIELD
The present invention relates to detergency builder systems useful in detergent compositions.
The term detergency builder can be applied to any component of a detergent composition which increases the ~etergent power of a surface active agent, hereinafter surfactant. Generally re-cognized functions of detergency builders include removal of 10alkaline earth~ e.g., calcium, and other undesirable metal ions from washing solutions by sequestration or precipitation, provid-ing alkalinity and buffer capacity, prevention of floculation, maintenance of ionic strength, protection of anionic surfactants from precipitation, extraction of metals from soils as an aid to 15their removal, soil suspension, and pep~ization and dispersion of soil. Polyphosphates such as tripolyphosphates and pyrophosphates are widely used as ingredlents in detergent compositions and are highly effective detergency builders. However, the effect of phosphorus on eutrophication of lakes and streams has been ques-20tioned and the use of phosphates in detergent compositions has been subject to government regulation or prohibition.
These circumstances have developed a need for highly effec-tive and efficient phosphorus-free detergency builders. Many materials and combinations o~ materials have been used or proposed 25as detergency builders, Carbonates and silicates are widely used in granular detergent compositions, but by themselves are deFi-cient as detergency builders in a number of respects. Alumino-silicates such as described in U.S. Patent 4,274,975, issued June 23, 1981, to Carkill et al., have also been used to replace 30polyphosphates. Aluminosilicates, however, have relatively low calcium and magnesium binding constants and can present solubility problems, particularly ln combination with sil~cates.
Very usePul phosphorus-Pree detergent builder materlals have been Found to include the ether polycarboxylates. A number oF
35ether carboxylate types have, ln fact, been dlsclosed in the ar~
for use as detergent builders. Many, but not all, ether ~A~
~25~76~
carboxylates are deficient in calcium binding power relative to inorganic polyphosphates. Some ether carboxylates, however~ such as oxydisuccinate as disclosed in Berg; U.S. Patent 3,128,287;
Issued April 7, 1964 and Lamberti et al; U.S. Patent 3,635,830;
Issued January 18, 1972, are quite effective in binding hardness ions such as calcium. These selected e~her carboxylates can therefore be utilized in detergent builder systems which are as effective as conventional phosphorus-type builders in enhancing cleaning performance of detergent products containing them.
Even though certain ether carboxylate compounds can be as effective in builder performance as phosphate materials, ether carboxylates tend to be relatively expensive materials. Accord-ingly, it would be desirable to formulate ether carboxylate-con-taining detergent compositions which provide builder performance that is superior to that of conventional phosphate builders. Such improved builder systems could then be utilized in somewhat lower concentrat~ons in detergent products or could be employed in detergent products which are superior in cleaning performance to conventional phosphate-containing formulations.
In view of the foregoing, it is an object of the present invention to provide ether carboxylate-containing builder composi-tions which, as a system, provide better builder performance than do conventional phosphate materials such as sodium tripolyphos-phate. It is a further object of the present invention to provide improved detergent and laundry additive compositions employing such ether carboxylate-containing builder systems.
SUMMARY OF THE INVENTION
.
The present invent~on provides detergent builder compositions which comprise a) from about 70~ to 99X by weight of an ether carboxylate sequestering agent having the general formula:
H-CH - CH - O - CH - CH-H
COOX COOX COOX COQX
wherein X is H or a salt-forming cation; and b) from about 1% to 30% by weight of a particular type of dispersing/anti-redeposition agent. Thls dispersing/antl-redeposltion agent can comprise e1ther a certain type of polycarboxylate material defined in ~ S 3~ 9 greater detail hereinafter (e.g., polyacrylates or acrylate/male-ate copolymers) or can comprise certain types of ethoxylated amine compounds also defined in greater detail hereinafter (e.g., ethoxylated polyethyleneamines and ethoxylated polyethylen~-imines~. Combinations of such polycarboxylates and ethoxylated amines may also be employed as the dispersing/anti-redeposition agent. The weight ratio of ether carboxylate to dispersingtanti-redeposition agent in such builder compositions ranges from about 99:1 to 70:30.
The present invention also provides detergent and laundry additive compositions containing the two-component, ether car-boxylate-based builder systems herein.
DETAILED DESCRIPTION OF THE INVENTION
The material of the general formula comprises oxydisuccinic acid and its water-soluble salts. This material, also known as 3-oxa-1,2,4,5-pentane-tetracarboxylic acid, in either its acid or water-soluble salt form, is hereinafter referred ~o as "ODS."
Preferred salt-forming cations for ODS include alkali metal (sodium, potassium, lithium), ammonium, C1-C4 substituted ammonium and C1-C4 alkanolamine.
ODS is a known mate~ial which can be prepared by reacting maleic anhydride, maleic acid and/or derivation thereof in the presence of an alkaline earth metal catalyst. ODS, its prepara-tion and its use as a detergent builder material are described more fully in Berg; U.S. Patent 3~128~287i Issued April 7~ 1964 and in Lamberti et al; U.S. Patent 3~635~830r Issued January 18, 1972.
The ODS ether carboxylate sequestering agent will generally comprise from about 70% to 99% by weight of the builder composi-tions. More preferably this ether carboxylate will comprise from about 80% to 95% by weight of the builder compositions. Most preferably, the ether carboxylate component will comprise from about 85% to 92% by weight of the bullder compositions herein.
The second essential component of the builder compositions herein comprlse~ one or more selected types of dispersing/anti-redepositinn ayents. These selected types of dispersin~/anti-~L2S37~
redeposition agents lnclude (1) certain types of polycarboxylate materials and (2) certain types of ethoxylated amine materials.
The polycarboxylate materials which can be employed as the dispersing/anti redeposition agent component herein are these polymers or copolymers which contain at least about 60% by weight o~ segments with the general formula _,( z_ -C_~_ I I
Y COOM n wherein X, Y, and Z are each selected from the group consisting of hydrogen~ methyl, carboxy9 carboxymethyl, hydroxy and hydroxy-lo methyl; a salt-forming cation and n is from about 30 to about 400.
Preferably, X is hydrogen or hydroxy, Y is hydrogen or carboxy, Z
is hydrogen and M is hydrogen, alkali metal, ammonia or substitut-ed ammonlum.
Polycarboxylate materials of this type can be prepared by polymerizing or copolymerizing suitable unsaturated monomers, preferably in their acid form. Unsaturated monomeric acids that can be polymerized to form suitable polymeric polycar~oxylates include acrylic acid, maleic acid (or maleic anhydride), fumaric acid~ itaconlc acid, aconitic acid, mesaconic acid, citracon~c acid and methylenemalonic acid. The presence in the polycarboxy-lates herein of monomeric segments, containing no carboxylate radicals such as vinylmethyl ether, styrene, ethylene, etc. is suitable provlded that such segments do not constitute more than about 40% by weight.
Particularly suitable polycarboxylates can be derived from acrylic acid. Such acrylic acld-based polymers which are useful herein are the water-soluble salts of polymerized acrylic acid.
The average molecular weight Q~ such polymers in the acid form ranges from about 4,000 tQ 10,000, more preferably from about 4000 ~0 to 7QOQ and most preferably from about 4QQO to 5QQO Water soluble salts o~ such acrylic acld polymers can lnclude, ~or example, the alkali metal, ammonium and substituted ammonium ~Z537~
salts. Soluble polymers of this type are known materials. Use of polyacrylates of this type in detergent compositions has been disclosed, for example, in Diehl; U.S. Patent 3,308,067; Issued March 7, 1967.
Acrylic/maleic-based copolymers may also be used as a pre-ferred component of the dispersing/anti-redeposition agent. Such materials include the water-soluble salts of copolymers of acrylic acid and maleic acid. The average molecular weight of such copolymers in the acid form ranges from about 5,000 to 20,~00, preferably from about 6000 to 15000~ more preferably from about 7000 to 12000. The ratio of acrylate to maleate segments in such copolymers will generally range from about 30:1 to about 1:1, more preferably from about 10:1 to 2:1. Water-soluble salts o~ such acrylic acid/maleic acid copolymers can include, for example~ the alkali metal, ammonium and substituted ammonium salts. ~oluble acrylate/maleate copolymers of this type are known materials which are described in European Patent Application No. 66915, published December 1~ 82.
Certain ethoxylated amine compounds may also be used as the dispersing/anti-redeposition component of the builder compositions herein. Such compounds are selected from the group consisting of:
(1) ethoxylated monoamines having the formula:
(X - L- )- N - (R2)2
(2) ethoxylated diamines having the formula:
R2 _ N - R1- N - R2 (R2)2 - N - R1- N - (R2)2 J
X X X
or (X-L-)2- N - R} - N - (R2)2 ~3) ethoxylated polyamines having the formula:
~253q6~
'~~ R3 - [(Al)q (R4)t h-L-X]p (4) ethoxyla~ed ~mine polymers having the genera1 formula:
N ]w ~-R -N-] X-~-Rl N-~ y [-Rl-N-L-X) O O O
and (5) mixtures thereof; wherein A1 is -~C-, -NC0-, -~C~-, R R R R
~0, ~0, ,0 0 0 9 O
RR R
R is H or C1-C4 alkyl or hydroxyalkyl3 Rl is C2-C12 alkylene, hydroxyalkylene, alkenylene, arylene or alkarylene, or a C2-C3 oxyalkylene moiety having from 2 to about 20 oxyalkylene units provided that no 0-N bonds are formed ; each R2 is Cl-C4 alkyl or :L0 hydroxyalkyl, the moiety -L-X, or two R2 together form the moiety -(CH2)r-A2-(CH2~S-, wherein A2 jS o.. or -CH2-, r is 1 or 2, s is 1 or 2, and r + s is 3 or 4; X is a nonionic group, an anionic group or mixture thereof; R3 is a substituted C3-C12 alkyl, hydroxyalkyl, alkenyl, aryl, or alkaryl group having p substi-tut~on sites; R4 is C1-C12 alkylene, hydroxyalkylene, alkenylene, arylene or alkarylene, or a C2-C3 oxyalkylene moiety have from 2 to about 20 oxyalkylene units provlded that no 0-0 or 0-N bonds are formed; L is a hydrophilic chain wh~ch contains the polyoxy-alkylene moiety -~(R50)m(CH2CH20)n~-, wherein R5 is C3-C4 alkylene or hydroxyalkylene and m and n are numbers such ~hat the moiety -(CH2CH20)n- comprises at least about SOX by weight of said polyoxyalkylene mo~ety; for said monoamines, m is from 0 to about 4, and n ls at least about 12~ for said diamines~ m is from 0 ~o abou~ 3, and n is at least about 6 when R1 is C2-C3 alkylene, hydroxyalkylene, or alkenylene, and at least about 3 when R1 is other than C2-C3 alkylene, hydroxyalkylene or alkenylene, for said polyamines and amine polymers, m ~5 frQm 0 to about 10 and n ~s at leas~ about 3; p ~s ~rom 3 to 8; q ~s 1 or 0; t is 1 or 0, . ,~, .~ ., ~:~53~769 provided that t is 1 when q is 1; w is 1 or 0; x ~ y + z is at least 2; and y + z is at least 2.
As indicated, in the preceding formulas, R1 can be branched ( .9. CH2 CH-, -CH2 ~ -), cyclic (e.g. ~ ), or m ~ preferably linear (e.g. -CH2CH2-9 -CH2-CH2-CH2-, -CH2-~H-) alkylene, hydroxyalkylene, alkenylene, alkarylene or oxyalkylene. R is preferably C2-C6 alkylene for the ethoxylated diamines and amine polymers. For the ethoxylated diamines, the minimum degree of ethoxylation required for suitable clay soil removal/anti-redeposition properties decreases on going from C2-C3 alkylene (ethylene, propylené) to hexamethylene. However, for the ethoxylated amine polymers, in particular the ethoxylated poly-alkyleneamines and polyalkyleneimines, especially at higher molecular weights, C2-C3 alkylenes (ethylene, propylene) are preferred for R with ethylene being most preferred. Each R2 is preferably the moiety -L-X.
In the preceding formulas, hydrophilic chain L usually consists entirely of the polyoxyalkylene moie~y -~(R50)m(CH2CH20)n]-. The moieties ~(R50)m~ and -(CH2CH20)n- of the polyoxyalkylene moiety can be mixed together or preferably form blocks of ~(R50)m~ and -(CH2CH20)n- moieties. R5 is prefer-ably C3H6 (propylene). For the ethoxylated polyamines and amine polymers, m is preferably from 0 to about 5. For all ethoxylated amlnes used in the present invention, m is most preferably 0, i.e.
the polyoxyalkylene moiety consists entirely of the moiety -(CH2CH20)n-. The moiety -(CH2CH20)n- preferably comprises at least about 85% by weight of the polyoxyalkylene moiety and most preferably 100% by weight (m is 0).
In the preceding formulas, X can be any campatible nonionic group, anionic group or mlxture thereof. Suitable nonionlc groups ~nclude C1-C4 alkyl or hydroxyalkyl ester or ether groups, pref erably acetate or methyl ether, respectively; hydrog~n ~H)~ or m~xtures thereof. The particularly pre~erred non~onic group ls H.
~L2~3~6~
With regard to anionic groups, po3 2 and 503 are suitable. The particularly preferred anionic group is S03 . It has been found that the percenta~e of anionic groups relative to nonionic groups can be important to the anti-redeposition properties provided by the ethoxylated amine. A mixture of from 0 to about 30% anionic groups and from about 70 to 100% nonionic groups provides pre-ferred properties. A mixture of from about 5 to about 10% anionic groups and from about 90 to about 95% nonionic groups provides the most preferred properties. Usually, a mixture of from 0 to about 80% anionic groups and from about 20 to 100~ nonionic groups provides suitable anti-redeposition properties.
Preferred ethoxylated mono- and diamines have the formula:
X (CH2CH2)n N-[CH2-CH2-(CH2)b-N]a (CH2CH2C)n X
(CH2CH20)n-X (CH2CH20)n-X
wherein X and n are defined as before, a is 0 or 1, and b is from 0 to 4. For preferred ethoxylated monoamines (a = o), n is at least about 15, with a typical range of from about 15 to about 35.
For preferred ethoxylated diamines (a ~ 1), n is at least about 12 with a typical range of from about 12 to about 42.
In the preceding formula for the ethoxylated polyamines, R3 (linear, branched or cyclic) is preferably a substituted C3-C6 alkyl, hydroxyalkyl or aryl group;
o A1 is preferably -CN-; n is preferably at least about 12~ with a typieal range of from about 12 to about 42; p is preferably from 3 to 6. When R3 is a substituted aryl or alkaryl graup, q is preferably 1 and R4 is preferably C2-C3 alkylene. When R3 is an alkyl, hydroxyalkyl, or alkenyl group, and when q is 0, Rl is preferably d C2-C3 oxyalkylene moiety; when q is 1, R4 is pre-ferably C2-C3 alkylene.
These ethoxylated polyamines can be derived from polyamino amides such as:
" ~2537~g -CN-(C3H6)-NH2 H0 - ~N-(C3H6)-NH2 or ~ CN(C3H6)-NH2 " ( 3H6)-NH2 These ethoxylated polyamines can also be derived from polyamino-propyleneoxide derivatives such as:
r ~oC3H6)c NH2 CH3 (C3H6)c NH2 ( C3H6 ) c N~2 wherein each c is a number of from 2 to about 20.
Preferred ethoxylated amine polymers are the ethoxylated C2-C3 polyalkyleneamines and polyalkyleneimines. Particularly preferred ethoxylated polyalkyleneamines and polyalkyleneimines are the ethoxylated polyethylen~amines (PEAs) and polyethylene-;mines '(PEIs). These preferred compounds comprise units havingthe general formula:
w--~CH2ctl2N]x--~CH2CH2N] y ~ [CH2CH2N]Z
~ (CH2CH20)n~X~2 (cH;~cH2o~n-x [(CH2CH20)n-X~2 wherein X, wt x, y, z and n are defined as before.
Prior to ethoxylation, the PEAs used in preparing compounds of the present invention have the following general formula:
[H2~ - [C~l2CH2~ - ~H2C~2~ - ~H2CH2 23 wherein x + y + z is from 2 to 9, y ~ 7 iS from 2 to ~ and w is 0 or 1 (molecular weight of from about 100 to about 400). Each hydrogen atom attached to each nitrogen atom represents an active site for subsequent ethoxylation. For preferred PEAs, y ~ z is from about 3 to about 7 (molecular weight of from about 140 to about 310) and most preferably from about 3 to about 4 (molecular wei~ht of ~rom about 140 to about 200). These PEAs can be ob-ta~ned by reactions ~nvolving ammon~a and eth,ylene dichloride, ~2~3'7~3 followed by fractional distillation. The common PEAs obtained are triethylenetetramine (TETA) and tetraethylenepentamine (TEPA).
Above the pentaminesl i.e., the hexamines, heptamines, octamines and possibly nonamines, the cogenerically derived mix$ure does not appear to separate by distillation and can include other materials such as cyclic amines and particularly piperazines. There can also be presen~ cyclic amines with side chains in which nitrogen atoms appear. See U.S. Patent 2,792,372 to Dickson~ issued May 14~ 1957, which describes the preparation of PEAs.
The minimum degree of ethoxylation required for preferred clay soil removal/anti-redeposition performance can vary depending upon the number of units in the PEA. Where y + z is 2 or 3, n is preferably at least about 6. Where y + z is ~rom 4 to 9, suitable benefits are achieved when n is at least about 3. For most preferred ethoxylated PEAs, n is a~ least about 12 with a typical range of from about 12 to about 42.
