CA2652467A1 - Liquid detergent compositions with low polydispersity polyacrylic acid based polymers - Google Patents
Liquid detergent compositions with low polydispersity polyacrylic acid based polymers Download PDFInfo
- Publication number
- CA2652467A1 CA2652467A1 CA002652467A CA2652467A CA2652467A1 CA 2652467 A1 CA2652467 A1 CA 2652467A1 CA 002652467 A CA002652467 A CA 002652467A CA 2652467 A CA2652467 A CA 2652467A CA 2652467 A1 CA2652467 A1 CA 2652467A1
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- CA
- Canada
- Prior art keywords
- units
- formula
- mixtures
- backbone
- liquid detergent
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Abandoned
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- 239000000203 mixture Substances 0.000 title claims abstract description 129
- 239000007788 liquid Substances 0.000 title claims abstract description 64
- 239000003599 detergent Substances 0.000 title claims abstract description 63
- 229920000642 polymer Polymers 0.000 title claims abstract description 62
- 229920002125 Sokalan® Polymers 0.000 title claims abstract description 22
- 239000004584 polyacrylic acid Substances 0.000 title claims abstract description 19
- 239000000178 monomer Substances 0.000 claims abstract description 30
- 239000002904 solvent Substances 0.000 claims abstract description 16
- 229920000768 polyamine Polymers 0.000 claims description 78
- -1 propoxy, butoxy Chemical group 0.000 claims description 48
- 239000001257 hydrogen Substances 0.000 claims description 35
- 229910052739 hydrogen Inorganic materials 0.000 claims description 35
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 claims description 32
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 27
- 125000000217 alkyl group Chemical group 0.000 claims description 23
- 125000000129 anionic group Chemical group 0.000 claims description 21
- 125000002947 alkylene group Chemical group 0.000 claims description 18
- 230000004048 modification Effects 0.000 claims description 17
- 238000012986 modification Methods 0.000 claims description 17
- WSFSSNUMVMOOMR-UHFFFAOYSA-N Formaldehyde Chemical compound O=C WSFSSNUMVMOOMR-UHFFFAOYSA-N 0.000 claims description 16
- 150000001768 cations Chemical class 0.000 claims description 16
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims description 16
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical group O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 16
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 claims description 15
- NIXOWILDQLNWCW-UHFFFAOYSA-N 2-Propenoic acid Natural products OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 claims description 15
- 235000019256 formaldehyde Nutrition 0.000 claims description 15
- 229910052757 nitrogen Inorganic materials 0.000 claims description 15
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 13
- 150000002431 hydrogen Chemical class 0.000 claims description 12
- 229920001577 copolymer Polymers 0.000 claims description 11
- 150000001875 compounds Chemical class 0.000 claims description 9
- 150000001204 N-oxides Chemical class 0.000 claims description 7
- 150000001450 anions Chemical class 0.000 claims description 6
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical group [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 5
- 230000002209 hydrophobic effect Effects 0.000 claims description 5
- 239000001301 oxygen Substances 0.000 claims description 5
- 229910052760 oxygen Inorganic materials 0.000 claims description 5
- 125000001797 benzyl group Chemical group [H]C1=C([H])C([H])=C(C([H])=C1[H])C([H])([H])* 0.000 claims description 4
- 229920001519 homopolymer Polymers 0.000 claims description 4
- 125000005702 oxyalkylene group Chemical group 0.000 claims description 3
- 229920001223 polyethylene glycol Polymers 0.000 claims description 3
- 229920001296 polysiloxane Polymers 0.000 claims description 3
- 239000002202 Polyethylene glycol Substances 0.000 claims description 2
- 125000003118 aryl group Chemical group 0.000 claims description 2
- 125000000732 arylene group Chemical group 0.000 claims description 2
- 125000000467 secondary amino group Chemical group [H]N([*:1])[*:2] 0.000 claims description 2
- 125000001302 tertiary amino group Chemical group 0.000 claims description 2
- 125000002853 C1-C4 hydroxyalkyl group Chemical group 0.000 claims 2
- 125000004178 (C1-C4) alkyl group Chemical group 0.000 claims 1
- 150000001252 acrylic acid derivatives Chemical class 0.000 claims 1
- 230000009286 beneficial effect Effects 0.000 abstract description 2
- 239000004094 surface-active agent Substances 0.000 description 24
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 description 20
- 239000005977 Ethylene Substances 0.000 description 20
- 239000002689 soil Substances 0.000 description 17
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 16
- 239000003795 chemical substances by application Substances 0.000 description 15
- 229920002873 Polyethylenimine Polymers 0.000 description 14
- 229920000742 Cotton Polymers 0.000 description 13
- 239000002736 nonionic surfactant Substances 0.000 description 13
- 239000000463 material Substances 0.000 description 12
- 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 11
- 239000011734 sodium Substances 0.000 description 11
- 229910052708 sodium Inorganic materials 0.000 description 11
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 10
- 150000008051 alkyl sulfates Chemical class 0.000 description 10
- 150000001412 amines Chemical class 0.000 description 10
- 239000003945 anionic surfactant Substances 0.000 description 10
- QJGQUHMNIGDVPM-UHFFFAOYSA-N nitrogen group Chemical group [N] QJGQUHMNIGDVPM-UHFFFAOYSA-N 0.000 description 10
- 239000000243 solution Substances 0.000 description 10
- 125000004432 carbon atom Chemical group C* 0.000 description 9
- 239000004615 ingredient Substances 0.000 description 9
- 125000001183 hydrocarbyl group Chemical group 0.000 description 7
- 150000003335 secondary amines Chemical class 0.000 description 7
- 238000006467 substitution reaction Methods 0.000 description 7
- 239000000654 additive Substances 0.000 description 6
- 238000013019 agitation Methods 0.000 description 6
- 150000004996 alkyl benzenes Chemical class 0.000 description 6
- 125000004122 cyclic group Chemical group 0.000 description 6
- 239000004744 fabric Substances 0.000 description 6
- 238000000034 method Methods 0.000 description 6
- IAYPIBMASNFSPL-UHFFFAOYSA-N Ethylene oxide Chemical group C1CO1 IAYPIBMASNFSPL-UHFFFAOYSA-N 0.000 description 5
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 description 5
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 description 5
- 238000004900 laundering Methods 0.000 description 5
- 229910052700 potassium Inorganic materials 0.000 description 5
- 239000011591 potassium Substances 0.000 description 5
- 150000003512 tertiary amines Chemical class 0.000 description 5
- 238000005406 washing Methods 0.000 description 5
- HZAXFHJVJLSVMW-UHFFFAOYSA-N 2-Aminoethan-1-ol Chemical compound NCCO HZAXFHJVJLSVMW-UHFFFAOYSA-N 0.000 description 4
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 4
- 102000004190 Enzymes Human genes 0.000 description 4
- 108090000790 Enzymes Proteins 0.000 description 4
- 239000002253 acid Substances 0.000 description 4
- 238000004140 cleaning Methods 0.000 description 4
- 150000002191 fatty alcohols Chemical class 0.000 description 4
- 150000002500 ions Chemical class 0.000 description 4
- 125000004433 nitrogen atom Chemical group N* 0.000 description 4
- 239000012071 phase Substances 0.000 description 4
- 238000005956 quaternization reaction Methods 0.000 description 4
- GETQZCLCWQTVFV-UHFFFAOYSA-N trimethylamine Chemical compound CN(C)C GETQZCLCWQTVFV-UHFFFAOYSA-N 0.000 description 4
- NARVIWMVBMUEOG-UHFFFAOYSA-N 2-Hydroxy-propylene Natural products CC(O)=C NARVIWMVBMUEOG-UHFFFAOYSA-N 0.000 description 3
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 3
- KWIUHFFTVRNATP-UHFFFAOYSA-N Betaine Natural products C[N+](C)(C)CC([O-])=O KWIUHFFTVRNATP-UHFFFAOYSA-N 0.000 description 3
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 description 3
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- KWIUHFFTVRNATP-UHFFFAOYSA-O N,N,N-trimethylglycinium Chemical compound C[N+](C)(C)CC(O)=O KWIUHFFTVRNATP-UHFFFAOYSA-O 0.000 description 3
- DNIAPMSPPWPWGF-UHFFFAOYSA-N Propylene glycol Chemical compound CC(O)CO DNIAPMSPPWPWGF-UHFFFAOYSA-N 0.000 description 3
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- 125000005529 alkyleneoxy group Chemical group 0.000 description 3
- 230000008901 benefit Effects 0.000 description 3
- 229960003237 betaine Drugs 0.000 description 3
- 239000003093 cationic surfactant Substances 0.000 description 3
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 description 3
- 235000014113 dietary fatty acids Nutrition 0.000 description 3
- MTHSVFCYNBDYFN-UHFFFAOYSA-N diethylene glycol Chemical compound OCCOCCO MTHSVFCYNBDYFN-UHFFFAOYSA-N 0.000 description 3
- 239000006185 dispersion Substances 0.000 description 3
- 229930195729 fatty acid Natural products 0.000 description 3
- 239000000194 fatty acid Substances 0.000 description 3
- 150000004665 fatty acids Chemical class 0.000 description 3
- 229940083124 ganglion-blocking antiadrenergic secondary and tertiary amines Drugs 0.000 description 3
- 230000003647 oxidation Effects 0.000 description 3
- 238000007254 oxidation reaction Methods 0.000 description 3
- 238000002360 preparation method Methods 0.000 description 3
- 239000007787 solid Substances 0.000 description 3
- 239000003381 stabilizer Substances 0.000 description 3
- 238000003786 synthesis reaction Methods 0.000 description 3
- 125000000383 tetramethylene group Chemical group [H]C([H])([*:1])C([H])([H])C([H])([H])C([H])([H])[*:2] 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
- GXVUZYLYWKWJIM-UHFFFAOYSA-N 2-(2-aminoethoxy)ethanamine Chemical compound NCCOCCN GXVUZYLYWKWJIM-UHFFFAOYSA-N 0.000 description 2
- RZVAJINKPMORJF-UHFFFAOYSA-N Acetaminophen Chemical compound CC(=O)NC1=CC=C(O)C=C1 RZVAJINKPMORJF-UHFFFAOYSA-N 0.000 description 2