The PEIs used in preparing the dispersing/anti-redeposition agents used in the present invention have a molecular weight of at least about 440 prior to ethoxylation, which represents at least 20 about 10 units. Preferred PEIs used in preparing these compounds have a molecular weight of from about 600 to about 1800. The polymer backbone of these PEls can be represented by the general formula:
H
H2N ~ [CH2cH2N]x ~ ~CH2CH2N] y ~CH2CH2 2]z 25 wherein the sum of x, y and z represents a number of sufficient magnitude to yield a polymer having the molecular weights pre~
viously specified. Although linear polymer backbones are pos-sible, branch chains can also occur. The relative proportions of primary, secondary and tertiary amine groups present in the polymer can vary, depending on the manner o~ preparation. The distribution of amine groups is typically as fallQws:
-CH~CH2-NH~ 30%
-CH2CH2-NH~ 40%
C~l2CH2 ~ 30%
Each hydrogen atom attached to each nitrogen atom of the PEI
~253r769 represents an active site for subsequent ethoxylation. These PEIs can be prepared, for example, by polymerizing ethyleneimine in the presence of a catalyst such as carbon dioxide, sodium bisulfite, sulfuric acid, hydrogen peroxide, hydrochloric acid, acetic acid, etc. Specific methods for preparing PEIs are d;sclosed in U.S.
Patent 2,182,306 to Ulrich et al., issued December 5, 1939i U.S.
Patent 3,033,746 to Mayle et al. 9 issued May 8, 1962; U.S. Patent 2,208,095 to Esselmann et al., issued July 16, 1940; U.S. Patent 2,806,839 to Crowther, issued September 17, 1957; and U.S. Patent 2,553,696 to Wilson, issued May 21, 1951.
As defined in the preceding formulas, n is at least about 3 for the ethoxylated PEIs. However, it should be noted that the minimum degree of ethoxylation required for suitable clay soil removal/anti-redeposition performance can increase as the mole-cular weight of the PEI increases, especially much beyond about1800. Also, the degree of ethoxylation for preferred compounds increases as the molecular weight o~ the PEI increases. For PEIs having a molecular weight of at least about 600, n is preferably at least about 12, with a typical range of from about 12 to about 20 42. For PEIs having a molecular weight of at least 1800, n is preferably at least about 24, with a typical range of from about 24 to about 42.
The ethoxylated amine compounds useful in dispersing/anti-redeposition agents in the builder compositions of the present 25 invention can be prepared by standard methods for ethoxylating amines. For the diamines, polyamines, and amine polymers such as the polyalkyleneamines and polyalkyleneimines, there is preferably an initial step of condensing sufficient ethylene oxide to provide 2-hydroxyethyl groups at each reactive site (hydroxyethylation).
This initial step can be omitted by starting with a 2-hydroxyethyl amine such as triethanolamine (TEA). The appropriate amount of ethylene oxide is then condensed with these 2-hydroxyethylamines using an alkali metal (e.g., sodium, potassium) hydride or hy-droxide as the catalyst to provide the respective ethoxylated amlnes~ The ~o~al de~ree of ethoxylatlon per reactive site (n) can be determined according to the follQwing formula:
~ZS3~6g Degree of Ethoxylation - E/(A x R) wherein E is the total number of moles of ethylene oxide condensed (including hydroxyethylation) , A is the number of moles of the starting amine, and R is the number of reactive sites (typically 3 for monoamines, 4 for diamines, 2 x p for polyamines, and 3 + y +
z for the amine polymers) for the starting amine.
Preferred embodiments of the builder compositions herein utilize a combination of polycarboxylates and ethoxylated amines as the dispersing/anti-redeposition agent components. In such embodiments, the weight ratio of polycarboxylate to ethoxylated amine generally ranges from about 5:1 to 1:5~ more preferably from about 3:2 to 2:3. Compositions containing such a combination of polycarboxylate and ethoxylated amine dispersing/anti-redeposition agents are especially effective at promoting certain types of fabric cleaning.
Whether a single material or a combination of compounds, the dispersing/anti-redeposition component will generally comprise from about 1% to 30% by weight of the builder composition, more preferably from about 5% to 20~ by weight, most preferably from about 8% to 15% by weight. Furthermore, it is preferred that within the builder compositions herein, the weight ratic of ether carboxylate to dispersing/anti-redeposition agent ranges from about 70:30 to 99:1, more pre~erably ~rom about 80:20 to 95:5.
The builder compositions herein can be prepared by simply combining the essential ether carboxylate sequestering agent and the polycarboxylate and/or ethoxylated amine dispersing/anti-rede-position agent in the desired proportions. This combination of components can be prepared as a builder composition per se. More frequently however, the essential components of the builder compositions herein will simply be incorporated individually into a detergent composition or laundry additive composit~on. In such detergent or laundry additive compasitions, the weight ratio of the essential ether carboxylate component to the essential dis-persing/anti-redepos~tion component will generally ranQe from about 70:30 to 99:1~ more preferably from about 80:20 to 9S:5.
53~
Detergent compositions incorporating the builder systems of the present invention contain as essential components from about 5% to about 40% of a surfactant, from about 5% to about 50% of the ether carboxylate sequestering agent and from about 0.2% to 5% by weight of the dispersing/anti-redeposition agent.
Typical laundry detergent compositions within the scope of the present invention contain from about 5% to about 30% of a surfactant and from about 5% to about 80% total detergency build-er. Of this builder component from about 20% to 100% by weight of lo builder component can be the two-compound builder systems of the present invention with the balance of the builder component being optional known builders.
Detergent compositions herein may also contain from about 0.1% to 95% by weight of a wide variety of additional optional components. Such optional components can include, for example, additional detergent builders, chelating agents, en2ymes, fabric whiteners and br~ghteners, sudsing control agents, solvents, hydrotropes, bleaching agents, bleach precursors, buffering agents9 additional soil removal/anti-redeposition agents, soil 20 release agents7 fabric softening agents, perfumes, colorants and opacifiers. A number of these additional optional components are hereinafter described in greater detail.
The detergent compositions of this invention are effective in cleaning solutions over the broad cleaning salution pH range of 25 from about ~ to about 13. The compositions can be formulated to provide a desired cleaning solution pH by proper selection of the acid form of appropriate salts or mixtures thereof. Pre~erred water-soluble salts of the builder compounds, for example, can be the alkali metal salts such as sodium, potassium, lithium and ammonium or substituted ammonium, e.g. triethanol ammonium.
Depending on the pH of the desired solution, the salts are par-tially or fully neutralized.
The detergent compositions of this invention can be prepared in solid or liquid physical form.
~L~25 3 The detergent compositions of this invention are particularly suitable for laundry use, but are also suitable for the cleaning of hard surfaces and for dishwashing.
In a laundry method using the detergent composition of this invention, typical laundry wash water solutions comprise from about 0.1~ to about 1% by weight of the de$ergent compositions of this invention.
The two-component builder systems herein may also be employed as builders in laundry additive compositions. Laundry additive compositions of the present invention contain as essential compo-nents from about 5% to about 95% of the ether carboxylate com-pounds hereinbefore described and from about 0.2% to 10% by weight of the dispersing/anti-redeposition agents hereinbefore described.
Such laundry additives compositions will also contain from about 0.5% to 98% by weight of a laundry adjuvant selected from the group consisting of surfactants, alternate builders, enzymes, fabric whiteners and brighteners, sudsing control agents, sol-vents, hydrotropes, bleaching agents, bleach precursors, buffering agents, additional soil removal/antideposition agents, soil ~o release agents, fabric softening agents, perfumes, colorants, opacifiers and mixtures of these adjuvants. Such adjuvants, whether used in the detergent or laundry additive co~positions herein, perform their expected functions in such composi~ions. A
number of these adjuvants are described in greater detail as follows:
Surfactants Various types of surfactants can be used in the detergent or laundry additive compositions of this invention. Useful surfac-tants include anionic, nonionic, ampholytic, zwitter~onic and cationic surfactants or mixtures of such materials. Detergent compositions for laundry use typically contain from about 5% to about 30% anlonic surfactants, mlxtures of anionic and nonionic surfactants or cation~c surfactants. Detergent compositions for use in automakic dishwashing machines typically contain from about 2% to about 6% by weight of a relatively 1QW SUdS;n9 nOnjQnjC
surfactant or mixtures thereof and~ opt~onally, suds control `` ~2537~
agents. Particularly suitable low sudsing nonionic surfactants are the alkoxylation products of compounds containing at least one reactive hydrogen wherein, preferably, at least abo~t 20% ~y weight of the alkyl~ne oxide by weight is propylene oxide.
Examples are products of ~he BASF-Wyandotte Corporation designated Pluroni ~, Tetroni ~, Plurado ~ and block polymerir variations in which propoxylation follows ethoxylation. Preferred suds control a~ents include mono-and distearyl acid phosphates.
The various classes of surfactants useful in the detergent and laundry additive compositions herein are exemplified as follows:
(A) Anionic soap and non-soap surfactants This class of surfactants includes alkali metal monocar-boxylates (soaps) such as the sodium, potassium, ammonium and alkylolammonium salts of higher fatty acids containing from about 8 to about 24 carbon atoms and preferably from about 12 to about 18 carbon atoms. Suitable fatty acids can be obtained from natural sources such as, for instance, from plant or animal esters (e.g., palm oil, coconut oil, babassu oil, soybean oil, castor oil, tallow, whale and fish oils, grease, lard, and mixtures thereof). The fatty acids also can be synthetically prepared (e.g., by the oxidation of petroleum, or by hydrogenation of carbon monoxide by the Fischer-Tropsch process). Resin acids are suitable such as rosin and those resin acids in tall oil. Naph-thenic acids are also suitable. Sodium and potassium soaps can bemade by direct sapnnification of the fats and oils or by the neutralizatlon of the free fatty acids which are prepared in a separate manufacturing process. Particularly useful are the sodium and potassium salts of the mixtures of fatty acids derived from coconut oil and tallow, i~e., sodium or potassium tallow and coconut soap. Soaps and fatty acids also act as detergency bullders in detergent composltions because they remove mul~ivalent ions by precipitatlon.
Anion~c surfactants also include water-soluble salts, par-
R2 _ N - R1- N - R2 (R2)2 - N - R1- N - (R2)2 J
X X X
or (X-L-)2- N - R} - N - (R2)2 ~3) ethoxylated polyamines having the formula:
~253q6~
'~~ R3 - [(Al)q (R4)t h-L-X]p (4) ethoxyla~ed ~mine polymers having the genera1 formula:
N ]w ~-R -N-] X-~-Rl N-~ y [-Rl-N-L-X) O O O
and (5) mixtures thereof; wherein A1 is -~C-, -NC0-, -~C~-, R R R R
~0, ~0, ,0 0 0 9 O
RR R
R is H or C1-C4 alkyl or hydroxyalkyl3 Rl is C2-C12 alkylene, hydroxyalkylene, alkenylene, arylene or alkarylene, or a C2-C3 oxyalkylene moiety having from 2 to about 20 oxyalkylene units provided that no 0-N bonds are formed ; each R2 is Cl-C4 alkyl or :L0 hydroxyalkyl, the moiety -L-X, or two R2 together form the moiety -(CH2)r-A2-(CH2~S-, wherein A2 jS o.. or -CH2-, r is 1 or 2, s is 1 or 2, and r + s is 3 or 4; X is a nonionic group, an anionic group or mixture thereof; R3 is a substituted C3-C12 alkyl, hydroxyalkyl, alkenyl, aryl, or alkaryl group having p substi-tut~on sites; R4 is C1-C12 alkylene, hydroxyalkylene, alkenylene, arylene or alkarylene, or a C2-C3 oxyalkylene moiety have from 2 to about 20 oxyalkylene units provlded that no 0-0 or 0-N bonds are formed; L is a hydrophilic chain wh~ch contains the polyoxy-alkylene moiety -~(R50)m(CH2CH20)n~-, wherein R5 is C3-C4 alkylene or hydroxyalkylene and m and n are numbers such ~hat the moiety -(CH2CH20)n- comprises at least about SOX by weight of said polyoxyalkylene mo~ety; for said monoamines, m is from 0 to about 4, and n ls at least about 12~ for said diamines~ m is from 0 ~o abou~ 3, and n is at least about 6 when R1 is C2-C3 alkylene, hydroxyalkylene, or alkenylene, and at least about 3 when R1 is other than C2-C3 alkylene, hydroxyalkylene or alkenylene, for said polyamines and amine polymers, m ~5 frQm 0 to about 10 and n ~s at leas~ about 3; p ~s ~rom 3 to 8; q ~s 1 or 0; t is 1 or 0, . ,~, .~ ., ~:~53~769 provided that t is 1 when q is 1; w is 1 or 0; x ~ y + z is at least 2; and y + z is at least 2.
As indicated, in the preceding formulas, R1 can be branched ( .9. CH2 CH-, -CH2 ~ -), cyclic (e.g. ~ ), or m ~ preferably linear (e.g. -CH2CH2-9 -CH2-CH2-CH2-, -CH2-~H-) alkylene, hydroxyalkylene, alkenylene, alkarylene or oxyalkylene. R is preferably C2-C6 alkylene for the ethoxylated diamines and amine polymers. For the ethoxylated diamines, the minimum degree of ethoxylation required for suitable clay soil removal/anti-redeposition properties decreases on going from C2-C3 alkylene (ethylene, propylené) to hexamethylene. However, for the ethoxylated amine polymers, in particular the ethoxylated poly-alkyleneamines and polyalkyleneimines, especially at higher molecular weights, C2-C3 alkylenes (ethylene, propylene) are preferred for R with ethylene being most preferred. Each R2 is preferably the moiety -L-X.
In the preceding formulas, hydrophilic chain L usually consists entirely of the polyoxyalkylene moie~y -~(R50)m(CH2CH20)n]-. The moieties ~(R50)m~ and -(CH2CH20)n- of the polyoxyalkylene moiety can be mixed together or preferably form blocks of ~(R50)m~ and -(CH2CH20)n- moieties. R5 is prefer-ably C3H6 (propylene). For the ethoxylated polyamines and amine polymers, m is preferably from 0 to about 5. For all ethoxylated amlnes used in the present invention, m is most preferably 0, i.e.
the polyoxyalkylene moiety consists entirely of the moiety -(CH2CH20)n-. The moiety -(CH2CH20)n- preferably comprises at least about 85% by weight of the polyoxyalkylene moiety and most preferably 100% by weight (m is 0).
In the preceding formulas, X can be any campatible nonionic group, anionic group or mlxture thereof. Suitable nonionlc groups ~nclude C1-C4 alkyl or hydroxyalkyl ester or ether groups, pref erably acetate or methyl ether, respectively; hydrog~n ~H)~ or m~xtures thereof. The particularly pre~erred non~onic group ls H.
~L2~3~6~
With regard to anionic groups, po3 2 and 503 are suitable. The particularly preferred anionic group is S03 . It has been found that the percenta~e of anionic groups relative to nonionic groups can be important to the anti-redeposition properties provided by the ethoxylated amine. A mixture of from 0 to about 30% anionic groups and from about 70 to 100% nonionic groups provides pre-ferred properties. A mixture of from about 5 to about 10% anionic groups and from about 90 to about 95% nonionic groups provides the most preferred properties. Usually, a mixture of from 0 to about 80% anionic groups and from about 20 to 100~ nonionic groups provides suitable anti-redeposition properties.
Preferred ethoxylated mono- and diamines have the formula:
X (CH2CH2)n N-[CH2-CH2-(CH2)b-N]a (CH2CH2C)n X
(CH2CH20)n-X (CH2CH20)n-X
wherein X and n are defined as before, a is 0 or 1, and b is from 0 to 4. For preferred ethoxylated monoamines (a = o), n is at least about 15, with a typical range of from about 15 to about 35.
For preferred ethoxylated diamines (a ~ 1), n is at least about 12 with a typical range of from about 12 to about 42.
In the preceding formula for the ethoxylated polyamines, R3 (linear, branched or cyclic) is preferably a substituted C3-C6 alkyl, hydroxyalkyl or aryl group;
o A1 is preferably -CN-; n is preferably at least about 12~ with a typieal range of from about 12 to about 42; p is preferably from 3 to 6. When R3 is a substituted aryl or alkaryl graup, q is preferably 1 and R4 is preferably C2-C3 alkylene. When R3 is an alkyl, hydroxyalkyl, or alkenyl group, and when q is 0, Rl is preferably d C2-C3 oxyalkylene moiety; when q is 1, R4 is pre-ferably C2-C3 alkylene.
These ethoxylated polyamines can be derived from polyamino amides such as:
" ~2537~g -CN-(C3H6)-NH2 H0 - ~N-(C3H6)-NH2 or ~ CN(C3H6)-NH2 " ( 3H6)-NH2 These ethoxylated polyamines can also be derived from polyamino-propyleneoxide derivatives such as:
r ~oC3H6)c NH2 CH3 (C3H6)c NH2 ( C3H6 ) c N~2 wherein each c is a number of from 2 to about 20.
Preferred ethoxylated amine polymers are the ethoxylated C2-C3 polyalkyleneamines and polyalkyleneimines. Particularly preferred ethoxylated polyalkyleneamines and polyalkyleneimines are the ethoxylated polyethylen~amines (PEAs) and polyethylene-;mines '(PEIs). These preferred compounds comprise units havingthe general formula:
w--~CH2ctl2N]x--~CH2CH2N] y ~ [CH2CH2N]Z
~ (CH2CH20)n~X~2 (cH;~cH2o~n-x [(CH2CH20)n-X~2 wherein X, wt x, y, z and n are defined as before.
Prior to ethoxylation, the PEAs used in preparing compounds of the present invention have the following general formula:
[H2~ - [C~l2CH2~ - ~H2C~2~ - ~H2CH2 23 wherein x + y + z is from 2 to 9, y ~ 7 iS from 2 to ~ and w is 0 or 1 (molecular weight of from about 100 to about 400). Each hydrogen atom attached to each nitrogen atom represents an active site for subsequent ethoxylation. For preferred PEAs, y ~ z is from about 3 to about 7 (molecular weight of from about 140 to about 310) and most preferably from about 3 to about 4 (molecular wei~ht of ~rom about 140 to about 200). These PEAs can be ob-ta~ned by reactions ~nvolving ammon~a and eth,ylene dichloride, ~2~3'7~3 followed by fractional distillation. The common PEAs obtained are triethylenetetramine (TETA) and tetraethylenepentamine (TEPA).
Above the pentaminesl i.e., the hexamines, heptamines, octamines and possibly nonamines, the cogenerically derived mix$ure does not appear to separate by distillation and can include other materials such as cyclic amines and particularly piperazines. There can also be presen~ cyclic amines with side chains in which nitrogen atoms appear. See U.S. Patent 2,792,372 to Dickson~ issued May 14~ 1957, which describes the preparation of PEAs.
The minimum degree of ethoxylation required for preferred clay soil removal/anti-redeposition performance can vary depending upon the number of units in the PEA. Where y + z is 2 or 3, n is preferably at least about 6. Where y + z is ~rom 4 to 9, suitable benefits are achieved when n is at least about 3. For most preferred ethoxylated PEAs, n is a~ least about 12 with a typical range of from about 12 to about 42.
The PEIs used in preparing the dispersing/anti-redeposition agents used in the present invention have a molecular weight of at least about 440 prior to ethoxylation, which represents at least 20 about 10 units. Preferred PEIs used in preparing these compounds have a molecular weight of from about 600 to about 1800. The polymer backbone of these PEls can be represented by the general formula:
H
H2N ~ [CH2cH2N]x ~ ~CH2CH2N] y ~CH2CH2 2]z 25 wherein the sum of x, y and z represents a number of sufficient magnitude to yield a polymer having the molecular weights pre~
viously specified. Although linear polymer backbones are pos-sible, branch chains can also occur. The relative proportions of primary, secondary and tertiary amine groups present in the polymer can vary, depending on the manner o~ preparation. The distribution of amine groups is typically as fallQws:
-CH~CH2-NH~ 30%
-CH2CH2-NH~ 40%
C~l2CH2 ~ 30%
Each hydrogen atom attached to each nitrogen atom of the PEI
~253r769 represents an active site for subsequent ethoxylation. These PEIs can be prepared, for example, by polymerizing ethyleneimine in the presence of a catalyst such as carbon dioxide, sodium bisulfite, sulfuric acid, hydrogen peroxide, hydrochloric acid, acetic acid, etc. Specific methods for preparing PEIs are d;sclosed in U.S.
Patent 2,182,306 to Ulrich et al., issued December 5, 1939i U.S.
Patent 3,033,746 to Mayle et al. 9 issued May 8, 1962; U.S. Patent 2,208,095 to Esselmann et al., issued July 16, 1940; U.S. Patent 2,806,839 to Crowther, issued September 17, 1957; and U.S. Patent 2,553,696 to Wilson, issued May 21, 1951.
As defined in the preceding formulas, n is at least about 3 for the ethoxylated PEIs. However, it should be noted that the minimum degree of ethoxylation required for suitable clay soil removal/anti-redeposition performance can increase as the mole-cular weight of the PEI increases, especially much beyond about1800. Also, the degree of ethoxylation for preferred compounds increases as the molecular weight o~ the PEI increases. For PEIs having a molecular weight of at least about 600, n is preferably at least about 12, with a typical range of from about 12 to about 20 42. For PEIs having a molecular weight of at least 1800, n is preferably at least about 24, with a typical range of from about 24 to about 42.
The ethoxylated amine compounds useful in dispersing/anti-redeposition agents in the builder compositions of the present 25 invention can be prepared by standard methods for ethoxylating amines. For the diamines, polyamines, and amine polymers such as the polyalkyleneamines and polyalkyleneimines, there is preferably an initial step of condensing sufficient ethylene oxide to provide 2-hydroxyethyl groups at each reactive site (hydroxyethylation).
This initial step can be omitted by starting with a 2-hydroxyethyl amine such as triethanolamine (TEA). The appropriate amount of ethylene oxide is then condensed with these 2-hydroxyethylamines using an alkali metal (e.g., sodium, potassium) hydride or hy-droxide as the catalyst to provide the respective ethoxylated amlnes~ The ~o~al de~ree of ethoxylatlon per reactive site (n) can be determined according to the follQwing formula:
~ZS3~6g Degree of Ethoxylation - E/(A x R) wherein E is the total number of moles of ethylene oxide condensed (including hydroxyethylation) , A is the number of moles of the starting amine, and R is the number of reactive sites (typically 3 for monoamines, 4 for diamines, 2 x p for polyamines, and 3 + y +
z for the amine polymers) for the starting amine.
Preferred embodiments of the builder compositions herein utilize a combination of polycarboxylates and ethoxylated amines as the dispersing/anti-redeposition agent components. In such embodiments, the weight ratio of polycarboxylate to ethoxylated amine generally ranges from about 5:1 to 1:5~ more preferably from about 3:2 to 2:3. Compositions containing such a combination of polycarboxylate and ethoxylated amine dispersing/anti-redeposition agents are especially effective at promoting certain types of fabric cleaning.
Whether a single material or a combination of compounds, the dispersing/anti-redeposition component will generally comprise from about 1% to 30% by weight of the builder composition, more preferably from about 5% to 20~ by weight, most preferably from about 8% to 15% by weight. Furthermore, it is preferred that within the builder compositions herein, the weight ratic of ether carboxylate to dispersing/anti-redeposition agent ranges from about 70:30 to 99:1, more pre~erably ~rom about 80:20 to 95:5.
The builder compositions herein can be prepared by simply combining the essential ether carboxylate sequestering agent and the polycarboxylate and/or ethoxylated amine dispersing/anti-rede-position agent in the desired proportions. This combination of components can be prepared as a builder composition per se. More frequently however, the essential components of the builder compositions herein will simply be incorporated individually into a detergent composition or laundry additive composit~on. In such detergent or laundry additive compasitions, the weight ratio of the essential ether carboxylate component to the essential dis-persing/anti-redepos~tion component will generally ranQe from about 70:30 to 99:1~ more preferably from about 80:20 to 9S:5.
53~
Detergent compositions incorporating the builder systems of the present invention contain as essential components from about 5% to about 40% of a surfactant, from about 5% to about 50% of the ether carboxylate sequestering agent and from about 0.2% to 5% by weight of the dispersing/anti-redeposition agent.
Typical laundry detergent compositions within the scope of the present invention contain from about 5% to about 30% of a surfactant and from about 5% to about 80% total detergency build-er. Of this builder component from about 20% to 100% by weight of lo builder component can be the two-compound builder systems of the present invention with the balance of the builder component being optional known builders.
Detergent compositions herein may also contain from about 0.1% to 95% by weight of a wide variety of additional optional components. Such optional components can include, for example, additional detergent builders, chelating agents, en2ymes, fabric whiteners and br~ghteners, sudsing control agents, solvents, hydrotropes, bleaching agents, bleach precursors, buffering agents9 additional soil removal/anti-redeposition agents, soil 20 release agents7 fabric softening agents, perfumes, colorants and opacifiers. A number of these additional optional components are hereinafter described in greater detail.
The detergent compositions of this invention are effective in cleaning solutions over the broad cleaning salution pH range of 25 from about ~ to about 13. The compositions can be formulated to provide a desired cleaning solution pH by proper selection of the acid form of appropriate salts or mixtures thereof. Pre~erred water-soluble salts of the builder compounds, for example, can be the alkali metal salts such as sodium, potassium, lithium and ammonium or substituted ammonium, e.g. triethanol ammonium.
Depending on the pH of the desired solution, the salts are par-tially or fully neutralized.
The detergent compositions of this invention can be prepared in solid or liquid physical form.
~L~25 3 The detergent compositions of this invention are particularly suitable for laundry use, but are also suitable for the cleaning of hard surfaces and for dishwashing.
In a laundry method using the detergent composition of this invention, typical laundry wash water solutions comprise from about 0.1~ to about 1% by weight of the de$ergent compositions of this invention.
The two-component builder systems herein may also be employed as builders in laundry additive compositions. Laundry additive compositions of the present invention contain as essential compo-nents from about 5% to about 95% of the ether carboxylate com-pounds hereinbefore described and from about 0.2% to 10% by weight of the dispersing/anti-redeposition agents hereinbefore described.
Such laundry additives compositions will also contain from about 0.5% to 98% by weight of a laundry adjuvant selected from the group consisting of surfactants, alternate builders, enzymes, fabric whiteners and brighteners, sudsing control agents, sol-vents, hydrotropes, bleaching agents, bleach precursors, buffering agents, additional soil removal/antideposition agents, soil ~o release agents, fabric softening agents, perfumes, colorants, opacifiers and mixtures of these adjuvants. Such adjuvants, whether used in the detergent or laundry additive co~positions herein, perform their expected functions in such composi~ions. A
number of these adjuvants are described in greater detail as follows:
Surfactants Various types of surfactants can be used in the detergent or laundry additive compositions of this invention. Useful surfac-tants include anionic, nonionic, ampholytic, zwitter~onic and cationic surfactants or mixtures of such materials. Detergent compositions for laundry use typically contain from about 5% to about 30% anlonic surfactants, mlxtures of anionic and nonionic surfactants or cation~c surfactants. Detergent compositions for use in automakic dishwashing machines typically contain from about 2% to about 6% by weight of a relatively 1QW SUdS;n9 nOnjQnjC
surfactant or mixtures thereof and~ opt~onally, suds control `` ~2537~
agents. Particularly suitable low sudsing nonionic surfactants are the alkoxylation products of compounds containing at least one reactive hydrogen wherein, preferably, at least abo~t 20% ~y weight of the alkyl~ne oxide by weight is propylene oxide.
Examples are products of ~he BASF-Wyandotte Corporation designated Pluroni ~, Tetroni ~, Plurado ~ and block polymerir variations in which propoxylation follows ethoxylation. Preferred suds control a~ents include mono-and distearyl acid phosphates.
The various classes of surfactants useful in the detergent and laundry additive compositions herein are exemplified as follows:
(A) Anionic soap and non-soap surfactants This class of surfactants includes alkali metal monocar-boxylates (soaps) such as the sodium, potassium, ammonium and alkylolammonium salts of higher fatty acids containing from about 8 to about 24 carbon atoms and preferably from about 12 to about 18 carbon atoms. Suitable fatty acids can be obtained from natural sources such as, for instance, from plant or animal esters (e.g., palm oil, coconut oil, babassu oil, soybean oil, castor oil, tallow, whale and fish oils, grease, lard, and mixtures thereof). The fatty acids also can be synthetically prepared (e.g., by the oxidation of petroleum, or by hydrogenation of carbon monoxide by the Fischer-Tropsch process). Resin acids are suitable such as rosin and those resin acids in tall oil. Naph-thenic acids are also suitable. Sodium and potassium soaps can bemade by direct sapnnification of the fats and oils or by the neutralizatlon of the free fatty acids which are prepared in a separate manufacturing process. Particularly useful are the sodium and potassium salts of the mixtures of fatty acids derived from coconut oil and tallow, i~e., sodium or potassium tallow and coconut soap. Soaps and fatty acids also act as detergency bullders in detergent composltions because they remove mul~ivalent ions by precipitatlon.
Anion~c surfactants also include water-soluble salts, par-
3~ ticularly the alkali metal and ethanolamine salts of organicsulfuric reaction produc~s hav~ng in their molecular structure an ~2S 3 7~`a~
alkyl radical containing from about 8 to about 22 carbon atoms and a sulfonic acid or sulfuric acid ester radical~ (Included in the term alkyl is the alkyl portion of alkylaryl radicals.) Examples of this group of non-soap anionic surfactants are the alkyl sulfates, especially those obtained by sulfa~ing ~he higher alcohols (C8-C18 carbon atoms); alkyl benzene sulfonates, in which the alkyl group contains from about 9 to about 15 carbon atoms, in straight chain or branched chain configuration, sodium alkyl glyceryl ether sul~onates; fatty acid monoglyceride sulfonates and sulfates; sulfuric acid esters of the reaction product of one mole of a C12 18 alcohol and about 1 to 6 moles of ethylene oxi~e and salts of alkyl phenol ethylene oxide ether sulfate with about 1 to about 10 units of ethylene oxide per molecule and in which the alkyl radicals contain about 8 to about 12 carbon atoms.
Additional examples of non-soap anionic surfactants are the reaction products of fatty acids esterified with isethionic acid and neutralized with sodium hydroxide where, for example, the fatty acids are derived from coconut oil and sodium or potassium salts of fatty acid amide of methyl lauride in which the fatty acids, for example are derived from coconut oil.
Still other anionic surfactants include the class designated as succinamates. This class includes such surface active agents as disodium N-octadecylsulfosuccinamate; tetrasodium N-(1~2-dicar-boxyethyl)-N-octadecylsulfosuccinama~e~ the diamyl ester of sodium sulfosucc~nic acid; the dihexyl ester of sodium sulfosuccinic acid and the dioctyl es~er of sodium sulfosuccinic acid.
Anionic phosphate surfactants are also useful ln the deter-gent or laundry additive compositions of the present invention.
These are surface active materials having substantial detergent capability in which the anionic solubilizing group connecting hydrophoblc moieties is an oxy acid o~ phosphorus. The more common solubilizing groups are -S04H, -S03H, and -C02~ Alkyl phosphate esters such as ~R-0)2P02H and ROP03H2 in which R repre-sents an alkyl chain containing from about 8 to about 20 carbon atoms are useful.
6~
These esters can be modified by including in the molecule from one to about 40 alkylene oxide units, e.g., ethylene oxide units.
Particularly useful anionic surfactants for incorporat;on into the compositions herein are alkyl ether sulfates. The alkyl ether sulfates are condensation products of ethylene oxide and monohydric alcohols having about 10 ~o about 20 carbon atoms.
Preferably, R has 12 to 18 carbon atoms. The alcohols can be derived from fa~s, e.g., coconut oil or tallow, or can be synthet-10ic. Such alcohols are reacted with 0.5 to 30, and especially 1 to 6~ molar proportions of ethylene oxide and the resulting mixture of molecular species, having, for example, an average of 3 to 6 moles of ethylene oxide per mole of alcohol, is sulfated and neutralized.
15Other suitable anionic surfactants are olefin and paraffin sulfonates having from about 12 to about 24 carbon atoms.
~B) Nonlonlc surfactants Alkoxylated nonionic surfactants may be broadly defined ascompounds produced by the condensation of alkylene oxide groups 20 (hydrophilic in nature) with an organic hydrophobic compound, which may be aliphatic or alkyl aromatic in nature. The length of the hydrophilic or polyoxyalkylene radical which is condensed with any particular hydrophobic group can be readily adjusted to yield a water-soluble compound having the desired degree o~ balance 25 between hydrophilic and hydrophobic elements.
Alkoxylated nonionic surfactants include:
(1) The condensation product of aliphatic alcohols having from 8 to 2~ carbon atoms, in either straight chain or branched chaln configuration, with from about 5 to about 20 moles of ethyl-ene oxide per mole of alcohol.
(2) The polyethylene oxide condensates of alkyl phenols,e.g., the condensation products of alkyl phenols having an alkyl group containing from about 6 to 12 carbon atoms in either a straight chaln or branched chain configuration, with ethylene oxide, the ethylene oxlde belng present in amounts of from about 5 to about 25 moles oF ethylene oxlde per mole of alkyl phenol. The i376~
alkyl substituent in such compounds may be derived from poly-merized propylene, diisobutylene, octene, or nonene, for example.
(3) Materials derived from the condensation of ethylene oxide with a product resulting from the reaction of propylene oxide and a compound with reactive hydrogen such as glycols and amines such as, for example, compounds containing from about 40%
to about 80% polyoxyethylen2 by weight resulting from the reaction of ethylene oxide with a hydrophobic base constituted of the re-action produc~ of ethylene diamine and propylene oxide.
Non-polar nonionic surfactants include the amine oxides and corresponding phosphine oxides. Useful amine oxide surfactants include those having the formula RlR2R3N_ 0 wherein Rl is an alkyl group containing from about 10 to about 28 carbon atoms, from 0 to about 2 hydroxy groups and from 0 to about 5 ether linkages, there being at least one moiety of R1 which is an alkyl group containing from about 10 to about 18 carbon atoms and R2 and R3 are selected from the group consisting of alkyl radicals and hydroxyalkyl radicals containing from 1 to about 3 carbon atoms.
Specific examples of amine oxide surfactants include: di-20 methyldodecylamine oxlde, dimethyltetradecylamine oxide, ethyl-methyltetradecylamine oxide, cetyldimethylamine oxide, diethyl-tetradecylamine oxide, dipropyldodecylamine oxide, bis-(2-hy-droxyethyl)dodecylamine oxide, bis-(2-hydroxypropyl)methyltetra-decylamine oxide, di~ethyl-(2-hydroxydodecyl)amine oxide, and the 25 corresponding decyl, hexadecyl and octadecyl homologs of the above compounds.
Additiona1 operable nonionic surfactants include alkyl glucosides and alkylamides of the formula Rl-- C--NHR2 wherein Rl is C10-cl8 alkyl and R2 is -H, -CH2 or -C2H5.
(C) Zwitterionic Surfactants Zwitterionic surfactants include derivatives of aliphatic quaternary ammonium, phosphonium, and sulfanium compounds in which the aliphatic moiety can be strai9ht or branched chain and wherein 3S one o~ the aliphat~c substituents contains from about 8 to 24 ~:53~6~
carbon atoms and one contains an anionic water-solubilizing group.
Particularly preferred zwitterionic materials are the ethoxylated ammonium sulfonates and sulfates disclosed in U.S. Patents 3,925,262, Laughlin et al, issued December 9, 1975 and 3,929,678, Laughlin et al, issue~ December 30, 1975. Ammonioamidates are also useful zwitterionic surfactants.
(D) Ampholytic Surfactants Ampholytic surfactants include derivatives of aliphatic heterocyclic secondary and tertiary amines in which the aliphatic moiety can be straight chain or branched and wherein one of the aliphatic substituents contains ~rom about 8 to about 24 carbon atoms and at least one aliphatic substituent contains an anionic water-solubilizing group.