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical group [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 description 2
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 description 2
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 2
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-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
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 2
- 125000001931 aliphatic group Chemical group 0.000 description 2
- 229910052783 alkali metal Inorganic materials 0.000 description 2
- 150000005215 alkyl ethers Chemical class 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 229910021538 borax Inorganic materials 0.000 description 2
- 229910052791 calcium Inorganic materials 0.000 description 2
- 229910002092 carbon dioxide Inorganic materials 0.000 description 2
- 239000003153 chemical reaction reagent Substances 0.000 description 2
- 239000000460 chlorine Substances 0.000 description 2
- 239000000470 constituent Substances 0.000 description 2
- 150000002009 diols Chemical class 0.000 description 2
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 2
- LYCAIKOWRPUZTN-UHFFFAOYSA-N ethylene glycol Natural products OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 2
- 238000009472 formulation Methods 0.000 description 2
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 description 2
- 239000003999 initiator Substances 0.000 description 2
- 239000002563 ionic surfactant Substances 0.000 description 2
- BDAGIHXWWSANSR-UHFFFAOYSA-N methanoic acid Natural products OC=O BDAGIHXWWSANSR-UHFFFAOYSA-N 0.000 description 2
- 239000002245 particle Substances 0.000 description 2
- 239000002304 perfume Substances 0.000 description 2
- 229920001495 poly(sodium acrylate) polymer Polymers 0.000 description 2
- 230000008569 process Effects 0.000 description 2
- 125000001453 quaternary ammonium group Chemical group 0.000 description 2
- 150000003839 salts Chemical class 0.000 description 2
- NNMHYFLPFNGQFZ-UHFFFAOYSA-M sodium polyacrylate Chemical compound [Na+].[O-]C(=O)C=C NNMHYFLPFNGQFZ-UHFFFAOYSA-M 0.000 description 2
- 159000000000 sodium salts Chemical class 0.000 description 2
- 239000004328 sodium tetraborate Substances 0.000 description 2
- 235000010339 sodium tetraborate Nutrition 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 239000000725 suspension Substances 0.000 description 2
- 125000003718 tetrahydrofuranyl group Chemical group 0.000 description 2
- 125000006832 (C1-C10) alkylene group Chemical group 0.000 description 1
- MAUMSNABMVEOGP-UHFFFAOYSA-N (methyl-$l^{2}-azanyl)methane Chemical compound C[N]C MAUMSNABMVEOGP-UHFFFAOYSA-N 0.000 description 1
- WSLDOOZREJYCGB-UHFFFAOYSA-N 1,2-Dichloroethane Chemical compound ClCCCl WSLDOOZREJYCGB-UHFFFAOYSA-N 0.000 description 1
- QLAJNZSPVITUCQ-UHFFFAOYSA-N 1,3,2-dioxathietane 2,2-dioxide Chemical compound O=S1(=O)OCO1 QLAJNZSPVITUCQ-UHFFFAOYSA-N 0.000 description 1
- TZJFRKWUJOXRKM-UHFFFAOYSA-N 1-ethoxypentan-1-ol Chemical compound CCCCC(O)OCC TZJFRKWUJOXRKM-UHFFFAOYSA-N 0.000 description 1
- QIXUNLGUNNUKGI-UHFFFAOYSA-N 2-(2-aminopropoxy)pentan-3-amine Chemical compound CCC(N)C(C)OCC(C)N QIXUNLGUNNUKGI-UHFFFAOYSA-N 0.000 description 1
- IAUMQQYSPOLIEE-UHFFFAOYSA-N 2-[2-(2-aminopropoxy)propoxy]propan-1-amine Chemical compound CC(N)COC(C)COC(C)CN IAUMQQYSPOLIEE-UHFFFAOYSA-N 0.000 description 1
- NIQFAJBKEHPUAM-UHFFFAOYSA-N 2-[2-[2-(2-aminoethoxy)ethoxy]ethoxy]ethanamine Chemical compound NCCOCCOCCOCCN NIQFAJBKEHPUAM-UHFFFAOYSA-N 0.000 description 1
- MEEQYWDFCGVGCR-UHFFFAOYSA-N 2-[2-[2-(2-aminoethoxy)ethylamino]ethoxy]ethanamine Chemical compound NCCOCCNCCOCCN MEEQYWDFCGVGCR-UHFFFAOYSA-N 0.000 description 1
- KZXOUIOAKUWAKB-UHFFFAOYSA-N 2-[3-(2-aminoethoxy)propoxy]ethanamine Chemical compound NCCOCCCOCCN KZXOUIOAKUWAKB-UHFFFAOYSA-N 0.000 description 1
- IVFLRGJMYXNABF-UHFFFAOYSA-N 2-[4-(2-aminoethoxy)butoxy]ethanamine Chemical compound NCCOCCCCOCCN IVFLRGJMYXNABF-UHFFFAOYSA-N 0.000 description 1
- ZEVPACPVGMDWTA-UHFFFAOYSA-N 2-[6-(2-aminoethoxy)hexoxy]ethanamine Chemical compound NCCOCCCCCCOCCN ZEVPACPVGMDWTA-UHFFFAOYSA-N 0.000 description 1
- PKSMSCYMRXLUIR-UHFFFAOYSA-N 2-[8-(2-aminoethoxy)octoxy]ethanamine Chemical compound NCCOCCCCCCCCOCCN PKSMSCYMRXLUIR-UHFFFAOYSA-N 0.000 description 1
- FDPCVOXXUBYMTQ-UHFFFAOYSA-N 4-(4-aminobutoxy)butan-1-amine Chemical compound NCCCCOCCCCN FDPCVOXXUBYMTQ-UHFFFAOYSA-N 0.000 description 1
- ZJGRZPCOLBDFIZ-UHFFFAOYSA-N 4-[4-(4-aminobutoxy)butoxy]butan-1-amine Chemical compound NCCCCOCCCCOCCCCN ZJGRZPCOLBDFIZ-UHFFFAOYSA-N 0.000 description 1
- QJRVOJKLQNSNDB-UHFFFAOYSA-N 4-dodecan-3-ylbenzenesulfonic acid Chemical compound CCCCCCCCCC(CC)C1=CC=C(S(O)(=O)=O)C=C1 QJRVOJKLQNSNDB-UHFFFAOYSA-N 0.000 description 1
- 239000004382 Amylase Substances 0.000 description 1
- 102000013142 Amylases Human genes 0.000 description 1
- 108010065511 Amylases Proteins 0.000 description 1
- NOWKCMXCCJGMRR-UHFFFAOYSA-N Aziridine Chemical compound C1CN1 NOWKCMXCCJGMRR-UHFFFAOYSA-N 0.000 description 1
- WKBOTKDWSSQWDR-UHFFFAOYSA-N Bromine atom Chemical compound [Br] WKBOTKDWSSQWDR-UHFFFAOYSA-N 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 1
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 1
- 101000605014 Homo sapiens Putative L-type amino acid transporter 1-like protein MLAS Proteins 0.000 description 1
- 101100448208 Human herpesvirus 6B (strain Z29) U69 gene Proteins 0.000 description 1
- 239000004367 Lipase Substances 0.000 description 1
- 102000004882 Lipase Human genes 0.000 description 1
- 108090001060 Lipase Proteins 0.000 description 1
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 description 1
- AFVFQIVMOAPDHO-UHFFFAOYSA-N Methanesulfonic acid Chemical compound CS(O)(=O)=O AFVFQIVMOAPDHO-UHFFFAOYSA-N 0.000 description 1
- 108091005804 Peptidases Proteins 0.000 description 1
- 239000004698 Polyethylene Substances 0.000 description 1
- GOOHAUXETOMSMM-UHFFFAOYSA-N Propylene oxide Chemical compound CC1CO1 GOOHAUXETOMSMM-UHFFFAOYSA-N 0.000 description 1
- 239000004365 Protease Substances 0.000 description 1
- 102100038206 Putative L-type amino acid transporter 1-like protein MLAS Human genes 0.000 description 1
- 102100037486 Reverse transcriptase/ribonuclease H Human genes 0.000 description 1
- DWAQJAXMDSEUJJ-UHFFFAOYSA-M Sodium bisulfite Chemical compound [Na+].OS([O-])=O DWAQJAXMDSEUJJ-UHFFFAOYSA-M 0.000 description 1
- FKNQFGJONOIPTF-UHFFFAOYSA-N Sodium cation Chemical compound [Na+] FKNQFGJONOIPTF-UHFFFAOYSA-N 0.000 description 1
- 239000004280 Sodium formate Substances 0.000 description 1
- 230000000996 additive effect Effects 0.000 description 1
- 150000001298 alcohols Chemical class 0.000 description 1
- 150000001340 alkali metals Chemical class 0.000 description 1
- 125000005210 alkyl ammonium group Chemical group 0.000 description 1
- 229910021529 ammonia Inorganic materials 0.000 description 1
- 239000002280 amphoteric surfactant Substances 0.000 description 1
- 235000019418 amylase Nutrition 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 239000012298 atmosphere Substances 0.000 description 1
- AGEZXYOZHKGVCM-UHFFFAOYSA-N benzyl bromide Chemical compound BrCC1=CC=CC=C1 AGEZXYOZHKGVCM-UHFFFAOYSA-N 0.000 description 1
- KGBXLFKZBHKPEV-UHFFFAOYSA-N boric acid Chemical compound OB(O)O KGBXLFKZBHKPEV-UHFFFAOYSA-N 0.000 description 1
- 239000004327 boric acid Substances 0.000 description 1
- GDTBXPJZTBHREO-UHFFFAOYSA-N bromine Substances BrBr GDTBXPJZTBHREO-UHFFFAOYSA-N 0.000 description 1
- 229910052794 bromium Inorganic materials 0.000 description 1
- 239000011575 calcium Substances 0.000 description 1
- 235000019255 calcium formate Nutrition 0.000 description 1
- 239000004281 calcium formate Substances 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 239000001569 carbon dioxide Substances 0.000 description 1
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 1
- 150000001732 carboxylic acid derivatives Chemical group 0.000 description 1
- 239000000969 carrier Substances 0.000 description 1
- 239000003054 catalyst Substances 0.000 description 1
- 125000002091 cationic group Chemical group 0.000 description 1
- 239000002738 chelating agent Substances 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 229910052801 chlorine Inorganic materials 0.000 description 1
- NEHMKBQYUWJMIP-NJFSPNSNSA-N chloro(114C)methane Chemical compound [14CH3]Cl NEHMKBQYUWJMIP-NJFSPNSNSA-N 0.000 description 1
- 150000001860 citric acid derivatives Chemical class 0.000 description 1
- 239000003086 colorant Substances 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
- 239000007822 coupling agent Substances 0.000 description 1
- 230000003247 decreasing effect Effects 0.000 description 1
- GYZLOYUZLJXAJU-UHFFFAOYSA-N diglycidyl ether Chemical compound C1OC1COCC1CO1 GYZLOYUZLJXAJU-UHFFFAOYSA-N 0.000 description 1
- 125000000118 dimethyl group Chemical group [H]C([H])([H])* 0.000 description 1
- VAYGXNSJCAHWJZ-UHFFFAOYSA-N dimethyl sulfate Chemical compound COS(=O)(=O)OC VAYGXNSJCAHWJZ-UHFFFAOYSA-N 0.000 description 1
- 238000004821 distillation Methods 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 150000002170 ethers Chemical class 0.000 description 1
- 125000001301 ethoxy group Chemical group [H]C([H])([H])C([H])([H])O* 0.000 description 1
- 238000007046 ethoxylation reaction Methods 0.000 description 1
- 229920001038 ethylene copolymer Polymers 0.000 description 1
- 239000012530 fluid Substances 0.000 description 1
- 239000006081 fluorescent whitening agent Substances 0.000 description 1
- 235000019253 formic acid Nutrition 0.000 description 1
- 238000004508 fractional distillation Methods 0.000 description 1
- 125000000524 functional group Chemical group 0.000 description 1
- 239000000499 gel Substances 0.000 description 1
- 229910052736 halogen Inorganic materials 0.000 description 1
- 150000002367 halogens Chemical class 0.000 description 1
- 125000000623 heterocyclic group Chemical group 0.000 description 1
- 235000010299 hexamethylene tetramine Nutrition 0.000 description 1