(E) Cationic Surfactants Cationic surfactants comprise a wide variety of compounds characterized by one or more organic hydrophobic groups in the cation and generally by a quaternary nitrogen associated with an acid radical. Pentavalent n;trogen ring compounds are also considered quaternary nitrogen compounds. Suitable anions are halides, methyl sulfate and hydroxide. Tert~ary amines can have characteristics similar to cationic surfactants at washing so-lutions pH values less than about 8.5.
A more complete disclosure of cationic surfactants can be found in U.S. Patent 4,228~44, issued Oc~ober 14, 1980, to Cambre.
When cationic surfactants are used in combination with anionic surfactants and certain detergency builders including polycarboxylates, compatibility must be considered. A type of cationic surfactant generally campatible with anionic surfactants and polycarboxylates is a C8_18 alkyl tri C1 3 alkyl ammonium chloride or methyl sulfate.
More complete disclosures of surfactants suitable for incor-porat~on in detergent and laundry additive compositions of the present invention are in U.S. Patents 4,056,481, Tate (No~ember 1, 1977); 4,049,586, Collier (September 20l 1977); 4,040~9~8, Vincent et al (August 9, 1~77); 4,035,257, Cherney (July 12, 1977);
~253~ii9
alkyl radical containing from about 8 to about 22 carbon atoms and a sulfonic acid or sulfuric acid ester radical~ (Included in the term alkyl is the alkyl portion of alkylaryl radicals.) Examples of this group of non-soap anionic surfactants are the alkyl sulfates, especially those obtained by sulfa~ing ~he higher alcohols (C8-C18 carbon atoms); alkyl benzene sulfonates, in which the alkyl group contains from about 9 to about 15 carbon atoms, in straight chain or branched chain configuration, sodium alkyl glyceryl ether sul~onates; fatty acid monoglyceride sulfonates and sulfates; sulfuric acid esters of the reaction product of one mole of a C12 18 alcohol and about 1 to 6 moles of ethylene oxi~e and salts of alkyl phenol ethylene oxide ether sulfate with about 1 to about 10 units of ethylene oxide per molecule and in which the alkyl radicals contain about 8 to about 12 carbon atoms.
Additional examples of non-soap anionic surfactants are the reaction products of fatty acids esterified with isethionic acid and neutralized with sodium hydroxide where, for example, the fatty acids are derived from coconut oil and sodium or potassium salts of fatty acid amide of methyl lauride in which the fatty acids, for example are derived from coconut oil.
Still other anionic surfactants include the class designated as succinamates. This class includes such surface active agents as disodium N-octadecylsulfosuccinamate; tetrasodium N-(1~2-dicar-boxyethyl)-N-octadecylsulfosuccinama~e~ the diamyl ester of sodium sulfosucc~nic acid; the dihexyl ester of sodium sulfosuccinic acid and the dioctyl es~er of sodium sulfosuccinic acid.
Anionic phosphate surfactants are also useful ln the deter-gent or laundry additive compositions of the present invention.
These are surface active materials having substantial detergent capability in which the anionic solubilizing group connecting hydrophoblc moieties is an oxy acid o~ phosphorus. The more common solubilizing groups are -S04H, -S03H, and -C02~ Alkyl phosphate esters such as ~R-0)2P02H and ROP03H2 in which R repre-sents an alkyl chain containing from about 8 to about 20 carbon atoms are useful.
6~
These esters can be modified by including in the molecule from one to about 40 alkylene oxide units, e.g., ethylene oxide units.
Particularly useful anionic surfactants for incorporat;on into the compositions herein are alkyl ether sulfates. The alkyl ether sulfates are condensation products of ethylene oxide and monohydric alcohols having about 10 ~o about 20 carbon atoms.
Preferably, R has 12 to 18 carbon atoms. The alcohols can be derived from fa~s, e.g., coconut oil or tallow, or can be synthet-10ic. Such alcohols are reacted with 0.5 to 30, and especially 1 to 6~ molar proportions of ethylene oxide and the resulting mixture of molecular species, having, for example, an average of 3 to 6 moles of ethylene oxide per mole of alcohol, is sulfated and neutralized.
15Other suitable anionic surfactants are olefin and paraffin sulfonates having from about 12 to about 24 carbon atoms.
~B) Nonlonlc surfactants Alkoxylated nonionic surfactants may be broadly defined ascompounds produced by the condensation of alkylene oxide groups 20 (hydrophilic in nature) with an organic hydrophobic compound, which may be aliphatic or alkyl aromatic in nature. The length of the hydrophilic or polyoxyalkylene radical which is condensed with any particular hydrophobic group can be readily adjusted to yield a water-soluble compound having the desired degree o~ balance 25 between hydrophilic and hydrophobic elements.
Alkoxylated nonionic surfactants include:
(1) The condensation product of aliphatic alcohols having from 8 to 2~ carbon atoms, in either straight chain or branched chaln configuration, with from about 5 to about 20 moles of ethyl-ene oxide per mole of alcohol.
(2) The polyethylene oxide condensates of alkyl phenols,e.g., the condensation products of alkyl phenols having an alkyl group containing from about 6 to 12 carbon atoms in either a straight chaln or branched chain configuration, with ethylene oxide, the ethylene oxlde belng present in amounts of from about 5 to about 25 moles oF ethylene oxlde per mole of alkyl phenol. The i376~
alkyl substituent in such compounds may be derived from poly-merized propylene, diisobutylene, octene, or nonene, for example.
(3) Materials derived from the condensation of ethylene oxide with a product resulting from the reaction of propylene oxide and a compound with reactive hydrogen such as glycols and amines such as, for example, compounds containing from about 40%
to about 80% polyoxyethylen2 by weight resulting from the reaction of ethylene oxide with a hydrophobic base constituted of the re-action produc~ of ethylene diamine and propylene oxide.
Non-polar nonionic surfactants include the amine oxides and corresponding phosphine oxides. Useful amine oxide surfactants include those having the formula RlR2R3N_ 0 wherein Rl is an alkyl group containing from about 10 to about 28 carbon atoms, from 0 to about 2 hydroxy groups and from 0 to about 5 ether linkages, there being at least one moiety of R1 which is an alkyl group containing from about 10 to about 18 carbon atoms and R2 and R3 are selected from the group consisting of alkyl radicals and hydroxyalkyl radicals containing from 1 to about 3 carbon atoms.
Specific examples of amine oxide surfactants include: di-20 methyldodecylamine oxlde, dimethyltetradecylamine oxide, ethyl-methyltetradecylamine oxide, cetyldimethylamine oxide, diethyl-tetradecylamine oxide, dipropyldodecylamine oxide, bis-(2-hy-droxyethyl)dodecylamine oxide, bis-(2-hydroxypropyl)methyltetra-decylamine oxide, di~ethyl-(2-hydroxydodecyl)amine oxide, and the 25 corresponding decyl, hexadecyl and octadecyl homologs of the above compounds.
Additiona1 operable nonionic surfactants include alkyl glucosides and alkylamides of the formula Rl-- C--NHR2 wherein Rl is C10-cl8 alkyl and R2 is -H, -CH2 or -C2H5.
(C) Zwitterionic Surfactants Zwitterionic surfactants include derivatives of aliphatic quaternary ammonium, phosphonium, and sulfanium compounds in which the aliphatic moiety can be strai9ht or branched chain and wherein 3S one o~ the aliphat~c substituents contains from about 8 to 24 ~:53~6~
carbon atoms and one contains an anionic water-solubilizing group.
Particularly preferred zwitterionic materials are the ethoxylated ammonium sulfonates and sulfates disclosed in U.S. Patents 3,925,262, Laughlin et al, issued December 9, 1975 and 3,929,678, Laughlin et al, issue~ December 30, 1975. Ammonioamidates are also useful zwitterionic surfactants.
(D) Ampholytic Surfactants Ampholytic surfactants include derivatives of aliphatic heterocyclic secondary and tertiary amines in which the aliphatic moiety can be straight chain or branched and wherein one of the aliphatic substituents contains ~rom about 8 to about 24 carbon atoms and at least one aliphatic substituent contains an anionic water-solubilizing group.
(E) Cationic Surfactants Cationic surfactants comprise a wide variety of compounds characterized by one or more organic hydrophobic groups in the cation and generally by a quaternary nitrogen associated with an acid radical. Pentavalent n;trogen ring compounds are also considered quaternary nitrogen compounds. Suitable anions are halides, methyl sulfate and hydroxide. Tert~ary amines can have characteristics similar to cationic surfactants at washing so-lutions pH values less than about 8.5.
A more complete disclosure of cationic surfactants can be found in U.S. Patent 4,228~44, issued Oc~ober 14, 1980, to Cambre.
When cationic surfactants are used in combination with anionic surfactants and certain detergency builders including polycarboxylates, compatibility must be considered. A type of cationic surfactant generally campatible with anionic surfactants and polycarboxylates is a C8_18 alkyl tri C1 3 alkyl ammonium chloride or methyl sulfate.
More complete disclosures of surfactants suitable for incor-porat~on in detergent and laundry additive compositions of the present invention are in U.S. Patents 4,056,481, Tate (No~ember 1, 1977); 4,049,586, Collier (September 20l 1977); 4,040~9~8, Vincent et al (August 9, 1~77); 4,035,257, Cherney (July 12, 1977);
~253~ii9
4,033,718, Holcolm et al (July 5, 1977); 4,019,999, Ohren et al (April 26, 1977)i 4,019,998, Vincent et al (April 26, 1977); and 3,985,669, Krummel et al (October 12, 1976).
Optional Detergency Builders The detergent and laundry additive compositions of the present invention can contain detergency builders in addition to the particular ether carboxylate compounds or mixtures described hereinbefore as essential components.
Suitable additional polycarboxylate detergency builders lo include the acid form and alkali metal, ammonium and substituted ammonium salts of citric, ascorbic, phytic, ~elliticl benzene pentacarboxylic, oxydiacetic, carboxymethyloxysuccinic, carboxy-methyloxymalonic, cis-cyclohexanehexacarboxylic, and cis-cyclopen-tanetetracarboxylic acids.
The polyacetal carboxylates disclosed in U.S. Patent 4,144,226 issued March 13, 1979, to Crutchfield et al and U.S.
Patent 4,146,495 issued March 27, 1979 to Crutchfield et al can be incorporated in the detergent and laundry additive compositions of the invention.
Also suitable in the detergent and laundry additive composi-tions of the invention are the 3,3~dicarboxy-4-oxa-1,6-hexane-dioates and the related compounds disclosed in U.S. Serial No.
672,302 filed November 169 1984.
Sul~able ether polycarboxylates also include cyclic com-25 pounds, particularly alicyclic compounds, such as described in U.S. Patents 3,923,679; 3,835,163; 4,158,635) 4,120,874 and 4,102,903.
Polyphosphonate detergency builderslcomprise a large range of organic compounds having two or more ~ F - P03M2 groups, wherein M is hydrogen or a salt-forming radical. Suitable phos-phonates include ethane-1-hydroxy~ diphosphonates, ethane-hydroxy-1,1,2-triphosphonates and their oligomeric ester chain condensates. Suitable polyphosphonates for use in the composi-t~ons o~ the invention also include nitrogen containin~ poly-~5 phosphQna~es such as ethylenediaminetetrakis ~methylenephosphQnic)acid and diethylenetr~aminepentakis (methylenephosphonic) acid and ~Z~;i3769 alkali metal, ammonium and substituted ammonium salts thereof. In common with other phosphorus-containing components, the incorpo-ration of phosphonates may be restricted or prohibited by govern-ment regulation.
As ~iscussed hereinbefore C8 24 alkyl monocarboxylic acid and soluble salts thereof have a detergent builder ~unction in addi-tion to surfactant characteristics. C8-C24 alkyl, alkenyl9 alkoxy and thio-substituted alkyl dicarboxylic acid compounds, such as 4-pentadecene -1,2-dicarboxylic acid, salts thereof and mixtures thereof, are also useful optional de~ergency builders.
Inorganic detergency builders useful in the detergent and laundry additive compositions of this invention at total combined levels of from O~ to about 75% by weight, include alkali me~al phosphates, sodium aluminosilicates, alkali metal silicates and alkali metal carbonates.
Phosphate detergency builders include alkali metal ortho-phosphates which remove multivalent m~al ca$ions from laundry solutions by precipitation and the polyphosphates such as pyro-phosphates, tripolyphosphates and water-soluble metaphosphates 20 that sequester multivalent me~al cations in the form of soluble complex salts or insoluble precipi$ating complexes. Sodium pyrophosphate and sodium tripolyphosphate are particularly suit-able in granular detergent and laundry additive compositions to the extent that governmental regulations do not restrict or 25 prohibit the use o~ phosphorus-containing compounds in such compositions. Granular detergent and laundry additive composition embodiments of the inven~ion particularly adapted for use in areas where the in~orporation of phosphorus-containing compounds is restricted contains low total phosphorus and, preferably, essen-tially no phosphorus.
Other optional builder material include aluminosilîcate ionexchange materials, e.g. zeolites. Crystalline aluminosilicate ion exchange materials useful in the practice of this invention have the formula Naz~(AlO2)z(SiO2)y]H20 wherein z and y are at least about ~, ~he molar ratio of z to y is from about 1.0 to about 0.5 and x is ~rom about lQ to about 2~4. In a preferred embodiment the aluminosilicate ion exchange material has the a Nal2~(Al02)12(SiO2)12]XH20 wherein x is from about 20 to about 30, especially about 27.
Amorphous hydrated aluminosilicate material use~ul herein has the empirical formula: Naz(zAlO2.ySiO2) 9 Z is from about 0.5 to about 2, y is 1 and said material has a magnesium ion exchange capacity of at least about 50 milligram equivalents of CaC03 hardness per gram of anhydrous aluminosilicate.
The aluminosilicate ion exchange builder materials herein are in hydrated form and contain from about 10% to about 28% of water by weight if crystalline and potentially even higher amounts of water if amorphous. Highly preferred crystalline aluminosilicate ion exchange materials contain from about 18X to about 22% water in their crystal matrix. The crystalline aluminosilicate ion exchange materials are further characterized by a particle size diameter of from about 0.1 micron to about 10 microns. Amorphous materials are often smaller, e.g., down to less than about 0.01 micron. Preferred ion exchange materials have a particle size diameter of from about 0.2 micron to about 4 microns. The term "particle size diameter" herein represents the average particle size diameter of a given ion exchange material as determined by conventional analytical techniques such as, for example, micro-scopic determination uti7izing a scanning electron microscope.
The crystalline aluminosilicate ion exchange materials herein are usually further characterized by their calcium ion exchange capacity, which is at least about 2ao mg. equivalent of CaC03 water hardness/gm. of aluminosilicate, calculated on an anhydrous basis, and which generally ls in the range of from about 300 mg.eq,/g. to about 352 mg. eq./g. The aluminosilicate ion ex-change materials herein are still ~urther characterized by theircalcium ion e~change rate which is at least about 2 grains Ca~/
gallon/ minute/gram of aluminosilicate (anhydrous basis), and generally lies within the range of from about 2 grains/gallon/
minute/gram to about 6 grains/gallon/minute/gram, based on calcium ion hardness. Optimum aluminosilicate for builder purposes 2 5 3 7 ~9 exhibit a calcium ion exchange rate of at least about 4 grains/gallon/minute/gram.
The amorphous aluminosilicate ion exchange materials usually have a Mg++ exchange capacity of at least about 50 mg. eq.
CaC03/gtl2 mg. Mg~/g.) and a Mg+~ exchange rate of at least about 1 gr./gal./min./g./gal. Amorphous materials do not exhibit an observable diffraction pattern when examined by Cu radiation (1.54 Angstrom Units).
Aluminosilicate ion exchange materials useful as optional builders in the detergent and laundry additive compositions of this invention are commercially available. The aluminosilicates useful in this invention can be crystalline or amorphous in struc-ture and can be naturally-occurring aluminos~licates or synthe-tically derived. A method for producing aluminosilicate ion ex-change materials is discussed in U.S. Pat. No. 3,985,669, issued October 129 1976. Preferred synthetic crystalline aluminosilicate ion exchange materials useful herein are available under the designation Zeolite A, Zeolite B~ and Zeolite X.
Other optional builders include alkali metal silicates.
Suitable alkali metal silicates have a mole ratio of SiO2: alkalimetal oxide in the range- of from about 1:1 to about 4:1. The alkali meta1 silicate suitable herein include commercial prepa-rations of the combination of silicon dioxide and alkali metal oxide or carbonate fused together in varying proportions according to, for example, the following reaction:
mSiO2 ~ Na2C03 2600~F mSiO2;Na20 ~ C02 The value of m, designating the molar ratio of SiO2:Na20, ranges from about 0.5 to about 4 depending on the proposed use of the sodium silicate~ The term "alkali metal silicate" as used herein refers to silicate solids with any ratio of SiQ2 to alkali metal oxide. Silicate solids normally possess a high alkalinity content; in addition water o~ hydration is frequently present as, for example, in metasilicates which can exist havin~ S, 6, or 9 molecules of water. Sodium silicate solids wi~h a SiO2:Na2Q mole ratio o~ from about 1.5 to about 3.5, are preferred in ~ranular laundry detergent composltions.
~L2S3769 Silicate solids are frequently added to granular detergent or laundry additive compositions as corrosion inhibitors to provide protection to the metal parts of the washing machine in which the detergent or laundry additive composition is utilized. Silicates have also been used to provide a degree o~ crispness and pour-ability to detergent or laundry additive granules which is very desirable to avoid lumping and caking.
Alkali metal carbonates are useful in the granular detergent or laundry additive compositions of the invention as a source of lo washing solution alkalinity and because of the ability of the carbonate ion to remove calcium and magnesium ions from washing solutions by precipitation.
Preferred granular compositions free of inorganic phosphates contain from about 8X to about 40X by weight sodium carbonate, from 0% to about 30% sodium aluminosilicate, from about 0.5~ to about 10% sodium silicate solids, from about 5X to about 35% of the particular ether carboxylate compounds of this invention, from about 0.2% to 5% by weight of the particular dispersing/anti-redeposition agents of th~s invention, and from about 10% to about ZS% surfactant.
Preferred liquid compositions free of inorganic phosphates contain from about 8% to about 30% by weight of non-soap anionic surfactants, from about 2% to about 25g ethoxytated nonionic surfactants, from about 5X to about 20% of a C8 24 alkyl or alkenyl mono~or dicarboxylic acid or salt thereof, from about. 2%
~o a~out 18% of the particular ether carboxylate compounds o~ the present invention and from about 0~2% to 5% by weight of the dispersing/anti-redeposition agents of the present invention.
Some liquid formulations may also contain from about 0.5 to about
Optional Detergency Builders The detergent and laundry additive compositions of the present invention can contain detergency builders in addition to the particular ether carboxylate compounds or mixtures described hereinbefore as essential components.
Suitable additional polycarboxylate detergency builders lo include the acid form and alkali metal, ammonium and substituted ammonium salts of citric, ascorbic, phytic, ~elliticl benzene pentacarboxylic, oxydiacetic, carboxymethyloxysuccinic, carboxy-methyloxymalonic, cis-cyclohexanehexacarboxylic, and cis-cyclopen-tanetetracarboxylic acids.
The polyacetal carboxylates disclosed in U.S. Patent 4,144,226 issued March 13, 1979, to Crutchfield et al and U.S.
Patent 4,146,495 issued March 27, 1979 to Crutchfield et al can be incorporated in the detergent and laundry additive compositions of the invention.
Also suitable in the detergent and laundry additive composi-tions of the invention are the 3,3~dicarboxy-4-oxa-1,6-hexane-dioates and the related compounds disclosed in U.S. Serial No.
672,302 filed November 169 1984.
Sul~able ether polycarboxylates also include cyclic com-25 pounds, particularly alicyclic compounds, such as described in U.S. Patents 3,923,679; 3,835,163; 4,158,635) 4,120,874 and 4,102,903.
Polyphosphonate detergency builderslcomprise a large range of organic compounds having two or more ~ F - P03M2 groups, wherein M is hydrogen or a salt-forming radical. Suitable phos-phonates include ethane-1-hydroxy~ diphosphonates, ethane-hydroxy-1,1,2-triphosphonates and their oligomeric ester chain condensates. Suitable polyphosphonates for use in the composi-t~ons o~ the invention also include nitrogen containin~ poly-~5 phosphQna~es such as ethylenediaminetetrakis ~methylenephosphQnic)acid and diethylenetr~aminepentakis (methylenephosphonic) acid and ~Z~;i3769 alkali metal, ammonium and substituted ammonium salts thereof. In common with other phosphorus-containing components, the incorpo-ration of phosphonates may be restricted or prohibited by govern-ment regulation.
As ~iscussed hereinbefore C8 24 alkyl monocarboxylic acid and soluble salts thereof have a detergent builder ~unction in addi-tion to surfactant characteristics. C8-C24 alkyl, alkenyl9 alkoxy and thio-substituted alkyl dicarboxylic acid compounds, such as 4-pentadecene -1,2-dicarboxylic acid, salts thereof and mixtures thereof, are also useful optional de~ergency builders.
Inorganic detergency builders useful in the detergent and laundry additive compositions of this invention at total combined levels of from O~ to about 75% by weight, include alkali me~al phosphates, sodium aluminosilicates, alkali metal silicates and alkali metal carbonates.
Phosphate detergency builders include alkali metal ortho-phosphates which remove multivalent m~al ca$ions from laundry solutions by precipitation and the polyphosphates such as pyro-phosphates, tripolyphosphates and water-soluble metaphosphates 20 that sequester multivalent me~al cations in the form of soluble complex salts or insoluble precipi$ating complexes. Sodium pyrophosphate and sodium tripolyphosphate are particularly suit-able in granular detergent and laundry additive compositions to the extent that governmental regulations do not restrict or 25 prohibit the use o~ phosphorus-containing compounds in such compositions. Granular detergent and laundry additive composition embodiments of the inven~ion particularly adapted for use in areas where the in~orporation of phosphorus-containing compounds is restricted contains low total phosphorus and, preferably, essen-tially no phosphorus.
Other optional builder material include aluminosilîcate ionexchange materials, e.g. zeolites. Crystalline aluminosilicate ion exchange materials useful in the practice of this invention have the formula Naz~(AlO2)z(SiO2)y]H20 wherein z and y are at least about ~, ~he molar ratio of z to y is from about 1.0 to about 0.5 and x is ~rom about lQ to about 2~4. In a preferred embodiment the aluminosilicate ion exchange material has the a Nal2~(Al02)12(SiO2)12]XH20 wherein x is from about 20 to about 30, especially about 27.
Amorphous hydrated aluminosilicate material use~ul herein has the empirical formula: Naz(zAlO2.ySiO2) 9 Z is from about 0.5 to about 2, y is 1 and said material has a magnesium ion exchange capacity of at least about 50 milligram equivalents of CaC03 hardness per gram of anhydrous aluminosilicate.
The aluminosilicate ion exchange builder materials herein are in hydrated form and contain from about 10% to about 28% of water by weight if crystalline and potentially even higher amounts of water if amorphous. Highly preferred crystalline aluminosilicate ion exchange materials contain from about 18X to about 22% water in their crystal matrix. The crystalline aluminosilicate ion exchange materials are further characterized by a particle size diameter of from about 0.1 micron to about 10 microns. Amorphous materials are often smaller, e.g., down to less than about 0.01 micron. Preferred ion exchange materials have a particle size diameter of from about 0.2 micron to about 4 microns. The term "particle size diameter" herein represents the average particle size diameter of a given ion exchange material as determined by conventional analytical techniques such as, for example, micro-scopic determination uti7izing a scanning electron microscope.
The crystalline aluminosilicate ion exchange materials herein are usually further characterized by their calcium ion exchange capacity, which is at least about 2ao mg. equivalent of CaC03 water hardness/gm. of aluminosilicate, calculated on an anhydrous basis, and which generally ls in the range of from about 300 mg.eq,/g. to about 352 mg. eq./g. The aluminosilicate ion ex-change materials herein are still ~urther characterized by theircalcium ion e~change rate which is at least about 2 grains Ca~/
gallon/ minute/gram of aluminosilicate (anhydrous basis), and generally lies within the range of from about 2 grains/gallon/
minute/gram to about 6 grains/gallon/minute/gram, based on calcium ion hardness. Optimum aluminosilicate for builder purposes 2 5 3 7 ~9 exhibit a calcium ion exchange rate of at least about 4 grains/gallon/minute/gram.
The amorphous aluminosilicate ion exchange materials usually have a Mg++ exchange capacity of at least about 50 mg. eq.
CaC03/gtl2 mg. Mg~/g.) and a Mg+~ exchange rate of at least about 1 gr./gal./min./g./gal. Amorphous materials do not exhibit an observable diffraction pattern when examined by Cu radiation (1.54 Angstrom Units).
Aluminosilicate ion exchange materials useful as optional builders in the detergent and laundry additive compositions of this invention are commercially available. The aluminosilicates useful in this invention can be crystalline or amorphous in struc-ture and can be naturally-occurring aluminos~licates or synthe-tically derived. A method for producing aluminosilicate ion ex-change materials is discussed in U.S. Pat. No. 3,985,669, issued October 129 1976. Preferred synthetic crystalline aluminosilicate ion exchange materials useful herein are available under the designation Zeolite A, Zeolite B~ and Zeolite X.
Other optional builders include alkali metal silicates.
Suitable alkali metal silicates have a mole ratio of SiO2: alkalimetal oxide in the range- of from about 1:1 to about 4:1. The alkali meta1 silicate suitable herein include commercial prepa-rations of the combination of silicon dioxide and alkali metal oxide or carbonate fused together in varying proportions according to, for example, the following reaction:
mSiO2 ~ Na2C03 2600~F mSiO2;Na20 ~ C02 The value of m, designating the molar ratio of SiO2:Na20, ranges from about 0.5 to about 4 depending on the proposed use of the sodium silicate~ The term "alkali metal silicate" as used herein refers to silicate solids with any ratio of SiQ2 to alkali metal oxide. Silicate solids normally possess a high alkalinity content; in addition water o~ hydration is frequently present as, for example, in metasilicates which can exist havin~ S, 6, or 9 molecules of water. Sodium silicate solids wi~h a SiO2:Na2Q mole ratio o~ from about 1.5 to about 3.5, are preferred in ~ranular laundry detergent composltions.
~L2S3769 Silicate solids are frequently added to granular detergent or laundry additive compositions as corrosion inhibitors to provide protection to the metal parts of the washing machine in which the detergent or laundry additive composition is utilized. Silicates have also been used to provide a degree o~ crispness and pour-ability to detergent or laundry additive granules which is very desirable to avoid lumping and caking.
Alkali metal carbonates are useful in the granular detergent or laundry additive compositions of the invention as a source of lo washing solution alkalinity and because of the ability of the carbonate ion to remove calcium and magnesium ions from washing solutions by precipitation.
Preferred granular compositions free of inorganic phosphates contain from about 8X to about 40X by weight sodium carbonate, from 0% to about 30% sodium aluminosilicate, from about 0.5~ to about 10% sodium silicate solids, from about 5X to about 35% of the particular ether carboxylate compounds of this invention, from about 0.2% to 5% by weight of the particular dispersing/anti-redeposition agents of th~s invention, and from about 10% to about ZS% surfactant.
Preferred liquid compositions free of inorganic phosphates contain from about 8% to about 30% by weight of non-soap anionic surfactants, from about 2% to about 25g ethoxytated nonionic surfactants, from about 5X to about 20% of a C8 24 alkyl or alkenyl mono~or dicarboxylic acid or salt thereof, from about. 2%
~o a~out 18% of the particular ether carboxylate compounds o~ the present invention and from about 0~2% to 5% by weight of the dispersing/anti-redeposition agents of the present invention.
Some liquid formulations may also contain from about 0.5 to about
5% of a cationic or amine oxide surfactant.
Additional Optional Components Granular detergent or laundry additive compositions of this invention can contain materials such as sulfates, borates, per-borates organic peroxy acid salts, peroxy bleach precursors and 3S activators and water of hydrat~on.
~2~3 7 6 Liquid detergent or laundry additive compositions of this invention can contain water and other solvents. Low molecular weight primary or secondary alcohol exemplified by methanoll ethanol, propanol, and isopropanol are suitable. Monohydric alcohols are preferred for solubilizing the surfactant but polyols containing from 2 to about 6 carbon atoms and from 2 to about 6 hydroxy groups can be used and can provide improved enzyme stabil-ity. Examples of polyols include propylene glycol, ethylene glycol, glycerine and 1,2-propanedlol. Ethanol is a particularly preferred alcohol.
The detergent or laundry additive compositions of the in-vention can also contain such materials as proteolyt~c and amyl-olytic enzymes, fabric whiteners and optical brighteners, sudsing control agents, hydrotropes such as sodium toluene, xylene or cumene sulfonate, perfumes, colorants, opacifiers, and alkalinity control or buffering agents such as monoethanolamine and tri ethanolamine. The use of these materials is known in the deter-gent art.
Soil release agents, such as disclosed in the art to reduce oily staining of polyester fabrics, are also useful in the deter-gent and laundry additive compositions of the present invent~on.
U.S. Patent 3,962,152 issued June 8, 19769 to Nicol et al. dis-closes copolymers of ethylene terephthalate and polyethylene oxide terephthalate as soll release agents. U.S. Patent 4,174,305 issued November 13, 1979, to 8urns et al. discloses cellulose ether soil release agents. Canadian Patent Application Serial No. 498,176, filed December 19, 1985, by Go~selink discloses block polyester compounds useful as soil release agents in detergent and laundry additive compositions.
The detergent and laundry additive compos~tions herein may also optionally contain one or more iron and magnesium chelating agents. Such chelating agents can be selected from the group consisting of am~no carbo~ylates, amino phosphonates, polyfunc-tionally - substituted aromatic chelatin~ agents and mixtures 3s thereof, all as hereinafter defined. Without relying on theory, it is speculated that the benef~t of these mater~als ~s due in ,.. .~ ..
2 5'~7 6 part to their exceptional ability to remove iron and manganese ions from washing solutions by formation of soluble chelates.
Amino carboxylates useful as optional chelating agents in compositions of the invention have one or more, pr~ferably at least two, units, of the substructure ;-C CH~
,,N ~ (CH2)X COOM, wherein M is hydrogen, alkali metal, ammonium or substituted ammonium (eOg. ethanolamine) and x is from 1 to about 3, prefer-ably 1. Preferably, these amino carboxylates do not contain alkyl or alkenyl groups with more ~han about 6 carbon atoms. Alkylene groups can be shared by substructures. Operable amine carboxyl-ates include ethylenediaminetetraacetates, N-hydroxyethylethyl-enediaminetriaceta~es, nitrilotriacetates, ethylenediamine tetra-propîonates, diethylenetriaminepentaacetates, and ethanoldi-glycines.
Amino phosphonates are also suitable for use as chelatingagents in the compositions of the in~ention when at least low levels of total phosphorus are permitted in detergent composi-tions. Compounds with one or more, preferably at least two, units 20 of the substructure ~ N - (CH2)x ~ P03M 2' wherein M is hydrogen, alkali metal, ammonium or substituted ammonium and x ;s ~rom 1 to about 3, pre~erably 1, are useful and include ethylenediaminetetrakis (methylenephosphonates), nitrilo-25 tris ~methylenephosphonates) and diethylenetriaminepentakis(methylenephosphonates). Preferably, these amino phosphonates do not contain alkyl or alkenyl groups with more than about 6 carbon atoms. Alkylene groups can be shared by substructures.
Polyfunctionally - substituted aromatic chelating agents are also use~ul in the compositions herein. These materials comprise compounds having the yeneral ~ormula 3~
OH
R ~ OH
R R
R
wherein at least one R is -S03H or -COOH or soluble salts thereof and mixtures thereof. U.S. Paten~ 3,812,044 issued May 21, 1974, to Connor et al discloses polyfunctionally - substituted aromatic chela~ing and sequestering agents.Preferred compounds of this type in acid form are dihydroxydisulfobenzenes and 1,?-dihydroxy -3,5-disulfobenzene or other disulfonated catechols in particular.
Alkaline detergent compositions can contain these materials in the form of alkali metal, ammonium or substi~uted ammonium (e.g.
mono-or triethanolamine) salts.
If utilized, optional chelating agents will generally com-prise from about 0.1% to 10% by weight of the detergent or laundry additive compositions herein. More preferably chelating agents will comprise from about 0.75% to 3% by weight of such composi-tions.
The detergent and laundry additive compositions of thisinvention can also include a bleach system comprising an inorganic or organic peroxy bleaching agent and, in preferred compositions, an organic peroxy acid bleach precursor. Suitable inorganic peroxygen bleaches include sodium perborate mono- and tetrahy-drate, sodium percarbonate, sodium persilicate and urea-hydrogen peroxide addition products and the clathrate 4Na2S04:2H202:1NaCl.
Suitable organic bleaches include peroxylauric acid, peroxy-octanoic acld, peroxynonanoic acid, peroxydecanoic acid, diper-oxydodecanedioic acid, diperoxyazela~c acid, mono- and diper-oxyphthalic acid and mono- and diperoxyisophthalic acid. The bleaching agent is generally present in the detergent and laundry additive compositions of this invention at a leYel of from about 5% to about 50% preferably from about 10% to about 25% by weight.
The detergent and laundry additive compositions of the invention may also contain an organic peroxy acid bleach precursor at a level of from about 0.5% to about 10~, preferably from about ~s3~6~
1% to about 6% by weight. Suitable bleach precursors are dis-closed in UK-A-2040983, and include for example~ the peracetic acid bleach precursors such as tetraacetylethylenediamine, tetra-acetylmethylenediamine, tetraacetylhexylenediamine, sodium p-ace-toxybenzene sulfonate, tetraacetylglycouril, pentaacetlyglucose,octaacetyllactose, and methyl o-acetoxy benzoate. Highly pre-ferred bleach precursors, however, have the general formula R
R-C-L
wherein R is an alkyl group containing from 6 to 12 carbon atoms lo wherein the longest linear alkyl chain extending from and in-cluding the carboxyl carbon contains from ~ to 10 carbon atoms and L is a leaving group~ the conjugate acid of which has a logarith-mic acidity constant in the range from 6 ~o 13.
The alkyl group, R, can be either linear or branched and, in preferred embodiments, it contains from 7 to 9 carbon atoms;
Preferred leaving groups L have a logarithmic acidity constant in the range from about 7 to about 11, more preferably from about 8 to about 10. Examples of leaving groups are those having the formula ~ ' ~ ( CH2 ~ xY
a) O
z and o b) -~-C-R
y wherein Z is H, R1 or halogen, R1 is an alkyl group having from 1 to 4 carbon atoms, X is O or an integer of from 1 to 4 and Y is selected from S03M, OS03M, C02M~ N ~R1)30 and N (R1)2-0 wherein M is H, alkali metal, alkaline earth metal~ ammoniwm or subs~itut-ed ammon~um, and O is halide or methosulfate.
~L~25 3 7Ç;g The preferred leaving group L has the formula (a) in which Z
is H, x is 0 and Y is sulfonate, carboxylate or dimethylamine oxide radical. Highly preferred materials are sodium 3,5,5,-trimethylhexanoyloxybenzene sulfonate, sodium 3,595-trimethyl-hexanoyloxyben~oate, sodium 2-ethylhexanoyl oxybenzenesulfonate, sodium nonanoyl oxybenzene sulfonate and sodium octanoyl oxy-benzenesulfonate, the acyloxy group in each instance pre~erably being p-substituted.