- XMBWDFGMSWQBCA-UHFFFAOYSA-N hydrogen iodide Chemical compound I XMBWDFGMSWQBCA-UHFFFAOYSA-N 0.000 description 1
- QAOWNCQODCNURD-UHFFFAOYSA-M hydrogensulfate Chemical compound OS([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-M 0.000 description 1
- 239000003752 hydrotrope Substances 0.000 description 1
- 125000004356 hydroxy functional group Chemical group O* 0.000 description 1
- 230000002401 inhibitory effect Effects 0.000 description 1
- 235000019421 lipase Nutrition 0.000 description 1
- 239000007791 liquid phase Substances 0.000 description 1
- 239000011777 magnesium Substances 0.000 description 1
- 229910052749 magnesium Inorganic materials 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 239000011159 matrix material Substances 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 150000004702 methyl esters Chemical class 0.000 description 1
- JZMJDSHXVKJFKW-UHFFFAOYSA-M methyl sulfate(1-) Chemical compound COS([O-])(=O)=O JZMJDSHXVKJFKW-UHFFFAOYSA-M 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 230000007935 neutral effect Effects 0.000 description 1
- 229910000069 nitrogen hydride Inorganic materials 0.000 description 1
- 230000003287 optical effect Effects 0.000 description 1
- 230000001590 oxidative effect Effects 0.000 description 1
- 239000003002 pH adjusting agent Substances 0.000 description 1
- 239000006072 paste Substances 0.000 description 1
- 150000004885 piperazines Chemical class 0.000 description 1
- 229920001983 poloxamer Polymers 0.000 description 1
- 229920000058 polyacrylate Polymers 0.000 description 1
- 229920000573 polyethylene Polymers 0.000 description 1
- 238000006116 polymerization reaction Methods 0.000 description 1
- 230000000379 polymerizing effect Effects 0.000 description 1
- 229920005862 polyol Polymers 0.000 description 1
- 150000003077 polyols Chemical class 0.000 description 1
- BDERNNFJNOPAEC-UHFFFAOYSA-N propan-1-ol Chemical compound CCCO BDERNNFJNOPAEC-UHFFFAOYSA-N 0.000 description 1
- ULWHHBHJGPPBCO-UHFFFAOYSA-N propane-1,1-diol Chemical compound CCC(O)O ULWHHBHJGPPBCO-UHFFFAOYSA-N 0.000 description 1
- 150000003856 quaternary ammonium compounds Chemical class 0.000 description 1
- 150000004023 quaternary phosphonium compounds Chemical class 0.000 description 1
- 150000003254 radicals Chemical class 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 238000009877 rendering Methods 0.000 description 1
- 229920006395 saturated elastomer Polymers 0.000 description 1
- 239000002002 slurry Substances 0.000 description 1
- 229910021647 smectite Inorganic materials 0.000 description 1
- 125000004436 sodium atom Chemical group 0.000 description 1
- 229940079842 sodium cumenesulfonate Drugs 0.000 description 1
- HLBBKKJFGFRGMU-UHFFFAOYSA-M sodium formate Chemical compound [Na+].[O-]C=O HLBBKKJFGFRGMU-UHFFFAOYSA-M 0.000 description 1
- 235000019254 sodium formate Nutrition 0.000 description 1
- 235000010267 sodium hydrogen sulphite Nutrition 0.000 description 1
- UXIDHQPACNSJJP-UHFFFAOYSA-M sodium;2-[2-[2-[bis(carboxymethyl)amino]ethyl-(carboxymethyl)amino]ethyl-(carboxymethyl)amino]acetate Chemical compound [Na+].OC(=O)CN(CC(O)=O)CCN(CC(=O)O)CCN(CC(O)=O)CC([O-])=O UXIDHQPACNSJJP-UHFFFAOYSA-M 0.000 description 1
- FHLDWQLHDYCXKI-UHFFFAOYSA-N sodium;4-(3,5-dichloro-4-hydroxyphenyl)iminocyclohexa-2,5-dien-1-one Chemical compound [Na+].C1=C(Cl)C(O)=C(Cl)C=C1N=C1C=CC(=O)C=C1 FHLDWQLHDYCXKI-UHFFFAOYSA-N 0.000 description 1
- QEKATQBVVAZOAY-UHFFFAOYSA-M sodium;4-propan-2-ylbenzenesulfonate Chemical compound [Na+].CC(C)C1=CC=C(S([O-])(=O)=O)C=C1 QEKATQBVVAZOAY-UHFFFAOYSA-M 0.000 description 1
- 239000013042 solid detergent Substances 0.000 description 1
- 239000007790 solid phase Substances 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 230000019635 sulfation Effects 0.000 description 1
- 238000005670 sulfation reaction Methods 0.000 description 1
- 125000000020 sulfo group Chemical group O=S(=O)([*])O[H] 0.000 description 1
- DIORMHZUUKOISG-UHFFFAOYSA-N sulfoformic acid Chemical compound OC(=O)S(O)(=O)=O DIORMHZUUKOISG-UHFFFAOYSA-N 0.000 description 1
- BDHFUVZGWQCTTF-UHFFFAOYSA-M sulfonate Chemical compound [O-]S(=O)=O BDHFUVZGWQCTTF-UHFFFAOYSA-M 0.000 description 1
- 150000003467 sulfuric acid derivatives Chemical class 0.000 description 1
- 239000000375 suspending agent Substances 0.000 description 1
- 150000004026 tertiary sulfonium compounds Chemical class 0.000 description 1
- 239000002562 thickening agent Substances 0.000 description 1
- 150000004072 triols Chemical class 0.000 description 1
- 239000002699 waste material Substances 0.000 description 1
- 239000004711 α-olefin Substances 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
- C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
- C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
- C11D3/16—Organic compounds
- C11D3/37—Polymers
- C11D3/3746—Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds
- C11D3/3757—(Co)polymerised carboxylic acids, -anhydrides, -esters in solid and liquid compositions
- C11D3/3765—(Co)polymerised carboxylic acids, -anhydrides, -esters in solid and liquid compositions in liquid compositions
-
- C—CHEMISTRY; METALLURGY
- C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
- C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
- C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
- C11D3/16—Organic compounds
- C11D3/37—Polymers
- C11D3/3703—Macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
- C11D3/3723—Polyamines or polyalkyleneimines
-
- C—CHEMISTRY; METALLURGY
- C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
- C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
- C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
- C11D3/16—Organic compounds
- C11D3/37—Polymers
- C11D3/3746—Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds
- C11D3/378—(Co)polymerised monomers containing sulfur, e.g. sulfonate
Landscapes
- Chemical & Material Sciences (AREA)
- Life Sciences & Earth Sciences (AREA)
- Engineering & Computer Science (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Oil, Petroleum & Natural Gas (AREA)
- Wood Science & Technology (AREA)
- Organic Chemistry (AREA)
- Detergent Compositions (AREA)
Abstract
Liquid detergent compositions comprising a polymer comprising polyacrylic acid monomers having a low number average molecular weight, ranging from about 1000 to about 10,000 amu, and a very low polydispersity, less than about 5, wherein the liquid detergent comprises less than about 50% of any non-aminofunctional solvent. The invention is also directed to liquid detergents compositions comprising beneficial mixtures of the low molecular weight, very low polydispersity polyacrylic acid based polymers with specific polymers.
Description
LIQUID DETERGENT COMPOSITIONS WITH
LOW POLYDISPERSITY POLYACRYLIC ACID BASED POLYMERS
FIELD OF THE INVENTION
The present invention is directed to liquid detergent compositions, and more particularly, to liquid laundry detergent compositions or liquid dish or surface cleaning detergents, comprising a polymer or copolymer comprising polyacrylic acid monomers and having a low polydispersity.
These liquid detergents exhibit improved ability to formulate at lower solvent vehicle levels and improved performance of polymeric detergent additives.
BACKGROUND OF THE INVENTION
Fluid laundry products, such as liquids, gels, pastes and the like are preferred by many consumers over solid detergents. Many of these consumers also have a desire to conserve resources and eliminate what they perceive as waste or unnecessary product, without a noticeable reduction in performance of the product. Consequently, there is renewed interest in concentrated or so called compact products. However, typical liquid detergent products cannot be easily formulated at lower levels of water or other solvents due to the need to keep detergent surfactants and polymeric additives which may become at least partially insoluble at higher concentrations.
Typical builders, such as citrates and fatty acids, and polymer additives, such as polyacrylates, and higher molecular weight/high charge density molecules, have shown a tendency to precipitate out of solution at lower solvent levels, thereby creating more instability in finished products. This instability may decrease the performance of the desired detergent products. Consequently, the need remains for a concentrated liquid detergent that is comparable to performance to existing noncompact detergents. Ideally any such comparable detergents will be presented in a fashion that is easy to use and which is aesthetically appealing to consumers.
Polyacrylic acid based polymers are known as builders or thickeners for detergent products. See U.S. 6,794,473 B2 issued to Yamaguchi et al. on September 21, 2004. However, it has been found that polymers comprising acrylic acid monomers having low molecular weight and very low polydispersity create a concentrated, clear isotropic liquid detergents with sufficient physical stability and strong detergent performance.
Separately, it has been found that polymers comprising acrylic acid monomers having such a low molecular weight and very low polydispersity also enhances the stability and performance of previously used polymer additives, such as water-soluble or dispersible, modified polyamines and/or zwitterionic polyamines.
SUMMARY OF THE INVENTION
Accordingly, it is an object of the present invention to provide improved liquid detergent compositions. Generally, the invention is directed to liquid detergent compositions comprising a polymer comprising polyacrylic acid monomers having a low number average molecular weight, ranging from about 1000 to about 10,000 amu, and a very low polydispersity, less than about 5, wherein the liquid detergent comprises less than about 50% of any non-aminofunctional solvent.
The invention is also directed to liquid detergents compositions comprising beneficial mixtures of the low molecular weight, very low polydispersity polyacrylic acid based polymers with specific polymers.