The bleach precursor (activator) herein will normally be iO added in the form of particles comprising finely-divided bleach activator and a binder. The binder is generally selected from nonionic surfactants such as the ethoxylated tallow alcohols, polyethylene glycols, anionic surfactants, film forming polymers, fatty acids and mixtures thereo~. Highly preferred are nonionic surfactant binders, the bleach acti~ator being admixed with the binder and extruded in the form of elongated particles through a radial extruder as described in European Patent Application No.
62523. Alternatively, the bleach activator particles can be prepared by spray drying.
The following embodiments illustrate, but are not limi~ing of, the builder compositions o~ the present invention, as well as detergent compositions containing the builder systems herein. All percentages herein are by weight unless indicated otherwise.
EXAMPLE I
In this Example a builder composition is formulated by preparing an oxydisuccinate ether carboxylate and by adding thereto an ethoxylated polyamine dispersing/anti-redeposition agent, A. Ether Carboxylate Preparation Maleic anhydride, 19.6 9 (0.2 mole), is dissolved in 200 ml.
water and heated to 100C. for 5 minutes. Calcium hydroxide, 16.0 g. (0.22 mole), is then added~ and the mixture is stirred and refluxed For ~ days. The insoluble calcium salts are filtered and dried. The dried product, 22 g , is slurried in water and passed throuyh an Amberlite IR-120 cation exchange column to remo~e ~he 2537~g calcium ions. The eluate is then evaporated to dryness to yield 14.5 g. of crude oxydisuccinic acid.
Eleven grams of crude oxydisuccinic acid obtained from the above procedure is digested with 10 ml. of boiling acetone and filtered. The acetone extraction is repeated five more times to give a 60/40 mixture of meso/d,1-oxydisuccinic acid, ODS, based on NMR analysis.
B. Ethoxylated Polyamine Preparation Tetraethylenepentamine ~TEPA) (M.W. 189, 61.44 9., 0.325 moles) is placed in a nominally dry flask and dried by stirring for 0.5 hours at 110-120C under a vacuum (pressure less than 1 mm.) The vacuum is released by drawing ethylene oxide (EO) from a prepurged trap connected to a supply tank. Once the flask is filled with EO, an outlet stopcock is carefully opened to a trap connected to an exhaust bubbler. After 3 hours stirring at 107-115C, 99.56 9. of EO is added to give a calculated degree of ethoxylation of 0.995. The reaction mixture is cooled while being swept with argon and 2.289 9. (0.057 moles) of 60% sodium hydride in mineral oil are then added~ The stirred reaction mixture is 20 swept wlth argon until hydrogen evolution ceased. EO is then added to the reaction mixture under atmospheric pressure at 109-118C with moderately fast stirring. After 23 hours, a total of 1503 9. (3~.17 moles) of EO has been added to give a calculated total degree of ethoxylation of 15.D2. The ethoxylated TEPA
25 obtained is a tan waxy solid.
C. Builder Composition Preparation 94 grams of ODS as generally prepared in Part A are admixed in its sodium salt form with 6 grams of the ethoxylated TEPA
material as prepared in Part B. Such a composition is especially suitable for use as a builder system in surfactant-containin~
de~ergent compositions or in a laundry additive composition.
~253~69 EXAMPLE II
A granular detergent composition for household laundry use is as follows:
Component Wt. %
Sodium C14 C15 alkylsulfate 13.3 Sodium C13 linear alkyl benzene sulfonate 5.7 C12-C13 alkylpolyethoxylate (6.5) 1.0 Sodium toluene sulfonate 1.0 ODS, sodium salt 25.0 10 Sodium N-hydroxyethylethylenediaminetriacetate 2.0 Sodium polyacrylate (Avg. M.W. approx. 5000) 2.0 Sodium carbonate 20.3 Sodium silicate 5.8 Polyethylene glycol (A~g. M.W. approx. 8000) 1.0 15 Sodium sulfate, water and miscellaneous Balance to 100%
The components are added together with continuous mixing with sufficient extra water (about 40% total) to form an aqueous slurry which is then spray dried to form the composition.
EXAMPLE III
A liquid detergent composition for household laundry use is as follows:
Component Wt. %
Potassium C14-C15 alkyl polyethoxy (2.5) sulfate 8.3 C12~C1~ alkyl dimethyl amine oxide 3.3 25 Potassium toluene sulfonate 5.0 Monoethanolamine 2.3 ODS, triethanolam;ne salt 15.0 Potasslum salt of 1,2-dihydroxy-3,5-disulfobenzene 1.5 Ethoxylated tetraethylenepentamine (Example I-type)1.5 Potassium polyacrylate (avg. M.W. approx. 9000) 1.5 Water and miscellaneous Balance to 100%
The components are added together with continuous mixing to form the composition.
~L~253~
.
EXAMPLE IV
A liquid detergent composition for household laundry use is prepared by mixing the following ingredients:
C13 alkylbenzenesulfonic acid 10.5%
5 Triethanolamine cocoalkyl sulfate 4.0 C14_15 alcohol ethoxy 7 12.0 C12-18 alkyl monocarboxylic acids 15.0 ODS, triethanolamine salt 5.0 Diethylenetriaminepentakis (methylenephosphonic) acid 0.8 Polyacrylic acid (avg. M.W. approx. 5000) 0.8 Triethanolamine 4.5 Ethanol 8.6 1,2-Propanediol 3.0 Water, perfume, buffers and miscellaneous Balance to 100~
EXAMPLE V
In the Compositions which follow9 the abbreviations used have the following designations:
C12LAS : Sodium linear C12 benzene sulfonate TAS : Sodium tallow alcohol sulfonate 20 TAEn : Hardened tallow alcohol ethoxylated with n moles of ethylene oxide per mole of alcohol Dobanol 45E7 A C14 15 primary alcohol condensed with 7 moles of ethylene oxide 25 TAED : Tetraacetyl ethylene diamine NOBS : Sodium nonanoyl oxybenzenesulfonate INOBS : Sodium 3,5,5 trimethyl hexanoyl oxy-benzene sulfonate Silicate : Sodium silicate having an SiO2:Na20 ratio of 1:6 Sulfate : Anhydrous sodium sulfate Carbonate : Anhydrous sodium carbonate CMC : Sodium carboxymethyl cellulose Silicone : Comprising 0.14 parts by weight of an ~5:15 by weight mixture of silanated silica and silicQne, granulated with 1.3 ~2 5 3~7 parts of sodium tripolyphosphate, and 0.56 parts of tallow alcohol condensed with 25 molar proportions of ethylene oxide PCl : Copolymer of 3:7 maleic/acrylic acid, average molecular weight about 70,000, as sodium salt PC2 : Polyacrylic acid, average molecular weight about 4,500, as sodium salt lo ODS : Sodium oxydisuccinate Perborate : Sodium perborate tetrahydrate of nominal formula NaB02.3H20.H202 En~yme : Protease EDTA : Sodium ethylene diamine tetra acetate Brightener : Disodium 4,4'-bis(2-morpholino-4-anilino-s-triazin-6-ylamino) stilbene-2:2'di-sulfonate DETPMP : Diethylene triamine penta~methylene phosphonic acid), marketed by Monsanto under the Trade name Dequest 2060 EDTMP : Ethylenediamine tetra (methylene phos-phonic acid), marketed by Monsanto, under the Trade name Dequest 2041 Granular detergent compositions are prepared as fallows. A
base powder composition is first prepared by mixing all components except, where present, Dobanol 45E7, bleach, bleach activator, enzyme, suds suppresser, phosphate and carbonate in crutcher as an aqueous slurry at a temperature of about 55C and containing about 35% water. The slurry is then spray dried at a yas inlet tempera-ture of about 330C to form base powder granules. The bleach activator~ where present, is then admixed with TAE25 as binder and extruded in the form of elongated particles through a radical extruder as described in European Patent Applicatian Number 62523.
The bleach activator noodles, bleach, enzyme, suds suppressor, phosphate and carbonate are then dry-mixed with the base powder ~5376g composition and finally Dobanol 45E7 is sprayed into the final mixture.
COMPOSITIONS
A B . C D
TAE~5 0.5 0.5 0.8 TAEll - 1 _ _ Dobanol 45E7 4 - 4 2 TAED 0.5 - 3 Perborate 19 20 10 24 EDTMP 0.3 - 0.4 0.1 DETPMP ~ 0~4 EDTA 0.20.2 0.2 0.1 Magnesium (ppm~ 1000 1000 750 PCl 2 1 2 2 Zeolite A* - 15 14 Sodium tripolyphosphate - - - 12 Coconut Soap - - 2 Carbonate 17 15 10 Silicate 3 2 2 7 Silicone 0.2 0.2 0.3 0.2 Enzyme 0.8 0.5 0.4 0.3 Brightener 0.2 0.2 0.2 0.2 Sulfate, Moisture Miscellaneous ~ to 100 *Zeolite A of 4 A pore size.
The above compositions are zero and low phosphate detergent compositions displaying excellent bleach stability~ fabric care and detergency performance across the range of wash temperatures with part~cularly outstanding per~ormance in the case o~
~253'769 Compositions A9 B and C on greasy and particulate soils at low wash temperatures.
Additional Optional Components Granular detergent or laundry additive compositions of this invention can contain materials such as sulfates, borates, per-borates organic peroxy acid salts, peroxy bleach precursors and 3S activators and water of hydrat~on.
~2~3 7 6 Liquid detergent or laundry additive compositions of this invention can contain water and other solvents. Low molecular weight primary or secondary alcohol exemplified by methanoll ethanol, propanol, and isopropanol are suitable. Monohydric alcohols are preferred for solubilizing the surfactant but polyols containing from 2 to about 6 carbon atoms and from 2 to about 6 hydroxy groups can be used and can provide improved enzyme stabil-ity. Examples of polyols include propylene glycol, ethylene glycol, glycerine and 1,2-propanedlol. Ethanol is a particularly preferred alcohol.
The detergent or laundry additive compositions of the in-vention can also contain such materials as proteolyt~c and amyl-olytic enzymes, fabric whiteners and optical brighteners, sudsing control agents, hydrotropes such as sodium toluene, xylene or cumene sulfonate, perfumes, colorants, opacifiers, and alkalinity control or buffering agents such as monoethanolamine and tri ethanolamine. The use of these materials is known in the deter-gent art.
Soil release agents, such as disclosed in the art to reduce oily staining of polyester fabrics, are also useful in the deter-gent and laundry additive compositions of the present invent~on.
U.S. Patent 3,962,152 issued June 8, 19769 to Nicol et al. dis-closes copolymers of ethylene terephthalate and polyethylene oxide terephthalate as soll release agents. U.S. Patent 4,174,305 issued November 13, 1979, to 8urns et al. discloses cellulose ether soil release agents. Canadian Patent Application Serial No. 498,176, filed December 19, 1985, by Go~selink discloses block polyester compounds useful as soil release agents in detergent and laundry additive compositions.
The detergent and laundry additive compos~tions herein may also optionally contain one or more iron and magnesium chelating agents. Such chelating agents can be selected from the group consisting of am~no carbo~ylates, amino phosphonates, polyfunc-tionally - substituted aromatic chelatin~ agents and mixtures 3s thereof, all as hereinafter defined. Without relying on theory, it is speculated that the benef~t of these mater~als ~s due in ,.. .~ ..
2 5'~7 6 part to their exceptional ability to remove iron and manganese ions from washing solutions by formation of soluble chelates.
Amino carboxylates useful as optional chelating agents in compositions of the invention have one or more, pr~ferably at least two, units, of the substructure ;-C CH~
,,N ~ (CH2)X COOM, wherein M is hydrogen, alkali metal, ammonium or substituted ammonium (eOg. ethanolamine) and x is from 1 to about 3, prefer-ably 1. Preferably, these amino carboxylates do not contain alkyl or alkenyl groups with more ~han about 6 carbon atoms. Alkylene groups can be shared by substructures. Operable amine carboxyl-ates include ethylenediaminetetraacetates, N-hydroxyethylethyl-enediaminetriaceta~es, nitrilotriacetates, ethylenediamine tetra-propîonates, diethylenetriaminepentaacetates, and ethanoldi-glycines.
Amino phosphonates are also suitable for use as chelatingagents in the compositions of the in~ention when at least low levels of total phosphorus are permitted in detergent composi-tions. Compounds with one or more, preferably at least two, units 20 of the substructure ~ N - (CH2)x ~ P03M 2' wherein M is hydrogen, alkali metal, ammonium or substituted ammonium and x ;s ~rom 1 to about 3, pre~erably 1, are useful and include ethylenediaminetetrakis (methylenephosphonates), nitrilo-25 tris ~methylenephosphonates) and diethylenetriaminepentakis(methylenephosphonates). Preferably, these amino phosphonates do not contain alkyl or alkenyl groups with more than about 6 carbon atoms. Alkylene groups can be shared by substructures.
Polyfunctionally - substituted aromatic chelating agents are also use~ul in the compositions herein. These materials comprise compounds having the yeneral ~ormula 3~
OH
R ~ OH
R R
R
wherein at least one R is -S03H or -COOH or soluble salts thereof and mixtures thereof. U.S. Paten~ 3,812,044 issued May 21, 1974, to Connor et al discloses polyfunctionally - substituted aromatic chela~ing and sequestering agents.Preferred compounds of this type in acid form are dihydroxydisulfobenzenes and 1,?-dihydroxy -3,5-disulfobenzene or other disulfonated catechols in particular.
Alkaline detergent compositions can contain these materials in the form of alkali metal, ammonium or substi~uted ammonium (e.g.
mono-or triethanolamine) salts.
If utilized, optional chelating agents will generally com-prise from about 0.1% to 10% by weight of the detergent or laundry additive compositions herein. More preferably chelating agents will comprise from about 0.75% to 3% by weight of such composi-tions.
The detergent and laundry additive compositions of thisinvention can also include a bleach system comprising an inorganic or organic peroxy bleaching agent and, in preferred compositions, an organic peroxy acid bleach precursor. Suitable inorganic peroxygen bleaches include sodium perborate mono- and tetrahy-drate, sodium percarbonate, sodium persilicate and urea-hydrogen peroxide addition products and the clathrate 4Na2S04:2H202:1NaCl.
Suitable organic bleaches include peroxylauric acid, peroxy-octanoic acld, peroxynonanoic acid, peroxydecanoic acid, diper-oxydodecanedioic acid, diperoxyazela~c acid, mono- and diper-oxyphthalic acid and mono- and diperoxyisophthalic acid. The bleaching agent is generally present in the detergent and laundry additive compositions of this invention at a leYel of from about 5% to about 50% preferably from about 10% to about 25% by weight.
The detergent and laundry additive compositions of the invention may also contain an organic peroxy acid bleach precursor at a level of from about 0.5% to about 10~, preferably from about ~s3~6~
1% to about 6% by weight. Suitable bleach precursors are dis-closed in UK-A-2040983, and include for example~ the peracetic acid bleach precursors such as tetraacetylethylenediamine, tetra-acetylmethylenediamine, tetraacetylhexylenediamine, sodium p-ace-toxybenzene sulfonate, tetraacetylglycouril, pentaacetlyglucose,octaacetyllactose, and methyl o-acetoxy benzoate. Highly pre-ferred bleach precursors, however, have the general formula R
R-C-L
wherein R is an alkyl group containing from 6 to 12 carbon atoms lo wherein the longest linear alkyl chain extending from and in-cluding the carboxyl carbon contains from ~ to 10 carbon atoms and L is a leaving group~ the conjugate acid of which has a logarith-mic acidity constant in the range from 6 ~o 13.
The alkyl group, R, can be either linear or branched and, in preferred embodiments, it contains from 7 to 9 carbon atoms;
Preferred leaving groups L have a logarithmic acidity constant in the range from about 7 to about 11, more preferably from about 8 to about 10. Examples of leaving groups are those having the formula ~ ' ~ ( CH2 ~ xY
a) O
z and o b) -~-C-R
y wherein Z is H, R1 or halogen, R1 is an alkyl group having from 1 to 4 carbon atoms, X is O or an integer of from 1 to 4 and Y is selected from S03M, OS03M, C02M~ N ~R1)30 and N (R1)2-0 wherein M is H, alkali metal, alkaline earth metal~ ammoniwm or subs~itut-ed ammon~um, and O is halide or methosulfate.
~L~25 3 7Ç;g The preferred leaving group L has the formula (a) in which Z
is H, x is 0 and Y is sulfonate, carboxylate or dimethylamine oxide radical. Highly preferred materials are sodium 3,5,5,-trimethylhexanoyloxybenzene sulfonate, sodium 3,595-trimethyl-hexanoyloxyben~oate, sodium 2-ethylhexanoyl oxybenzenesulfonate, sodium nonanoyl oxybenzene sulfonate and sodium octanoyl oxy-benzenesulfonate, the acyloxy group in each instance pre~erably being p-substituted.
The bleach precursor (activator) herein will normally be iO added in the form of particles comprising finely-divided bleach activator and a binder. The binder is generally selected from nonionic surfactants such as the ethoxylated tallow alcohols, polyethylene glycols, anionic surfactants, film forming polymers, fatty acids and mixtures thereo~. Highly preferred are nonionic surfactant binders, the bleach acti~ator being admixed with the binder and extruded in the form of elongated particles through a radial extruder as described in European Patent Application No.
62523. Alternatively, the bleach activator particles can be prepared by spray drying.
The following embodiments illustrate, but are not limi~ing of, the builder compositions o~ the present invention, as well as detergent compositions containing the builder systems herein. All percentages herein are by weight unless indicated otherwise.
EXAMPLE I
In this Example a builder composition is formulated by preparing an oxydisuccinate ether carboxylate and by adding thereto an ethoxylated polyamine dispersing/anti-redeposition agent, A. Ether Carboxylate Preparation Maleic anhydride, 19.6 9 (0.2 mole), is dissolved in 200 ml.
water and heated to 100C. for 5 minutes. Calcium hydroxide, 16.0 g. (0.22 mole), is then added~ and the mixture is stirred and refluxed For ~ days. The insoluble calcium salts are filtered and dried. The dried product, 22 g , is slurried in water and passed throuyh an Amberlite IR-120 cation exchange column to remo~e ~he 2537~g calcium ions. The eluate is then evaporated to dryness to yield 14.5 g. of crude oxydisuccinic acid.