DETAILED DESCRIPTION OF THE INVENTION
The liquid detergent compositions of the present invention comprise acrylic acid based polymers. By "acrylic acid based polymer" it is meant herein, a compound comprising repeating units called monomer units, wherein a fraction of the monomer units consist of acrylic acid or a salt of acrylic acid. In selected embodiments of the present invention, the polymer may be a homopolymer of acrylic acid where substantially 100% of the monomers are acrylic acid. In other embodiments of the invention the polymer may be a copolymer comprising some acrylic acid monomers and some other monomers.
The size of the polymers of the present invention may be measured by standard measurements of the average molecular weight. The molecular weight may be a number average molecular weight, Mn, or a weight average molecular weight, Mw. The polymers of the present invention may have a number average molecular weight ranging from about 1000 amu to about 10,000 amu. The distribution of the molecular weight of specific compounds of the polymer may be reflected in the ratio of the weight average molecular weight over the number average molecular weight (Mw/Mn). This ratio is also called the polydispersity of the polymer. The polymers of the present invention may have a polydispersity of less than about 5Ø
As discussed above, an embodiment of the polymer of the present invention may be a homopolymer of polyacrylic acid. The embodiment may have a number average molecular weight of from about 1000 to about 4000 and a polydispersity less than about 5, with certain embodiments having a number average molecular weight ranging from about 1100 to about 3000 and a polydispersity less than about 3.5.
The acrylic acid based polymer of the present invention may also be a copolymer comprising monomers of acrylic acid and 10% or less, based on the total weight of the polymer of a hydrophilic comonomer. Hydrophilic comonomers are monomers that when added to the acrylic acid polymer makes the copolymer less soluble in the liquid detergent composition.
Typical hydrophilic monomers include polyethyleneglycol-acrylates, dicarboxylates, sulfonated monomers and mixtures thereof. Certain embodiments of polymers having hydrophilic comonomers may have a number average molecular weight of from about 1000 to about 4000 and a polydispersity less than about 5, with certain embodiments having a number average molecular weight ranging from about 1100 to about 3000 and a polydispersity less than about 3.5.
Other embodiments of the acrylic acid based polymer of the present invention may be a copolymer comprising monomers of acrylic acid and 20% or less, based on the total weight of the polymer of a hydrophobic comonomer. Hydrophobic comonomers are monomers that when added to the acrylic acid polymer makes the copolymer more soluble in the liquid detergent composition. Typical hydrophobic monomers include alkyl, aryl, silicone, propoxylated or butoxylated monomers and mixtures thereof. Certain embodiments of polymers having hydrophobic comonomers may have a number average molecular weight of from about 1000 to about 10000 and a polydispersity less than about 5, with certain embodiments having a number average molecular weight ranging from about 1100 to about 3000 and a polydispersity less than about 5Ø
The liquid detergent compositions of the present invention may be any liquid detergent including, but not limited to, liquid laundry detergents and liquid dish and surface cleaning compositions.
Liquid Laundry Detergent Compositions In one specific embodiment, the compositions are laundry detergent composition and are liquid in form and comprise heavy duty liquid compositions. The compositions of the present invention comprise surfactants, along with other typical detergent ingredients, and a polymer comprising polyacrylic acid monomers having a low number average molecular weight and very low polydispersity.
LOW POLYDISPERSITY POLYACRYLIC ACID BASED POLYMERS
FIELD OF THE INVENTION
The present invention is directed to liquid detergent compositions, and more particularly, to liquid laundry detergent compositions or liquid dish or surface cleaning detergents, comprising a polymer or copolymer comprising polyacrylic acid monomers and having a low polydispersity.
These liquid detergents exhibit improved ability to formulate at lower solvent vehicle levels and improved performance of polymeric detergent additives.
BACKGROUND OF THE INVENTION
Fluid laundry products, such as liquids, gels, pastes and the like are preferred by many consumers over solid detergents. Many of these consumers also have a desire to conserve resources and eliminate what they perceive as waste or unnecessary product, without a noticeable reduction in performance of the product. Consequently, there is renewed interest in concentrated or so called compact products. However, typical liquid detergent products cannot be easily formulated at lower levels of water or other solvents due to the need to keep detergent surfactants and polymeric additives which may become at least partially insoluble at higher concentrations.
Typical builders, such as citrates and fatty acids, and polymer additives, such as polyacrylates, and higher molecular weight/high charge density molecules, have shown a tendency to precipitate out of solution at lower solvent levels, thereby creating more instability in finished products. This instability may decrease the performance of the desired detergent products. Consequently, the need remains for a concentrated liquid detergent that is comparable to performance to existing noncompact detergents. Ideally any such comparable detergents will be presented in a fashion that is easy to use and which is aesthetically appealing to consumers.
Polyacrylic acid based polymers are known as builders or thickeners for detergent products. See U.S. 6,794,473 B2 issued to Yamaguchi et al. on September 21, 2004. However, it has been found that polymers comprising acrylic acid monomers having low molecular weight and very low polydispersity create a concentrated, clear isotropic liquid detergents with sufficient physical stability and strong detergent performance.
Separately, it has been found that polymers comprising acrylic acid monomers having such a low molecular weight and very low polydispersity also enhances the stability and performance of previously used polymer additives, such as water-soluble or dispersible, modified polyamines and/or zwitterionic polyamines.
SUMMARY OF THE INVENTION
Accordingly, it is an object of the present invention to provide improved liquid detergent compositions. Generally, the invention is directed to liquid detergent compositions comprising a polymer comprising polyacrylic acid monomers having a low number average molecular weight, ranging from about 1000 to about 10,000 amu, and a very low polydispersity, less than about 5, wherein the liquid detergent comprises less than about 50% of any non-aminofunctional solvent.
The invention is also directed to liquid detergents compositions comprising beneficial mixtures of the low molecular weight, very low polydispersity polyacrylic acid based polymers with specific polymers.
DETAILED DESCRIPTION OF THE INVENTION
The liquid detergent compositions of the present invention comprise acrylic acid based polymers. By "acrylic acid based polymer" it is meant herein, a compound comprising repeating units called monomer units, wherein a fraction of the monomer units consist of acrylic acid or a salt of acrylic acid. In selected embodiments of the present invention, the polymer may be a homopolymer of acrylic acid where substantially 100% of the monomers are acrylic acid. In other embodiments of the invention the polymer may be a copolymer comprising some acrylic acid monomers and some other monomers.
The size of the polymers of the present invention may be measured by standard measurements of the average molecular weight. The molecular weight may be a number average molecular weight, Mn, or a weight average molecular weight, Mw. The polymers of the present invention may have a number average molecular weight ranging from about 1000 amu to about 10,000 amu. The distribution of the molecular weight of specific compounds of the polymer may be reflected in the ratio of the weight average molecular weight over the number average molecular weight (Mw/Mn). This ratio is also called the polydispersity of the polymer. The polymers of the present invention may have a polydispersity of less than about 5Ø
As discussed above, an embodiment of the polymer of the present invention may be a homopolymer of polyacrylic acid. The embodiment may have a number average molecular weight of from about 1000 to about 4000 and a polydispersity less than about 5, with certain embodiments having a number average molecular weight ranging from about 1100 to about 3000 and a polydispersity less than about 3.5.
The acrylic acid based polymer of the present invention may also be a copolymer comprising monomers of acrylic acid and 10% or less, based on the total weight of the polymer of a hydrophilic comonomer. Hydrophilic comonomers are monomers that when added to the acrylic acid polymer makes the copolymer less soluble in the liquid detergent composition.
Typical hydrophilic monomers include polyethyleneglycol-acrylates, dicarboxylates, sulfonated monomers and mixtures thereof. Certain embodiments of polymers having hydrophilic comonomers may have a number average molecular weight of from about 1000 to about 4000 and a polydispersity less than about 5, with certain embodiments having a number average molecular weight ranging from about 1100 to about 3000 and a polydispersity less than about 3.5.
Other embodiments of the acrylic acid based polymer of the present invention may be a copolymer comprising monomers of acrylic acid and 20% or less, based on the total weight of the polymer of a hydrophobic comonomer. Hydrophobic comonomers are monomers that when added to the acrylic acid polymer makes the copolymer more soluble in the liquid detergent composition. Typical hydrophobic monomers include alkyl, aryl, silicone, propoxylated or butoxylated monomers and mixtures thereof. Certain embodiments of polymers having hydrophobic comonomers may have a number average molecular weight of from about 1000 to about 10000 and a polydispersity less than about 5, with certain embodiments having a number average molecular weight ranging from about 1100 to about 3000 and a polydispersity less than about 5Ø
The liquid detergent compositions of the present invention may be any liquid detergent including, but not limited to, liquid laundry detergents and liquid dish and surface cleaning compositions.
Liquid Laundry Detergent Compositions In one specific embodiment, the compositions are laundry detergent composition and are liquid in form and comprise heavy duty liquid compositions. The compositions of the present invention comprise surfactants, along with other typical detergent ingredients, and a polymer comprising polyacrylic acid monomers having a low number average molecular weight and very low polydispersity.
The laundry detergent composition comprises a surfactant in an amount sufficient to provide desired cleaning properties. In one embodiment, the laundry detergent composition comprises, by weight, from about 5% to about 90% of the surfactant, and more specifically from about 5% to about 70% of the surfactant, and even more specifically from about 5% to about 40%. The surfactant may comprise anionic, nonionic, cationic, zwitterionic and/or amphoteric surfactants. In a more specific embodiment, the detergent composition comprises anionic surfactant, nonionic surfactant, or mixtures thereof.
Suitable anionic surfactants useful herein can comprise any of the conventional anionic surfactant types typically used in liquid detergent products. These include the alkyl benzene sulfonic acids and their salts as well as alkoxylated or non-alkoxylated alkyl sulfate materials.
Exemplary anionic surfactants are the alkali metal salts of Cio_16 alkyl benzene sulfonic acids, preferably C11_14 alkyl benzene sulfonic acids. Preferably the alkyl group is linear and such linear alkyl benzene sulfonates are known as "LAS". Alkyl benzene sulfonates, and particularly LAS, are well known in the art. Such surfactants and their preparation are described for example in U.S. Patents 2,220,099 and 2,477,383. Especially preferred are the sodium and potassium linear straight chain alkylbenzene sulfonates in which the average number of carbon atoms in the alkyl group is from about 11 to 14. Sodium Cii-Ci4, e.g., C12, LAS is a specific example of such surfactants.
Another exemplary type of anionic surfactant comprises ethoxylated alkyl sulfate surfactants. Such materials, also known as alkyl ether sulfates or alkyl polyethoxylate sulfates, are those which correspond to the formula: R'-O-(C2H4O)n-SO3M wherein R' is a C8-C20 alkyl group, n is from about 1 to 20, and M is a salt-forming cation. In a specific embodiment, R' is Cio-Cig alkyl, n is from about 1 to 15, and M is sodium, potassium, ammonium, alkylammonium, or alkanolammonium. In more specific embodiments, R' is a C12-Ci6, n is from about 1 to 6 and M is sodium.
The alkyl ether sulfates will generally be used in the form of mixtures comprising varying R' chain lengths and varying degrees of ethoxylation. Frequently such mixtures will inevitably also contain some non-ethoxylated alkyl sulfate materials, i.e., surfactants of the above ethoxylated alkyl sulfate formula wherein n=0. Non-ethoxylated alkyl sulfates may also be added separately to the compositions of this invention and used as or in any anionic surfactant component which may be present. Specific examples of non-alkoyxylated, e.g., non-ethoxylated, alkyl ether sulfate surfactants are those produced by the sulfation of higher C8-C20 fatty alcohols.
Conventional primary alkyl sulfate surfactants have the general formula: ROSO3-M+ wherein R
is typically a linear C8-C20 hydrocarbyl group, which may be straight chain or branched chain, and M is a water-solubilizing cation. In specific embodiments, R is a Cio-Ci5 alkyl, and M is 5 alkali metal, more specifically R is C12-C14 and M is sodium.
Specific, nonlimiting examples of anionic surfactants useful herein include:
a) C11-C18 alkyl benzene sulfonates (LAS); b) Cio-C2o primary, branched-chain and random alkyl sulfates (AS); c) Cio-Cig secondary (2,3) alkyl sulfates having formulae (1) and (Il):
OSO3 M+ OSO3 M+
CH3(CH2)R(CH)CH3 or CH3(CH2)y(CH)CH2CH3 (I) (Il) wherein M in formulae (I) and (II) is hydrogen or a cation which provides charge neutrality, and all M units, whether associated with a surfactant or adjunct ingredient, can either be a hydrogen atom or a cation depending upon the form isolated by the artisan or the relative pH of the system wherein the compound is used, with non-limiting examples of preferred cations including sodium, potassium, ammonium, and mixtures thereof, and x is an integer of at least about 7, preferably at least about 9, and y is an integer of at least 8, preferably at least about 9; d) Cio-Ci8 alkyl alkoxy sulfates (AExS) wherein preferably x is from 1-30; e) Clo-C18 alkyl alkoxy carboxylates preferably comprising 1-5 ethoxy units; f) mid-chain branched alkyl sulfates as discussed in US 6,020,303 and US 6,060,443; g) mid-chain branched alkyl alkoxy sulfates as discussed in US 6,008,181 and US 6,020,303; h) modified alkylbenzene sulfonate (MLAS) as discussed in WO 99/05243, WO 99/05242, WO 99/05244, WO 99/05082, WO 99/05084, WO
99/05241, WO 99/07656, WO 00/23549, and WO 00/23548.; i) methyl ester sulfonate (MES);
and j) alpha-olefin sulfonate (AOS).
Suitable nonionic surfactants useful herein can comprise any of the conventional nonionic surfactant types typically used in liquid detergent products. These include alkoxylated fatty alcohols and amine oxide surfactants. Preferred for use in the liquid detergent products herein are those nonionic surfactants which are normally liquid.
Suitable nonionic surfactants for use herein include the alcohol alkoxylate nonionic surfactants. Alcohol alkoxylates are materials which correspond to the general formula:
Ri(C,7,H21T1O)nOH wherein Ri is a C8 - C16 alkyl group, m is from 2 to 4, and n ranges from about 2 to 12. Preferably Ri is an alkyl group, which may be primary or secondary, that contains from about 9 to 15 carbon atoms, more preferably from about 10 to 14 carbon atoms.
In one embodiment, the alkoxylated fatty alcohols will also be ethoxylated materials that contain from about 2 to 12 ethylene oxide moieties per molecule, more preferably from about 3 to 10 ethylene oxide moieties per molecule.
Thet alkoxylated fatty alcohol materials useful in the liquid detergent compositions herein will frequently have a hydrophilic-lipophilic balance (HLB) which ranges from about 3 to 17.
More preferably, the HLB of this material will range from about 6 to 15, most preferably from about 8 to 15. Alkoxylated fatty alcohol nonionic surfactants have been marketed under the tradenames Neodol and Dobanol by the Shell Chemical Company.
Another suitable type of nonionic surfactant useful herein comprises the amine oxide surfactants. Amine oxides are mateials which are often referred to in the art as "semi-polar"
nonionics. Amine oxides have the formula: R(EO)x(PO)y(BO)zN(O)(CH2R')2.qH2O.
In this formula, R is a relatively long-chain hydrocarbyl moiety which can be saturated or unsaturated, linear or branched, and can contain from 8 to 20, preferably from 10 to 16 carbon atoms, and is more preferably C12-C16 primary alkyl. R' is a short-chain moiety, preferably selected from hydrogen, methyl and -CH2OH. When x+y+z is different from 0, EO is ethyleneoxy, PO is propyleneneoxy and BO is butyleneoxy. Amine oxide surfactants are illustrated by C12_14 alkyldimethyl amine oxide.
Non-limiting examples of nonionic surfactants include: a) C12-C18 alkyl ethoxylates, such as, NEODOL nonionic surfactants from Shell; b) C6-C12 alkyl phenol alkoxylates wherein the alkoxylate units are a mixture of ethyleneoxy and propyleneoxy units; c) C12-C18 alcohol and C6-C12 alkyl phenol condensates with ethylene oxide/propylene oxide block polymers such as Pluronic from BASF; d) C14-C22 mid-chain branched alcohols, BA, as discussed in US
6,150,322; e) C14-C22 mid-chain branched alkyl alkoxylates, BAEx, wherein x 1-30, as discussed in US 6,153,577, US 6,020,303 and US 6,093,856; f) Alkylpolysaccharides as discussed in U.S.
4,565,647 Llenado, issued January 26, 1986; specifically alkylpolyglycosides as discussed in US
4,483,780 and US 4,483,779; g) Polyhydroxy fatty acid amides as discussed in US 5,332,528, WO 92/06162, WO 93/19146, WO 93/19038, and WO 94/09099; and h) ether capped poly(oxyalkylated) alcohol surfactants as discussed in US 6,482,994 and WO
01/42408.
Suitable anionic surfactants useful herein can comprise any of the conventional anionic surfactant types typically used in liquid detergent products. These include the alkyl benzene sulfonic acids and their salts as well as alkoxylated or non-alkoxylated alkyl sulfate materials.
Exemplary anionic surfactants are the alkali metal salts of Cio_16 alkyl benzene sulfonic acids, preferably C11_14 alkyl benzene sulfonic acids. Preferably the alkyl group is linear and such linear alkyl benzene sulfonates are known as "LAS". Alkyl benzene sulfonates, and particularly LAS, are well known in the art. Such surfactants and their preparation are described for example in U.S. Patents 2,220,099 and 2,477,383. Especially preferred are the sodium and potassium linear straight chain alkylbenzene sulfonates in which the average number of carbon atoms in the alkyl group is from about 11 to 14. Sodium Cii-Ci4, e.g., C12, LAS is a specific example of such surfactants.
Another exemplary type of anionic surfactant comprises ethoxylated alkyl sulfate surfactants. Such materials, also known as alkyl ether sulfates or alkyl polyethoxylate sulfates, are those which correspond to the formula: R'-O-(C2H4O)n-SO3M wherein R' is a C8-C20 alkyl group, n is from about 1 to 20, and M is a salt-forming cation. In a specific embodiment, R' is Cio-Cig alkyl, n is from about 1 to 15, and M is sodium, potassium, ammonium, alkylammonium, or alkanolammonium. In more specific embodiments, R' is a C12-Ci6, n is from about 1 to 6 and M is sodium.
The alkyl ether sulfates will generally be used in the form of mixtures comprising varying R' chain lengths and varying degrees of ethoxylation. Frequently such mixtures will inevitably also contain some non-ethoxylated alkyl sulfate materials, i.e., surfactants of the above ethoxylated alkyl sulfate formula wherein n=0. Non-ethoxylated alkyl sulfates may also be added separately to the compositions of this invention and used as or in any anionic surfactant component which may be present. Specific examples of non-alkoyxylated, e.g., non-ethoxylated, alkyl ether sulfate surfactants are those produced by the sulfation of higher C8-C20 fatty alcohols.
Conventional primary alkyl sulfate surfactants have the general formula: ROSO3-M+ wherein R
is typically a linear C8-C20 hydrocarbyl group, which may be straight chain or branched chain, and M is a water-solubilizing cation. In specific embodiments, R is a Cio-Ci5 alkyl, and M is 5 alkali metal, more specifically R is C12-C14 and M is sodium.
Specific, nonlimiting examples of anionic surfactants useful herein include:
a) C11-C18 alkyl benzene sulfonates (LAS); b) Cio-C2o primary, branched-chain and random alkyl sulfates (AS); c) Cio-Cig secondary (2,3) alkyl sulfates having formulae (1) and (Il):
OSO3 M+ OSO3 M+
CH3(CH2)R(CH)CH3 or CH3(CH2)y(CH)CH2CH3 (I) (Il) wherein M in formulae (I) and (II) is hydrogen or a cation which provides charge neutrality, and all M units, whether associated with a surfactant or adjunct ingredient, can either be a hydrogen atom or a cation depending upon the form isolated by the artisan or the relative pH of the system wherein the compound is used, with non-limiting examples of preferred cations including sodium, potassium, ammonium, and mixtures thereof, and x is an integer of at least about 7, preferably at least about 9, and y is an integer of at least 8, preferably at least about 9; d) Cio-Ci8 alkyl alkoxy sulfates (AExS) wherein preferably x is from 1-30; e) Clo-C18 alkyl alkoxy carboxylates preferably comprising 1-5 ethoxy units; f) mid-chain branched alkyl sulfates as discussed in US 6,020,303 and US 6,060,443; g) mid-chain branched alkyl alkoxy sulfates as discussed in US 6,008,181 and US 6,020,303; h) modified alkylbenzene sulfonate (MLAS) as discussed in WO 99/05243, WO 99/05242, WO 99/05244, WO 99/05082, WO 99/05084, WO
99/05241, WO 99/07656, WO 00/23549, and WO 00/23548.; i) methyl ester sulfonate (MES);
and j) alpha-olefin sulfonate (AOS).
Suitable nonionic surfactants useful herein can comprise any of the conventional nonionic surfactant types typically used in liquid detergent products. These include alkoxylated fatty alcohols and amine oxide surfactants. Preferred for use in the liquid detergent products herein are those nonionic surfactants which are normally liquid.
Suitable nonionic surfactants for use herein include the alcohol alkoxylate nonionic surfactants. Alcohol alkoxylates are materials which correspond to the general formula:
Ri(C,7,H21T1O)nOH wherein Ri is a C8 - C16 alkyl group, m is from 2 to 4, and n ranges from about 2 to 12. Preferably Ri is an alkyl group, which may be primary or secondary, that contains from about 9 to 15 carbon atoms, more preferably from about 10 to 14 carbon atoms.