Eleven grams of crude oxydisuccinic acid obtained from the above procedure is digested with 10 ml. of boiling acetone and filtered. The acetone extraction is repeated five more times to give a 60/40 mixture of meso/d,1-oxydisuccinic acid, ODS, based on NMR analysis.
B. Ethoxylated Polyamine Preparation Tetraethylenepentamine ~TEPA) (M.W. 189, 61.44 9., 0.325 moles) is placed in a nominally dry flask and dried by stirring for 0.5 hours at 110-120C under a vacuum (pressure less than 1 mm.) The vacuum is released by drawing ethylene oxide (EO) from a prepurged trap connected to a supply tank. Once the flask is filled with EO, an outlet stopcock is carefully opened to a trap connected to an exhaust bubbler. After 3 hours stirring at 107-115C, 99.56 9. of EO is added to give a calculated degree of ethoxylation of 0.995. The reaction mixture is cooled while being swept with argon and 2.289 9. (0.057 moles) of 60% sodium hydride in mineral oil are then added~ The stirred reaction mixture is 20 swept wlth argon until hydrogen evolution ceased. EO is then added to the reaction mixture under atmospheric pressure at 109-118C with moderately fast stirring. After 23 hours, a total of 1503 9. (3~.17 moles) of EO has been added to give a calculated total degree of ethoxylation of 15.D2. The ethoxylated TEPA
25 obtained is a tan waxy solid.
C. Builder Composition Preparation 94 grams of ODS as generally prepared in Part A are admixed in its sodium salt form with 6 grams of the ethoxylated TEPA
material as prepared in Part B. Such a composition is especially suitable for use as a builder system in surfactant-containin~
de~ergent compositions or in a laundry additive composition.
~253~69 EXAMPLE II
A granular detergent composition for household laundry use is as follows:
Component Wt. %
Sodium C14 C15 alkylsulfate 13.3 Sodium C13 linear alkyl benzene sulfonate 5.7 C12-C13 alkylpolyethoxylate (6.5) 1.0 Sodium toluene sulfonate 1.0 ODS, sodium salt 25.0 10 Sodium N-hydroxyethylethylenediaminetriacetate 2.0 Sodium polyacrylate (Avg. M.W. approx. 5000) 2.0 Sodium carbonate 20.3 Sodium silicate 5.8 Polyethylene glycol (A~g. M.W. approx. 8000) 1.0 15 Sodium sulfate, water and miscellaneous Balance to 100%
The components are added together with continuous mixing with sufficient extra water (about 40% total) to form an aqueous slurry which is then spray dried to form the composition.
EXAMPLE III
A liquid detergent composition for household laundry use is as follows:
Component Wt. %
Potassium C14-C15 alkyl polyethoxy (2.5) sulfate 8.3 C12~C1~ alkyl dimethyl amine oxide 3.3 25 Potassium toluene sulfonate 5.0 Monoethanolamine 2.3 ODS, triethanolam;ne salt 15.0 Potasslum salt of 1,2-dihydroxy-3,5-disulfobenzene 1.5 Ethoxylated tetraethylenepentamine (Example I-type)1.5 Potassium polyacrylate (avg. M.W. approx. 9000) 1.5 Water and miscellaneous Balance to 100%
The components are added together with continuous mixing to form the composition.
~L~253~
.
EXAMPLE IV
A liquid detergent composition for household laundry use is prepared by mixing the following ingredients:
C13 alkylbenzenesulfonic acid 10.5%
5 Triethanolamine cocoalkyl sulfate 4.0 C14_15 alcohol ethoxy 7 12.0 C12-18 alkyl monocarboxylic acids 15.0 ODS, triethanolamine salt 5.0 Diethylenetriaminepentakis (methylenephosphonic) acid 0.8 Polyacrylic acid (avg. M.W. approx. 5000) 0.8 Triethanolamine 4.5 Ethanol 8.6 1,2-Propanediol 3.0 Water, perfume, buffers and miscellaneous Balance to 100~
EXAMPLE V
In the Compositions which follow9 the abbreviations used have the following designations:
C12LAS : Sodium linear C12 benzene sulfonate TAS : Sodium tallow alcohol sulfonate 20 TAEn : Hardened tallow alcohol ethoxylated with n moles of ethylene oxide per mole of alcohol Dobanol 45E7 A C14 15 primary alcohol condensed with 7 moles of ethylene oxide 25 TAED : Tetraacetyl ethylene diamine NOBS : Sodium nonanoyl oxybenzenesulfonate INOBS : Sodium 3,5,5 trimethyl hexanoyl oxy-benzene sulfonate Silicate : Sodium silicate having an SiO2:Na20 ratio of 1:6 Sulfate : Anhydrous sodium sulfate Carbonate : Anhydrous sodium carbonate CMC : Sodium carboxymethyl cellulose Silicone : Comprising 0.14 parts by weight of an ~5:15 by weight mixture of silanated silica and silicQne, granulated with 1.3 ~2 5 3~7 parts of sodium tripolyphosphate, and 0.56 parts of tallow alcohol condensed with 25 molar proportions of ethylene oxide PCl : Copolymer of 3:7 maleic/acrylic acid, average molecular weight about 70,000, as sodium salt PC2 : Polyacrylic acid, average molecular weight about 4,500, as sodium salt lo ODS : Sodium oxydisuccinate Perborate : Sodium perborate tetrahydrate of nominal formula NaB02.3H20.H202 En~yme : Protease EDTA : Sodium ethylene diamine tetra acetate Brightener : Disodium 4,4'-bis(2-morpholino-4-anilino-s-triazin-6-ylamino) stilbene-2:2'di-sulfonate DETPMP : Diethylene triamine penta~methylene phosphonic acid), marketed by Monsanto under the Trade name Dequest 2060 EDTMP : Ethylenediamine tetra (methylene phos-phonic acid), marketed by Monsanto, under the Trade name Dequest 2041 Granular detergent compositions are prepared as fallows. A
base powder composition is first prepared by mixing all components except, where present, Dobanol 45E7, bleach, bleach activator, enzyme, suds suppresser, phosphate and carbonate in crutcher as an aqueous slurry at a temperature of about 55C and containing about 35% water. The slurry is then spray dried at a yas inlet tempera-ture of about 330C to form base powder granules. The bleach activator~ where present, is then admixed with TAE25 as binder and extruded in the form of elongated particles through a radical extruder as described in European Patent Applicatian Number 62523.
The bleach activator noodles, bleach, enzyme, suds suppressor, phosphate and carbonate are then dry-mixed with the base powder ~5376g composition and finally Dobanol 45E7 is sprayed into the final mixture.
COMPOSITIONS
A B . C D
TAE~5 0.5 0.5 0.8 TAEll - 1 _ _ Dobanol 45E7 4 - 4 2 TAED 0.5 - 3 Perborate 19 20 10 24 EDTMP 0.3 - 0.4 0.1 DETPMP ~ 0~4 EDTA 0.20.2 0.2 0.1 Magnesium (ppm~ 1000 1000 750 PCl 2 1 2 2 Zeolite A* - 15 14 Sodium tripolyphosphate - - - 12 Coconut Soap - - 2 Carbonate 17 15 10 Silicate 3 2 2 7 Silicone 0.2 0.2 0.3 0.2 Enzyme 0.8 0.5 0.4 0.3 Brightener 0.2 0.2 0.2 0.2 Sulfate, Moisture Miscellaneous ~ to 100 *Zeolite A of 4 A pore size.
The above compositions are zero and low phosphate detergent compositions displaying excellent bleach stability~ fabric care and detergency performance across the range of wash temperatures with part~cularly outstanding per~ormance in the case o~
~253'769 Compositions A9 B and C on greasy and particulate soils at low wash temperatures.
Claims (16)
1. A detergent builder composition especially useful in phosphorus-free detergent or laundry additive products, said composition comprising:
(A) from 70% to 99% by weight of an ether carboxylate sequester-ing agent having the formula:
wherein X is H or a salt-forming cation; and (B) from 1% to 30% by weight of a dispersing/anti-redeposition agent selected from the group consisting of:
i) polycarboxylates which are polymers or copolymers which contain at least 60% by weight of segments having the general formula:
wherein X, Y and Z are, independently, selected from hydrogen, methyl, carboxy, carboxymethyl, hydroxy and hydroxymethyl; M is H or a salt-forming cation and n ranges from 30 to 400;
ii) ethoxylated amine material selected from the group consisting of (a) ethoxylated monoamines having the formula:
(b) ethoxylated diamines having the formula:
or (c) ethoxylated polyamines having the formula:
(d) ethoxylated amine polymers having the general formula:
and (e) mixtures of such ethoxylated amines;
wherein A1 is R is H or C1-C4 alkyl or hydroxyalkyl; R1 is C2-C12 alkylene, hydroxyalkylene, alkenylene, arylene or alkarylene, or a C2-C3 oxyalkylene moiety having from 2 to 20 oxyalkylene units provided that no O-N
bonds are formed ; each R2 is C1-C4 alkyl or hydroxyalkyl, the moiety -L-X, or two R2 together form the moiety -(CH2)r-A2-(CH2)s-, wherein A2 is -O- or -CH2-, r is 1 or 2, s is 1 or 2, and r + s is 3 or 4; X is a nonionic group, an anionic group or mixture thereof; R3 is a substituted C3-C12 alkyl, hydroxyalkyl, alkenyl, aryl, or alkaryl group having p substitution sites; R4 is C1-C12 alkylene, hydroxyalkylene, alkenylene, arylene or alkarylene, or a C2-C3 oxyalkylene moiety have from 2 to 20 oxyalkylene units provided that no O-O or O-N bonds are formed; L is a hydrophilic chain which contains the polyoxyalkylene moiety -[(R5O)m(CH2CH2O)n]-, wherein R5 is C3-C4 alkylene or hydroxyalkylene and m and n are numbers such that the moiety -(CH2CH2O)n- comprises at least 50%
by weight of said polyoxyalkylene moiety; for said monoamines, m is from 0 to 4, and n is at least 12;
for said diamines, m is from 0 to 3, and n is at least 6 when R1 is C2-C3 alkylene, hydroxyalkylene, or alkenylene, and at least 3 when R1 is other than C2-C3 alkylene, hydroxyalkylene or alkenylene; for said polyamines and amine polymers, m is from 0 to 10 and n is at least 3; p is from 3 to 8; q is 1 or 0; t is 1 or 0, provided that t is 1 when q is 1; w is 1 or 0; x + y + z is at least 2; and y + z is at least 2; and iii) combinations of said polycarboxylate and ethoxylat-ed amine dispersing/anti-redeposition agents;
the weight ratio of sequestering agent to dispersing/anti-rede-position agent within said composition being within the range of from 70:30 to 99:1.
(A) from 70% to 99% by weight of an ether carboxylate sequester-ing agent having the formula:
wherein X is H or a salt-forming cation; and (B) from 1% to 30% by weight of a dispersing/anti-redeposition agent selected from the group consisting of:
i) polycarboxylates which are polymers or copolymers which contain at least 60% by weight of segments having the general formula:
wherein X, Y and Z are, independently, selected from hydrogen, methyl, carboxy, carboxymethyl, hydroxy and hydroxymethyl; M is H or a salt-forming cation and n ranges from 30 to 400;
ii) ethoxylated amine material selected from the group consisting of (a) ethoxylated monoamines having the formula:
(b) ethoxylated diamines having the formula:
or (c) ethoxylated polyamines having the formula:
(d) ethoxylated amine polymers having the general formula:
and (e) mixtures of such ethoxylated amines;
wherein A1 is R is H or C1-C4 alkyl or hydroxyalkyl; R1 is C2-C12 alkylene, hydroxyalkylene, alkenylene, arylene or alkarylene, or a C2-C3 oxyalkylene moiety having from 2 to 20 oxyalkylene units provided that no O-N
bonds are formed ; each R2 is C1-C4 alkyl or hydroxyalkyl, the moiety -L-X, or two R2 together form the moiety -(CH2)r-A2-(CH2)s-, wherein A2 is -O- or -CH2-, r is 1 or 2, s is 1 or 2, and r + s is 3 or 4; X is a nonionic group, an anionic group or mixture thereof; R3 is a substituted C3-C12 alkyl, hydroxyalkyl, alkenyl, aryl, or alkaryl group having p substitution sites; R4 is C1-C12 alkylene, hydroxyalkylene, alkenylene, arylene or alkarylene, or a C2-C3 oxyalkylene moiety have from 2 to 20 oxyalkylene units provided that no O-O or O-N bonds are formed; L is a hydrophilic chain which contains the polyoxyalkylene moiety -[(R5O)m(CH2CH2O)n]-, wherein R5 is C3-C4 alkylene or hydroxyalkylene and m and n are numbers such that the moiety -(CH2CH2O)n- comprises at least 50%
by weight of said polyoxyalkylene moiety; for said monoamines, m is from 0 to 4, and n is at least 12;
for said diamines, m is from 0 to 3, and n is at least 6 when R1 is C2-C3 alkylene, hydroxyalkylene, or alkenylene, and at least 3 when R1 is other than C2-C3 alkylene, hydroxyalkylene or alkenylene; for said polyamines and amine polymers, m is from 0 to 10 and n is at least 3; p is from 3 to 8; q is 1 or 0; t is 1 or 0, provided that t is 1 when q is 1; w is 1 or 0; x + y + z is at least 2; and y + z is at least 2; and iii) combinations of said polycarboxylate and ethoxylat-ed amine dispersing/anti-redeposition agents;
the weight ratio of sequestering agent to dispersing/anti-rede-position agent within said composition being within the range of from 70:30 to 99:1.
2. A builder composition according to Claim 1 wherein (A) the ether carboxylate sequestering agent comprises from 80% to 95% by weight of the composition;
(B) the dispersing/anti-redeposition agent comprises from 5%
to 20% by weight of the composition; and (C) the weight ratio of sequestering agent to dispers-ing/anti-redeposition agent in the composition ranges from 80:20 to 95:5.
(B) the dispersing/anti-redeposition agent comprises from 5%
to 20% by weight of the composition; and (C) the weight ratio of sequestering agent to dispers-ing/anti-redeposition agent in the composition ranges from 80:20 to 95:5.
3. A builder composition according to Claim 1 or Claim 2 wherein (A) the ether carboxylate sequestering agent is an alkali metal or alkanolamine salt of oxydisuccinic acid; and (B) the dispersing/anti-redeposition agent is selected from i) water-soluble salts of polyacrylic acid;
ii) ethoxylated amine polymers; and iii) combinations of said polyacrylic acid salts and said ethoxylated amine polymers in a weight ratio of polyacrylic acid salt to ethoxylated amine polymer of from 5:1 to 1:5.
ii) ethoxylated amine polymers; and iii) combinations of said polyacrylic acid salts and said ethoxylated amine polymers in a weight ratio of polyacrylic acid salt to ethoxylated amine polymer of from 5:1 to 1:5.
4. A detergent composition comprising:
(A) from 5% to 50% by weight of an ether carboxylate sequestering agent having the formula:
wherein X is H or a salt-forming cation; and (B) from 0.2% to 5% by weight of a dispersing/anti-redeposition agent selected from the group consisting of:
i) polycarboxylates which are polymers or copolymers which contain at least 60% by weight of segments having the general formula:
wherein X, Y and Z are, independently, selected from hydrogen, methyl, carboxy, carboxymethyl, hydroxy and hydroxymethyl; M is H or a salt-forming cation and n ranges from 30 to 400;
ii) ethoxylated amine materials selected from the group consisting of (a) ethoxylated monoamines having the formula:
(b) ethoxylated diamines having the formula:
(c) ethoxylated polyamines having the formula:
R3 - [(A1)q-(R4)t-N-L-X]p (d) ethoxylated amine polymers having the general formula:
(e) mixtures of such ethoxylated amines;
wherein A1 is or -O-;
R is H or C1-C4 alkyl or hydroxyalkyl; R1 is C2-C12 alkylene, hydroxyalkylene, alkenylene, arylene or alkarylene, or a C2-C3 oxyalkylene moiety having from 2 to 20 oxyalkylene units provided that no O-N
bonds are formed ; each R2 is C1-C4 alkyl or hydroxyalkyl, the moiety -L-X, or two R2 together form the moiety -(CH2)r-A2-(CH2)s-, wherein A2 is -O- or -CH2-, r is 1 or 2, s is 1 or 2, and r + s is 3 or 4; X is a nonionic group, an anionic group or mixture thereof; R3 is a substituted C3-C12 alkyl, hydroxyalkyl, alkenyl, aryl, or alkaryl group having p substitution sites; R4 is C1-C12 alkylene, hydroxyalkylene, alkenylene, arylene or alkarylene, or a C2-C3 oxyalkylene moiety have from 2 to 20 oxyalkylene units provided that no O-O or O-N bonds are formed; L is a hydrophilic chain which contains the polyoxyalkylene moiety -[(R5O)m(CH2CH2O)n]-, wherein R5 is C3-C4 alkylene or hydroxyalkylene and m and n are numbers such that the moiety -(CH2CH2O)n- comprises at least 50%
by weight of said polyoxyalkylene moiety; for said monoamines, m is from 0 to 4, and n is at least 12;
for said diamines, m is from 0 to 3, and n is at least 6 when R1 is C2-C3 alkylene, hydroxyalkylene, or alkenylene, and at least 3 when R1 is other than C2-C3 alkylene, hydroxyalkylene or alkenylene; for said polyamines and amine polymers, m is from 0 to 10 and n is at least 3; p is from 3 to 8; q is 1 or 0; t is 1 or 0, provided that t is 1 when q is 1; w is 1 or 0; x + y + z is at least 2; and y + z is at least 2; and iii) combinations of said polycarboxylate and ethoxylated amine dispersing/anti-redeposition agents;
the weight ratio of sequestering agent to dispers-ing/anti-redeposition agent within said composition being within the range of from 99:1 to 70:30;
(C) from 5% to 40% of a surfactant; and (D) from 5% to 95% by weight of an additional component selected from the group consisting of additional detergent builders, chelating agents, enzymes, fabric whiteners and brighteners, sudsing control agents, solvents, hydrotropes, bleaching agents, bleach precursors, buffering agents, additional soil removal/anti-redeposition agents, soil release agents, fabric softening agents, perfumes, solvents, opacifiers and combinations of said additional components.