In one embodiment, the alkoxylated fatty alcohols will also be ethoxylated materials that contain from about 2 to 12 ethylene oxide moieties per molecule, more preferably from about 3 to 10 ethylene oxide moieties per molecule.
Thet alkoxylated fatty alcohol materials useful in the liquid detergent compositions herein will frequently have a hydrophilic-lipophilic balance (HLB) which ranges from about 3 to 17.
More preferably, the HLB of this material will range from about 6 to 15, most preferably from about 8 to 15. Alkoxylated fatty alcohol nonionic surfactants have been marketed under the tradenames Neodol and Dobanol by the Shell Chemical Company.
Another suitable type of nonionic surfactant useful herein comprises the amine oxide surfactants. Amine oxides are mateials which are often referred to in the art as "semi-polar"
nonionics. Amine oxides have the formula: R(EO)x(PO)y(BO)zN(O)(CH2R')2.qH2O.
In this formula, R is a relatively long-chain hydrocarbyl moiety which can be saturated or unsaturated, linear or branched, and can contain from 8 to 20, preferably from 10 to 16 carbon atoms, and is more preferably C12-C16 primary alkyl. R' is a short-chain moiety, preferably selected from hydrogen, methyl and -CH2OH. When x+y+z is different from 0, EO is ethyleneoxy, PO is propyleneneoxy and BO is butyleneoxy. Amine oxide surfactants are illustrated by C12_14 alkyldimethyl amine oxide.
Non-limiting examples of nonionic surfactants include: a) C12-C18 alkyl ethoxylates, such as, NEODOL nonionic surfactants from Shell; b) C6-C12 alkyl phenol alkoxylates wherein the alkoxylate units are a mixture of ethyleneoxy and propyleneoxy units; c) C12-C18 alcohol and C6-C12 alkyl phenol condensates with ethylene oxide/propylene oxide block polymers such as Pluronic from BASF; d) C14-C22 mid-chain branched alcohols, BA, as discussed in US
6,150,322; e) C14-C22 mid-chain branched alkyl alkoxylates, BAEx, wherein x 1-30, as discussed in US 6,153,577, US 6,020,303 and US 6,093,856; f) Alkylpolysaccharides as discussed in U.S.
4,565,647 Llenado, issued January 26, 1986; specifically alkylpolyglycosides as discussed in US
4,483,780 and US 4,483,779; g) Polyhydroxy fatty acid amides as discussed in US 5,332,528, WO 92/06162, WO 93/19146, WO 93/19038, and WO 94/09099; and h) ether capped poly(oxyalkylated) alcohol surfactants as discussed in US 6,482,994 and WO
01/42408.
In the laundry detergent compositions herein, the detersive surfactant component may comprise combinations of anionic and nonionic surfactant materials. When this is the case, the weight ratio of anionic to nonionic will typically range from 10:90 to 90:10, more typically from 30:70 to 70:30.
Cationic surfactants are well known in the art and non-limiting examples of these include quaternary ammonium surfactants, which can have up to 26 carbon atoms.
Additional examples include a) alkoxylate quaternary ammonium (AQA) surfactants as discussed in US
6,136,769; b) dimethyl hydroxyethyl quaternary ammonium as discussed in 6,004,922; c) polyamine cationic surfactants as discussed in WO 98/35002, WO 98/35003, WO 98/35004, WO
98/35005, and WO
98/35006; d) cationic ester surfactants as discussed in US Patents Nos.
4,228,042, 4,239,660 4,260,529 and US 6,022,844; and e) amino surfactants as discussed in US
6,221,825 and WO
00/47708, specifically amido propyldimethyl amine (APA).
Non-limiting examples of zwitterionic surfactants include: derivatives of secondary and tertiary amines, derivatives of heterocyclic secondary and tertiary amines, or derivatives of quaternary ammonium, quaternary phosphonium or tertiary sulfonium compounds.
See U.S.
Patent No. 3,929,678 to Laughlin et al., issued December 30, 1975 at column 19, line 38 through column 22, line 48, for examples of zwitterionic surfactants; betaine, including alkyl dimethyl betaine and cocodimethyl amidopropyl betaine, C8 to C18 (preferably C12 to C18) amine oxides and sulfo and hydroxy betaines, such as N-alkyl-N,N-dimethylammino-l-propane sulfonate where the alkyl group can be C8 to C18, preferably Cio to C14.
Non-limiting examples of ampholytic surfactants include: aliphatic derivatives of secondary or tertiary amines, or aliphatic derivatives of heterocyclic secondary and tertiary amines in which the aliphatic radical can be straight- or branched-chain. One of the aliphatic substituents contains at least about 8 carbon atoms, typically from about 8 to about 18 carbon atoms, and at least one contains an anionic water-solubilizing group, e.g.
carboxy, sulfonate, sulfate. See U.S. Patent No. 3,929,678 to Laughlin et al., issued December 30, 1975 at column 19, lines 18-35, for examples of ampholytic surfactants.
As used herein, "non-aminofunctional solvent" refers to any solvent which contains no amino functional groups. Non-aminofunctional solvent include, for example:
water, C1-C5 alkanols such as methanol, ethanol, propanol and 1-ethoxypentanol; C2-C6 diols; C3-C8 alkylene glycols; C3-C8 alkylene glycol mono lower alkyl ethers; glycol dialkyl ether;
lower molecular weight polyethylene glycols; C3-C9 triols such as glycerol; and mixtures thereof. More specifically non-aminofunctional solvent are liquids at ambient temperature and pressure (i.e.
21 C and 1 atmosphere), and comprise carbon, hydrogen and oxygen.
Generally in noncompacted product formulations, all non-aminofunctional solvent, including water, may comprise from about 5% to about 90%, more specifically from about 10%
to about 70%, and even more specifically from about 20% to about 60%. Recently developed compacted liquid detergent formulae may comprise no more than about 50%, more specifically no more than 35%, more specifically still no more than 30%, even more specifically still no more than 25%, by weight of the composition, and specifically having about 0% to 45%, specifically 1% to 30% , more specifically from about 2% to about 25%, more specifically from about 3% to about 20%, more specifically still from about 5% to about 15%, by weight of the composition, of the non-aminofunctional solvent.
The most cost effective type of non-aminofunctional solvent is, of course, water itself.
Accordingly, the non-aminofunctional solvent will generally be mostly, if not completely, comprised of water. While other types of water-miscible liquids, such as alkanols, diols, other polyols, ethers, amines, and the like, have been conventionally been added to liquid detergent compositions as co-solvents or stabilizers, the utilization of such water-miscible liquids should be minimized to hold down composition cost.
The liquid detergent compositions of the present invention can also include any number of additional optional ingredients. These include conventional laundry detergent composition components such as detersive builders, enzymes, enzyme stabilizers (such as propylene glycol, boric acid and/or borax), suds suppressors, soil suspending agents, soil release agents, other fabric care benefit agents, pH adjusting agents, chelating agents, smectite clays, solvents, hydrotropes and phase stabilizers, structuring agents, dye transfer inhibiting agents, optical brighteners, perfumes and coloring agents. The various optional detergent composition ingredients, if present in the compositions herein, should be utilized at concentrations conventionally employed to bring about their desired contribution to the composition or the laundering operation. Frequently, the total amount of such optional detergent composition ingredients can range from about 0.1% to about 50%, more preferably from about 1% to about 30%, by weight of the composition.
Cationic surfactants are well known in the art and non-limiting examples of these include quaternary ammonium surfactants, which can have up to 26 carbon atoms.
Additional examples include a) alkoxylate quaternary ammonium (AQA) surfactants as discussed in US
6,136,769; b) dimethyl hydroxyethyl quaternary ammonium as discussed in 6,004,922; c) polyamine cationic surfactants as discussed in WO 98/35002, WO 98/35003, WO 98/35004, WO
98/35005, and WO
98/35006; d) cationic ester surfactants as discussed in US Patents Nos.
4,228,042, 4,239,660 4,260,529 and US 6,022,844; and e) amino surfactants as discussed in US
6,221,825 and WO
00/47708, specifically amido propyldimethyl amine (APA).
Non-limiting examples of zwitterionic surfactants include: derivatives of secondary and tertiary amines, derivatives of heterocyclic secondary and tertiary amines, or derivatives of quaternary ammonium, quaternary phosphonium or tertiary sulfonium compounds.
See U.S.
Patent No. 3,929,678 to Laughlin et al., issued December 30, 1975 at column 19, line 38 through column 22, line 48, for examples of zwitterionic surfactants; betaine, including alkyl dimethyl betaine and cocodimethyl amidopropyl betaine, C8 to C18 (preferably C12 to C18) amine oxides and sulfo and hydroxy betaines, such as N-alkyl-N,N-dimethylammino-l-propane sulfonate where the alkyl group can be C8 to C18, preferably Cio to C14.
Non-limiting examples of ampholytic surfactants include: aliphatic derivatives of secondary or tertiary amines, or aliphatic derivatives of heterocyclic secondary and tertiary amines in which the aliphatic radical can be straight- or branched-chain. One of the aliphatic substituents contains at least about 8 carbon atoms, typically from about 8 to about 18 carbon atoms, and at least one contains an anionic water-solubilizing group, e.g.
carboxy, sulfonate, sulfate. See U.S. Patent No. 3,929,678 to Laughlin et al., issued December 30, 1975 at column 19, lines 18-35, for examples of ampholytic surfactants.
As used herein, "non-aminofunctional solvent" refers to any solvent which contains no amino functional groups. Non-aminofunctional solvent include, for example:
water, C1-C5 alkanols such as methanol, ethanol, propanol and 1-ethoxypentanol; C2-C6 diols; C3-C8 alkylene glycols; C3-C8 alkylene glycol mono lower alkyl ethers; glycol dialkyl ether;
lower molecular weight polyethylene glycols; C3-C9 triols such as glycerol; and mixtures thereof. More specifically non-aminofunctional solvent are liquids at ambient temperature and pressure (i.e.
21 C and 1 atmosphere), and comprise carbon, hydrogen and oxygen.
Generally in noncompacted product formulations, all non-aminofunctional solvent, including water, may comprise from about 5% to about 90%, more specifically from about 10%
to about 70%, and even more specifically from about 20% to about 60%. Recently developed compacted liquid detergent formulae may comprise no more than about 50%, more specifically no more than 35%, more specifically still no more than 30%, even more specifically still no more than 25%, by weight of the composition, and specifically having about 0% to 45%, specifically 1% to 30% , more specifically from about 2% to about 25%, more specifically from about 3% to about 20%, more specifically still from about 5% to about 15%, by weight of the composition, of the non-aminofunctional solvent.
The most cost effective type of non-aminofunctional solvent is, of course, water itself.
Accordingly, the non-aminofunctional solvent will generally be mostly, if not completely, comprised of water. While other types of water-miscible liquids, such as alkanols, diols, other polyols, ethers, amines, and the like, have been conventionally been added to liquid detergent compositions as co-solvents or stabilizers, the utilization of such water-miscible liquids should be minimized to hold down composition cost.
The liquid detergent compositions of the present invention can also include any number of additional optional ingredients. These include conventional laundry detergent composition components such as detersive builders, enzymes, enzyme stabilizers (such as propylene glycol, boric acid and/or borax), suds suppressors, soil suspending agents, soil release agents, other fabric care benefit agents, pH adjusting agents, chelating agents, smectite clays, solvents, hydrotropes and phase stabilizers, structuring agents, dye transfer inhibiting agents, optical brighteners, perfumes and coloring agents. The various optional detergent composition ingredients, if present in the compositions herein, should be utilized at concentrations conventionally employed to bring about their desired contribution to the composition or the laundering operation. Frequently, the total amount of such optional detergent composition ingredients can range from about 0.1% to about 50%, more preferably from about 1% to about 30%, by weight of the composition.
Specifically it has been found that combinations of the polyacrylic acid based polymer with certain previously known polymer additive provide improved benefits.
The polyacrylic based polymer may be beneficially combined with the water soluble or dispersible, modified polyamine soil release polymers. Such polymers are discussed in U.S.
Patent 3,087,316. These polyamines comprise backbones that can be either linear or cyclic. The polyamine backbones can also comprise polyamine branching chains to a greater or lesser degree.
In general, the polyamine backbones described herein are modified in such a manner that each nitrogen of the polyamine chain is thereafter described in terms of a unit that is substituted, quaternized, oxidized, or combinations thereof.
For the purposes of the present invention the term "modification" is defined as replacing a backbone -NH hydrogen atom by an E unit (substitution), quaternizing a backbone nitrogen (quaternized) or oxidizing a backbone nitrogen to the N-oxide (oxidized). The terms "modification" and "substitution" are used interchangably when referring to the process of replacing a hydrogen atom attached to a backbone nitrogen with an E unit.
Quaternization or oxidation may take place in some circumstances without substitution, but substitution must be accompanied by oxidation or quaternization of at least one backbone nitrogen.
The linear or non-cyclic polyamine backbones that comprise the cotton soil release agents of the present invention have the general formula:
H
[H2N-R]n+1-[N-R]m [N-R]n NHz said backbones prior to subsequent modification, comprise primary, secondary and tertiary amine nitrogens connected by R "linking" units. The cyclic polyamine backbones comprising the cotton soil release agents of the present invention have the general formula:
H
[HzN-R]n-k+r[N-R]m [N-R]n--N-R]k-NHz said backbones prior to subsequent modification, comprise primary, secondary and tertiary amine nitrogens connected by R "linking" units For the purpose of the present invention, primary amine nitrogens comprising the backbone or branching chain once modified are defined as V or Z "terminal"
units. For example, when a primary amine moiety, located at the end of the main polyamine backbone or branching chain having the structure H2N-R] -is modified according to the present invention, it is thereafter defined as a V "terminal" unit, or 5 simply a V unit. However, for the purposes of the present invention, some or all of the primary amine moieties can remain unmodified subject to the restrictions furthere described herein below.
These unmodified primary amine moieties by virtue of their position in the backbone chain remain "terminal" units. Likewise, when a primary amine moiety, located at the end of the main polyamine backbone having the structure is modified according to the present invention, it is thereafter defined as a Z "terminal" unit, or simply a Z unit. This unit can remain unmodified subject to the restrictions further described herein below.
In a similar manner, secondary amine nitrogens comprising the backbone or branching chain once modified are defined as W "backbone" units. For example, when a secondary amine moiety, the major constituent of the backbones and branching chains of the present invention, having the structure H
-[N-R]-is modified according to the present invention, it is thereafter defined as a W "backbone" unit, or simply a W unit. However, for the purposes of the present invention, some or all of the secondary amine moieties can remain unmodified, but according to the present invention some backbone units must be modified. These unmodified secondary amine moieties by virtue of their position in the backbone chain remain "backbone" units.
In a further similar manner, tertiary amine nitrogens comprising the backbone or branching chain once modified are further referred to as Y "branching" units.
For example, when a tertiary amine moiety, which is a chain branch point of either the polyamine backbone or other branching chains or rings, having the structure -[N-R]-is modified according to the present invention, it is thereafter defined as a Y "branching" unit, or simply a Y unit. However, for the purposes of the present invention, some or all or the tertiary amine moieties can remain unmodified. These unmodified tertiary amine moieties by virtue of their position in the backbone chain remain "branching" units. The R units associated with the V, W and Y unit nitrogens which serve to connect the polyamine nitrogens, are described herein below.
The final modified structure of the polyamines of the present invention can be therefore represented by the general formula V(n+1)WmynZ
for linear or branched polyamine cotton soil release polymers and by the general formula V(n-k+1)WmynykZ
for cyclic polyamine cotton soil release polymers. For the case of polyamines comprising rings, a Y' unit of the formula -[N-R]-serves as a branch point for a backbone or branch ring. Except in the cases wherein the backbone comprises a ring, then for every Y' unit there is a Y unit having the formula I
-[N-R]-that will form the connection point of the ring to the main polymer chain or branch. In the unique case where the backbone is a complete ring, the polyamine backbone has the formula H I
[H2N-R]ri [N-R]m [N-R]ri therefore comprising no Z terminal unit and having the formula Vn-kWmynyk wherein k is the number of ring forming branching units.
The polyacrylic based polymer may be beneficially combined with the water soluble or dispersible, modified polyamine soil release polymers. Such polymers are discussed in U.S.
Patent 3,087,316. These polyamines comprise backbones that can be either linear or cyclic. The polyamine backbones can also comprise polyamine branching chains to a greater or lesser degree.
In general, the polyamine backbones described herein are modified in such a manner that each nitrogen of the polyamine chain is thereafter described in terms of a unit that is substituted, quaternized, oxidized, or combinations thereof.
For the purposes of the present invention the term "modification" is defined as replacing a backbone -NH hydrogen atom by an E unit (substitution), quaternizing a backbone nitrogen (quaternized) or oxidizing a backbone nitrogen to the N-oxide (oxidized). The terms "modification" and "substitution" are used interchangably when referring to the process of replacing a hydrogen atom attached to a backbone nitrogen with an E unit.
Quaternization or oxidation may take place in some circumstances without substitution, but substitution must be accompanied by oxidation or quaternization of at least one backbone nitrogen.
The linear or non-cyclic polyamine backbones that comprise the cotton soil release agents of the present invention have the general formula:
H
[H2N-R]n+1-[N-R]m [N-R]n NHz said backbones prior to subsequent modification, comprise primary, secondary and tertiary amine nitrogens connected by R "linking" units. The cyclic polyamine backbones comprising the cotton soil release agents of the present invention have the general formula:
H
[HzN-R]n-k+r[N-R]m [N-R]n--N-R]k-NHz said backbones prior to subsequent modification, comprise primary, secondary and tertiary amine nitrogens connected by R "linking" units For the purpose of the present invention, primary amine nitrogens comprising the backbone or branching chain once modified are defined as V or Z "terminal"
units. For example, when a primary amine moiety, located at the end of the main polyamine backbone or branching chain having the structure H2N-R] -is modified according to the present invention, it is thereafter defined as a V "terminal" unit, or 5 simply a V unit. However, for the purposes of the present invention, some or all of the primary amine moieties can remain unmodified subject to the restrictions furthere described herein below.
These unmodified primary amine moieties by virtue of their position in the backbone chain remain "terminal" units. Likewise, when a primary amine moiety, located at the end of the main polyamine backbone having the structure is modified according to the present invention, it is thereafter defined as a Z "terminal" unit, or simply a Z unit. This unit can remain unmodified subject to the restrictions further described herein below.
In a similar manner, secondary amine nitrogens comprising the backbone or branching chain once modified are defined as W "backbone" units. For example, when a secondary amine moiety, the major constituent of the backbones and branching chains of the present invention, having the structure H
-[N-R]-is modified according to the present invention, it is thereafter defined as a W "backbone" unit, or simply a W unit. However, for the purposes of the present invention, some or all of the secondary amine moieties can remain unmodified, but according to the present invention some backbone units must be modified. These unmodified secondary amine moieties by virtue of their position in the backbone chain remain "backbone" units.
In a further similar manner, tertiary amine nitrogens comprising the backbone or branching chain once modified are further referred to as Y "branching" units.
For example, when a tertiary amine moiety, which is a chain branch point of either the polyamine backbone or other branching chains or rings, having the structure -[N-R]-is modified according to the present invention, it is thereafter defined as a Y "branching" unit, or simply a Y unit. However, for the purposes of the present invention, some or all or the tertiary amine moieties can remain unmodified. These unmodified tertiary amine moieties by virtue of their position in the backbone chain remain "branching" units. The R units associated with the V, W and Y unit nitrogens which serve to connect the polyamine nitrogens, are described herein below.
The final modified structure of the polyamines of the present invention can be therefore represented by the general formula V(n+1)WmynZ
for linear or branched polyamine cotton soil release polymers and by the general formula V(n-k+1)WmynykZ
for cyclic polyamine cotton soil release polymers. For the case of polyamines comprising rings, a Y' unit of the formula -[N-R]-serves as a branch point for a backbone or branch ring. Except in the cases wherein the backbone comprises a ring, then for every Y' unit there is a Y unit having the formula I
-[N-R]-that will form the connection point of the ring to the main polymer chain or branch. In the unique case where the backbone is a complete ring, the polyamine backbone has the formula H I
[H2N-R]ri [N-R]m [N-R]ri therefore comprising no Z terminal unit and having the formula Vn-kWmynyk wherein k is the number of ring forming branching units.
In the case of non-cyclic polyamines, the ratio of the index n to the index m relates to the relative degree of branching. A fully non-branched linear modified polyamine according to the present invention has the formula VWmZ
that is, n is equal to 0. The greater the value of n (the lower the ratio of m to n), the greater the degree of branching in the molecule. Typically the value for m ranges from a minimum value of 4 to about 400, however larger values of m, especially when the value of the index n is very low or nearly 0, are also preferred. As further defined herein below, when the ratio of m : n is approximately 2: 1 m is preferably less than 200.
Each polyamine nitrogen whether primary, secondary or tertiary, once modified according to the present invention, is further defined as being a member of one of three general classes;
simple substituted, quaternized or oxidized. Those polyamine nitrogen units not modified are classed into V, W, Y, or Z units depending on whether they are primary, secondary or tertiary nitrogens. That is unmodified primary amine nitrogens are V or Z units, unmodified secondary amine nitrogens are W units and unmodified tertiary amine nitrogens are Y
units for the purposes of the present invention.