(A) from 5% to 50% by weight of an ether carboxylate sequestering agent having the formula:
wherein X is H or a salt-forming cation; and (B) from 0.2% to 5% by weight of a dispersing/anti-redeposition agent selected from the group consisting of:
i) polycarboxylates which are polymers or copolymers which contain at least 60% by weight of segments having the general formula:
wherein X, Y and Z are, independently, selected from hydrogen, methyl, carboxy, carboxymethyl, hydroxy and hydroxymethyl; M is H or a salt-forming cation and n ranges from 30 to 400;
ii) ethoxylated amine materials selected from the group consisting of (a) ethoxylated monoamines having the formula:
(b) ethoxylated diamines having the formula:
(c) ethoxylated polyamines having the formula:
R3 - [(A1)q-(R4)t-N-L-X]p (d) ethoxylated amine polymers having the general formula:
(e) mixtures of such ethoxylated amines;
wherein A1 is or -O-;
R is H or C1-C4 alkyl or hydroxyalkyl; R1 is C2-C12 alkylene, hydroxyalkylene, alkenylene, arylene or alkarylene, or a C2-C3 oxyalkylene moiety having from 2 to 20 oxyalkylene units provided that no O-N
bonds are formed ; each R2 is C1-C4 alkyl or hydroxyalkyl, the moiety -L-X, or two R2 together form the moiety -(CH2)r-A2-(CH2)s-, wherein A2 is -O- or -CH2-, r is 1 or 2, s is 1 or 2, and r + s is 3 or 4; X is a nonionic group, an anionic group or mixture thereof; R3 is a substituted C3-C12 alkyl, hydroxyalkyl, alkenyl, aryl, or alkaryl group having p substitution sites; R4 is C1-C12 alkylene, hydroxyalkylene, alkenylene, arylene or alkarylene, or a C2-C3 oxyalkylene moiety have from 2 to 20 oxyalkylene units provided that no O-O or O-N bonds are formed; L is a hydrophilic chain which contains the polyoxyalkylene moiety -[(R5O)m(CH2CH2O)n]-, wherein R5 is C3-C4 alkylene or hydroxyalkylene and m and n are numbers such that the moiety -(CH2CH2O)n- comprises at least 50%
by weight of said polyoxyalkylene moiety; for said monoamines, m is from 0 to 4, and n is at least 12;
for said diamines, m is from 0 to 3, and n is at least 6 when R1 is C2-C3 alkylene, hydroxyalkylene, or alkenylene, and at least 3 when R1 is other than C2-C3 alkylene, hydroxyalkylene or alkenylene; for said polyamines and amine polymers, m is from 0 to 10 and n is at least 3; p is from 3 to 8; q is 1 or 0; t is 1 or 0, provided that t is 1 when q is 1; w is 1 or 0; x + y + z is at least 2; and y + z is at least 2; and iii) combinations of said polycarboxylate and ethoxylated amine dispersing/anti-redeposition agents;
the weight ratio of sequestering agent to dispers-ing/anti-redeposition agent within said composition being within the range of from 99:1 to 70:30;
(C) from 5% to 40% of a surfactant; and (D) from 5% to 95% by weight of an additional component selected from the group consisting of additional detergent builders, chelating agents, enzymes, fabric whiteners and brighteners, sudsing control agents, solvents, hydrotropes, bleaching agents, bleach precursors, buffering agents, additional soil removal/anti-redeposition agents, soil release agents, fabric softening agents, perfumes, solvents, opacifiers and combinations of said additional components.
5. A detergent composition according to Claim 4 wherein (A) the ether carboxylate sequestering agent comprises from 10% to 30% by weight of the composition;
(B) the dispersing/anti-redeposition agent comprises from 0.5% to 3% by weight of the composition;
(C) the weight ratio of sequestering agent to dispers-ing/anti-redeposition agent in the composition ranges from 80:20 to 95:5; and (D) the surfactant comprises from 10% to 30% by weight of the composition.
(B) the dispersing/anti-redeposition agent comprises from 0.5% to 3% by weight of the composition;
(C) the weight ratio of sequestering agent to dispers-ing/anti-redeposition agent in the composition ranges from 80:20 to 95:5; and (D) the surfactant comprises from 10% to 30% by weight of the composition.
6. A detergent composition according to Claim 4 wherein (A) the ether carboxylate sequestering agent is an alkali metal or alkanolamine salt of oxydisuccinic acid; and (B) the dispersing/anti-redeposition agent is selected from i) water-soluble salts of polyacrylic acid;
ii) ethoxylated amine polymers; and iii) combinations of said polyacrylate acid salts and said ethoxylated amine polymers in a weight ratio of polyacrylic acid salt to ethoxylated amine polymer of from 5:1 to 1:5.
ii) ethoxylated amine polymers; and iii) combinations of said polyacrylate acid salts and said ethoxylated amine polymers in a weight ratio of polyacrylic acid salt to ethoxylated amine polymer of from 5:1 to 1:5.
7. A detergent composition according to Claim 4, 5 or 6 wherein the ethoxylated amine polymer compo-nent is selected from (A) an ethoxylated polyethyleneamine having a molecular weight of from 140 to 310 prior to ethoxylation; and (b) an ethoxylated polyethyleneimine having a molecular weight of from 600 to 1800 prior to ethoxylation.
8. A detergent composition according to Claim 4, 5 or 6 wherein the dispersing/anti-redeposition agent comprises a com-bination of sodium polyacrylate having a molecular weight of from 4,000 to 10,000 and an ethoxylated amine polymer in a weight ratio of polyacrylate to ethoxylated amine polymer which ranges from 3:2 to 2:3.
9. A detergent composition according to Claim 4 which comprises (A) from 5% to 40% by weight of a surfactant;
(B) from 5% to 50% by weight of an ether carboxylate sequestering agent which is sodium oxydisuccinate; and (C) from 0.2% to 5% by weight of a dispersing/anti-redeposition agent selected from i) sodium polyacrylate having a molecular weight of from 4,000 to 10,000;
ii) ethoxylated polyethyleneamines having a molecular weight of from 100 to 400 prior to ethoxylation and a degree of ethoxylation of at least 3; and iii) combinations of said polyacrylate and said ethoxylated polyethyleneamine in a weight ratio of from 5:1 to 1:5;
the weight ratio of sequestering agent to dispersing/anti-redeposition agent in said composition ranging from 99:1 to 70:30.
(B) from 5% to 50% by weight of an ether carboxylate sequestering agent which is sodium oxydisuccinate; and (C) from 0.2% to 5% by weight of a dispersing/anti-redeposition agent selected from i) sodium polyacrylate having a molecular weight of from 4,000 to 10,000;
ii) ethoxylated polyethyleneamines having a molecular weight of from 100 to 400 prior to ethoxylation and a degree of ethoxylation of at least 3; and iii) combinations of said polyacrylate and said ethoxylated polyethyleneamine in a weight ratio of from 5:1 to 1:5;
the weight ratio of sequestering agent to dispersing/anti-redeposition agent in said composition ranging from 99:1 to 70:30.
10. A detergent composition according to Claim 4, 5 or 9 wherein the dispersing/anti-redeposition agent is a combination of sodium polyacrylate and an ethoxylated polyethyleneamine having a molecular weight of from 140 to 200 prior to ethoxylation and a degree of ethoxylation of from 12 to 42.
11. A detergent composition according to Claim 4 which additionally contains from 0.1% to 10% by weight of a chelating agent selected from amino carboxylates, amino phos-phonates, poly-functionally substituted aromatic chelating agents and combinations of these materials.
12. A detergent composition according to Claim 11 wherein the chelating agent is a diethylenetriaminepentaacetate.
13. A laundry additive composition comprising:
(A) from 5% to 95% by weight of an ether carboxylate sequestering agent having the formula:
wherein X is H or a salt-forming cation; and (B) from 0.2% to 10% by weight of a dispersing/anti-redeposition agent selected from the group consisting of:
i) polycarboxylates which are polymers or copolymers which contain at least 60% by weight of segments having the general formula:
wherein X, Y and Z are, independently, selected from hydrogen, methyl, carboxy, carboxymethyl, hydroxy and hydroxymethyl; M is H or a salt-forming cation and n ranges from 30 to 400;
ii) ethoxylated amine materials selected from the group consisting of (a) ethoxylated monoamines having the formula:
(b) ethoxylated diamines having the formula:
(c) ethoxylated polyamines having the formula:
R3 - [(A1)q-(R4)t-N-L-X]p (d) ethoxylated amine polymers having the general formula:
(e) mixtures of such ethoxylated amines;
wherein A1 is R is H or C1-C4 alkyl or hydroxyalkyl; R1 is C2-C12 alkylene, hydroxyalkylene, alkenylene, arylene or alkarylene, or a C2-C3 oxyalkylene moiety having from 2 to 20 oxyalkylene units provided that no O-N
bonds are formed ; each R2 is C1-C4 alkyl or hydroxyalkyl, the moiety -L-X, or two R2 together form the moiety -(CH2)r-A2-(CH2)s-, wherein A2 is -O- or -CH2-, r is 1 or 2, s is 1 or 2, and r + s is 3 or 4; X is a nonionic group, an anionic group or mixture thereof; R3 is a substituted C3-C12 alkyl, hydroxyalkyl, alkenyl, aryl, or alkaryl group having p substitution sites; R4 is C1-C12 alkylene, hydroxyalkylene, alkenylene, arylene or alkarylene, or a C2-C3 oxyalkylene moiety have from 2 to 20 oxyalkylene units provided that no O-O or O-N bonds are formed; L is a hydrophilic chain which contains the polyoxyalkylene moiety -[(R5O)m(CH2CH2O)n]-, wherein R5 is C3-C4 alkylene or hydroxyalkylene and m and n are numbers such that the moiety -(CH2CH2O)n- comprises at least 50%
by weight of said polyoxyalkylene moiety; for said monoamines, m is from 0 to 4, and n is at least 12;
for said diamines, m is from 0 to 3, and n is at least 6 when R1 is C2-C3 alkylene, hydroxyalkylene, or alkenylene, and at least 3 when R1 is other than C2-C3 alkylene, hydroxyalkylene or alkenylene; for said polyamines and amine polymers, m is from 0 to 10 and n is at least 3; p is from 3 to 8; q is 1 or 0; t is 1 or 0, provided that t is 1 when q is 1; w is 1 or 0; x + y + z is at least 2; and y + z is at least 2; and iii) combinations of said polycarboxylate and ethoxylated amine dispersing/anti-redeposition agents;
the weight ratio of sequestering agent to dispers-ing/anti-redeposition agent within said composition being within the range of from 99:1 to 70:30; and (C) from 0.5% to 98% by weight of an additional component selected from the group consisting of surfactants, additional detergent builders, chelating agents, enzymes, fabric whiteners and brighteners, sudsing control agents, solvents, hydrotropes, bleaching agents, bleach precursors, buffering agents, additional soil removal/anti-redeposition agents, soil release agents, fabric softening agents, perfumes, solvents, opacifiers and combinations of said additional components.
(A) from 5% to 95% by weight of an ether carboxylate sequestering agent having the formula:
wherein X is H or a salt-forming cation; and (B) from 0.2% to 10% by weight of a dispersing/anti-redeposition agent selected from the group consisting of:
i) polycarboxylates which are polymers or copolymers which contain at least 60% by weight of segments having the general formula:
wherein X, Y and Z are, independently, selected from hydrogen, methyl, carboxy, carboxymethyl, hydroxy and hydroxymethyl; M is H or a salt-forming cation and n ranges from 30 to 400;
ii) ethoxylated amine materials selected from the group consisting of (a) ethoxylated monoamines having the formula:
(b) ethoxylated diamines having the formula:
(c) ethoxylated polyamines having the formula:
R3 - [(A1)q-(R4)t-N-L-X]p (d) ethoxylated amine polymers having the general formula:
(e) mixtures of such ethoxylated amines;
wherein A1 is R is H or C1-C4 alkyl or hydroxyalkyl; R1 is C2-C12 alkylene, hydroxyalkylene, alkenylene, arylene or alkarylene, or a C2-C3 oxyalkylene moiety having from 2 to 20 oxyalkylene units provided that no O-N
bonds are formed ; each R2 is C1-C4 alkyl or hydroxyalkyl, the moiety -L-X, or two R2 together form the moiety -(CH2)r-A2-(CH2)s-, wherein A2 is -O- or -CH2-, r is 1 or 2, s is 1 or 2, and r + s is 3 or 4; X is a nonionic group, an anionic group or mixture thereof; R3 is a substituted C3-C12 alkyl, hydroxyalkyl, alkenyl, aryl, or alkaryl group having p substitution sites; R4 is C1-C12 alkylene, hydroxyalkylene, alkenylene, arylene or alkarylene, or a C2-C3 oxyalkylene moiety have from 2 to 20 oxyalkylene units provided that no O-O or O-N bonds are formed; L is a hydrophilic chain which contains the polyoxyalkylene moiety -[(R5O)m(CH2CH2O)n]-, wherein R5 is C3-C4 alkylene or hydroxyalkylene and m and n are numbers such that the moiety -(CH2CH2O)n- comprises at least 50%
by weight of said polyoxyalkylene moiety; for said monoamines, m is from 0 to 4, and n is at least 12;
for said diamines, m is from 0 to 3, and n is at least 6 when R1 is C2-C3 alkylene, hydroxyalkylene, or alkenylene, and at least 3 when R1 is other than C2-C3 alkylene, hydroxyalkylene or alkenylene; for said polyamines and amine polymers, m is from 0 to 10 and n is at least 3; p is from 3 to 8; q is 1 or 0; t is 1 or 0, provided that t is 1 when q is 1; w is 1 or 0; x + y + z is at least 2; and y + z is at least 2; and iii) combinations of said polycarboxylate and ethoxylated amine dispersing/anti-redeposition agents;
the weight ratio of sequestering agent to dispers-ing/anti-redeposition agent within said composition being within the range of from 99:1 to 70:30; and (C) from 0.5% to 98% by weight of an additional component selected from the group consisting of surfactants, additional detergent builders, chelating agents, enzymes, fabric whiteners and brighteners, sudsing control agents, solvents, hydrotropes, bleaching agents, bleach precursors, buffering agents, additional soil removal/anti-redeposition agents, soil release agents, fabric softening agents, perfumes, solvents, opacifiers and combinations of said additional components.
14. A laundry additive composition according to Claim 13 wherein (A) the ether carboxylate sequestering agent comprises from 10% to 30% by weight of the composition;
(B) the dispersing/anti-redeposition agent comprises from 0.5% to 3% by weight of the composition;
(C) the weight ratio of sequestering agent to dispers-ing/anti-redeposition agent in the composition ranges from 80:20 to 95:5.
(B) the dispersing/anti-redeposition agent comprises from 0.5% to 3% by weight of the composition;
(C) the weight ratio of sequestering agent to dispers-ing/anti-redeposition agent in the composition ranges from 80:20 to 95:5.
15. A laundry additive composition according to Claim 14 wherein (A) the ether carboxylate sequestering agent is an alkali metal or alkanolamine salt of oxydisuccinic acid; and (B) the dispersing/anti-redeposition agent is selected from i) water-soluble salts of polyacrylic acid;
ii) ethoxylated amine polymers; and iii) combinations of said polyacrylate acid salts and said ethoxylated amine polymers in a weight ratio of polyacrylic acid salt to ethoxylated amine polymer of from 5:1 to 1:5.
ii) ethoxylated amine polymers; and iii) combinations of said polyacrylate acid salts and said ethoxylated amine polymers in a weight ratio of polyacrylic acid salt to ethoxylated amine polymer of from 5:1 to 1:5.
16. A laundry additive composition according to any of Claim 13 to 15 wherein the ethoxylated amine polymer compo-nent is selected from (A) an ethoxylated polyethyleneamine having a molecular weight of from 140 to 310 prior to ethoxylation; and (b) an ethoxylated polyethyleneimine having a molecular weight of from 600 to 1800 prior to ethoxylation.
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| US70252185A | 1985-02-19 | 1985-02-19 | |
| US702,521 | 1985-02-19 |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CA1253769A true CA1253769A (en) | 1989-05-09 |
Family
ID=24821544
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CA000501968A Expired CA1253769A (en) | 1985-02-19 | 1986-02-17 | Detergency builder system |
Country Status (2)
| Country | Link |
|---|---|
| JP (1) | JPS61246298A (en) |
| CA (1) | CA1253769A (en) |
Families Citing this family (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| PL1754781T3 (en) * | 2005-08-19 | 2013-09-30 | Procter & Gamble | A solid laundry detergent composition comprising anionic detersive surfactant and a calcium-augmented technology |
| WO2007049249A1 (en) * | 2005-10-28 | 2007-05-03 | The Procter & Gamble Company | Compositions containing anionically modified catechol and soil suspending polymers |
| JP6967939B2 (en) * | 2017-10-31 | 2021-11-17 | ライオン株式会社 | Liquid cleaner |
Family Cites Families (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4597898A (en) * | 1982-12-23 | 1986-07-01 | The Proctor & Gamble Company | Detergent compositions containing ethoxylated amines having clay soil removal/anti-redeposition properties |
-
1986
- 1986-02-17 CA CA000501968A patent/CA1253769A/en not_active Expired
- 1986-02-19 JP JP61034929A patent/JPS61246298A/en active Pending
Also Published As
| Publication number | Publication date |
|---|---|
| JPS61246298A (en) | 1986-11-01 |
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