Modified primary amine moieties are defined as V "terminal" units having one of three forms:
a) simple substituted units having the structure:
E-N-R-E
b) quaternized units having the structure:
i X-E-N R-E
wherein X is a suitable counter ion providing charge balance; and c) oxidized units having the structure:
that is, n is equal to 0. The greater the value of n (the lower the ratio of m to n), the greater the degree of branching in the molecule. Typically the value for m ranges from a minimum value of 4 to about 400, however larger values of m, especially when the value of the index n is very low or nearly 0, are also preferred. As further defined herein below, when the ratio of m : n is approximately 2: 1 m is preferably less than 200.
Each polyamine nitrogen whether primary, secondary or tertiary, once modified according to the present invention, is further defined as being a member of one of three general classes;
simple substituted, quaternized or oxidized. Those polyamine nitrogen units not modified are classed into V, W, Y, or Z units depending on whether they are primary, secondary or tertiary nitrogens. That is unmodified primary amine nitrogens are V or Z units, unmodified secondary amine nitrogens are W units and unmodified tertiary amine nitrogens are Y
units for the purposes of the present invention.
Modified primary amine moieties are defined as V "terminal" units having one of three forms:
a) simple substituted units having the structure:
E-N-R-E
b) quaternized units having the structure:
i X-E-N R-E
wherein X is a suitable counter ion providing charge balance; and c) oxidized units having the structure:
t E-N-R-I
E
Modified secondary amine moieties are defined as W "backbone" units having one of three forms:
a) simple substituted units having the structure:
-N-R-E
b) quaternized units having the structure:
i X-+
-N-R-E
wherein X is a suitable counter ion providing charge balance; and c) oxidized units having the structure:
t -N-R-E
Modified tertiary amine moieties are defined as Y "branching" units having one of three forms:
a) unmodified units having the structure:
-N-R-b) quaternized units having the structure:
E
Modified secondary amine moieties are defined as W "backbone" units having one of three forms:
a) simple substituted units having the structure:
-N-R-E
b) quaternized units having the structure:
i X-+
-N-R-E
wherein X is a suitable counter ion providing charge balance; and c) oxidized units having the structure:
t -N-R-E
Modified tertiary amine moieties are defined as Y "branching" units having one of three forms:
a) unmodified units having the structure:
-N-R-b) quaternized units having the structure:
i X-+
-N-R-wherein X is a suitable counter ion providing charge balance; and c) oxidized units having the structure:
t -N-R-I
Certain modified primary amine moieties are defined as Z "terminal" units having one of three forms:
a) simple substituted units having the structure:
-N-E
E
b) quaternized units having the structure:
i X--N E
E
wherein X is a suitable counter ion providing charge balance; and c) oxidized units having the structure:
t -N-E
E
When any position on a nitrogen is unsubstituted of unmodified, it is understood that hydrogen will substitute for E. For example, a primary amine unit comprising one E unit in the form of a hydroxyethyl moiety is a V terminal unit having the formula (HOCHZCHZ)HN-.
For the purposes of the present invention there are two types of chain terminating units, the V and Z units. The Z "terminal" unit derives from a terminal primary amino moiety of the structure -NH2. Non-cyclic polyamine backbones according to the present invention comprise only one Z unit whereas cyclic polyamines can comprise no Z units. The Z
"terminal" unit can be 5 substituted with any of the E units described further herein below, except when the Z unit is modified to form an N-oxide. In the case where the Z unit nitrogen is oxidized to an N-oxide, the nitrogen must be modified and therefor E cannot be a hydrogen.
The polyamines of the present invention comprise backbone R units that serve to connect the nitrogen atoms of the backbone. R units comprise units that for the purposes of the present 10 invention are referred to as "hydrocarbyl R" units and "oxy R" units. The "hydrocarbyl" R units are C2-C12 alkylene, preferably ethylene, 1,2-propylene, and mixtures thereof, more preferably ethylene. The "oxy" R units comprise -(R10)xR3(OR1)x-, -CH2CH(OR2)CH2O)z(R1O)y1O-(CH2CH(OR2)CH2)w-, -CH2CH(OR2)CH2-, and mixtures thereof; preferred "oxy" R
units are -CH2CH(OR2)CH2-, -(CH2CH(OH)CH2O)z(R1O)yR1-O(CH2CH(OH)CH2)w-, and mixtures 15 thereof. The backbone R units of the present invention must comprise at least one -CH2CH(OR2)CH2-, -(CH2CH(OH)CH2O)z-(R1O)yR1O(CH2CH(OH)CH2)w-, -CH2CH(OR2)CH2-, or mixtures thereof.
R1 units are C2-C6 alkylene, and mixtures thereof, preferably ethylene.
R2 is hydrogen, and -(R10)xB, preferably hydrogen.
R3 is C1-C12 alkylene, C3-C12 hydroxyalkylene, C4-C12 dihydroxyalkylene, C8-dialkylarylene, -C(O)-, -C(O)NHR6NHC(O)-, -C(O)(R4)rC(O)-, -R1(OR1)-, -CH2CH(OH)CH2O(R1O)yR1OCH2CH(OH)CH2-, -C(O)(R4)rC(O)-, -CH2CH(OH)CH2-, R3 is preferably ethylene, -C(O)-, -C(O)NHR5NHC(O)-, -R1(OR1)-, -CH2CH(OH)CH2-, -CH2CH(OH)CH2O(R1O)yR1OCH2CH-(OH)CH2-, more preferably -CH2CH(OH)CH2-.
-N-R-wherein X is a suitable counter ion providing charge balance; and c) oxidized units having the structure:
t -N-R-I
Certain modified primary amine moieties are defined as Z "terminal" units having one of three forms:
a) simple substituted units having the structure:
-N-E
E
b) quaternized units having the structure:
i X--N E
E
wherein X is a suitable counter ion providing charge balance; and c) oxidized units having the structure:
t -N-E
E
When any position on a nitrogen is unsubstituted of unmodified, it is understood that hydrogen will substitute for E. For example, a primary amine unit comprising one E unit in the form of a hydroxyethyl moiety is a V terminal unit having the formula (HOCHZCHZ)HN-.
For the purposes of the present invention there are two types of chain terminating units, the V and Z units. The Z "terminal" unit derives from a terminal primary amino moiety of the structure -NH2. Non-cyclic polyamine backbones according to the present invention comprise only one Z unit whereas cyclic polyamines can comprise no Z units. The Z
"terminal" unit can be 5 substituted with any of the E units described further herein below, except when the Z unit is modified to form an N-oxide. In the case where the Z unit nitrogen is oxidized to an N-oxide, the nitrogen must be modified and therefor E cannot be a hydrogen.
The polyamines of the present invention comprise backbone R units that serve to connect the nitrogen atoms of the backbone. R units comprise units that for the purposes of the present 10 invention are referred to as "hydrocarbyl R" units and "oxy R" units. The "hydrocarbyl" R units are C2-C12 alkylene, preferably ethylene, 1,2-propylene, and mixtures thereof, more preferably ethylene. The "oxy" R units comprise -(R10)xR3(OR1)x-, -CH2CH(OR2)CH2O)z(R1O)y1O-(CH2CH(OR2)CH2)w-, -CH2CH(OR2)CH2-, and mixtures thereof; preferred "oxy" R
units are -CH2CH(OR2)CH2-, -(CH2CH(OH)CH2O)z(R1O)yR1-O(CH2CH(OH)CH2)w-, and mixtures 15 thereof. The backbone R units of the present invention must comprise at least one -CH2CH(OR2)CH2-, -(CH2CH(OH)CH2O)z-(R1O)yR1O(CH2CH(OH)CH2)w-, -CH2CH(OR2)CH2-, or mixtures thereof.
R1 units are C2-C6 alkylene, and mixtures thereof, preferably ethylene.
R2 is hydrogen, and -(R10)xB, preferably hydrogen.
R3 is C1-C12 alkylene, C3-C12 hydroxyalkylene, C4-C12 dihydroxyalkylene, C8-dialkylarylene, -C(O)-, -C(O)NHR6NHC(O)-, -C(O)(R4)rC(O)-, -R1(OR1)-, -CH2CH(OH)CH2O(R1O)yR1OCH2CH(OH)CH2-, -C(O)(R4)rC(O)-, -CH2CH(OH)CH2-, R3 is preferably ethylene, -C(O)-, -C(O)NHR5NHC(O)-, -R1(OR1)-, -CH2CH(OH)CH2-, -CH2CH(OH)CH2O(R1O)yR1OCH2CH-(OH)CH2-, more preferably -CH2CH(OH)CH2-.
R4 is C1-C12 alkylene, C4-C12 alkenylene, C8-C12 arylalkylene, C6-C10 arylene, preferably C1-C10 alkylene, C8-C12 arylalkylene, more preferably C2-C8 alkylene, most preferably ethylene or butylene.
R5 is C2-C12 alkylene or C6-C12 arylene The preferred "oxy" R units are further defined in terms of the R1, R2, and R3 units.
Preferred "oxy" R units comprise the preferred R1, R2, and R3 units. The preferred cotton soil release agents of the present invention comprise at least 50% R1 units that are ethylene.
Preferred R1, R2, and R3 units are combined with the "oxy" R units to yield the preferred "oxy"
R units in the following manner.
i) Substituting more preferred R3 into -(CH2CH2O)xR3(OCH2CH2)x- yields -(CH2CH2O)xCH2CHOHCH2(OCH2CH2)x-.
ii) Substituting preferred R1 and R2 into -(CH2CH(OR2)CH2O)z-(R1O)yR1O(CH2CH(OR2)CH2)w- yields -(CH2CH(OH)CH2O)z-(CH2CH2O)yCH2CH2O(CH2CH(OH)CH2)w-.
iii) Substituting preferred R2 into -CH2CH(OR2)CH2- yields -CHZCH(OH)CHZ-.
E units are selected from the group consisting of -(CH2)pCO2M, -(CH2)q-SO3M, -CH(CH2CO2M)CO2M, -(CH2)pPO3M, -(R1O)xB, preferably -(R1O)xB, -(CH2)pCO2M, -(CH2)qSO3M, CH(CH2CO2M)CO2M, more preferably -(R10)xB. When no modification or substitution is made on a nitrogen then hydrogen atom will remain as the moiety representing E.
E units do not comprise hydrogen atom when the V, W or Z units are oxidized, that is the nitrogens are N-oxides. For example, the backbone chain or branching chains do not comprise units of the following structure:
R5 is C2-C12 alkylene or C6-C12 arylene The preferred "oxy" R units are further defined in terms of the R1, R2, and R3 units.
Preferred "oxy" R units comprise the preferred R1, R2, and R3 units. The preferred cotton soil release agents of the present invention comprise at least 50% R1 units that are ethylene.
Preferred R1, R2, and R3 units are combined with the "oxy" R units to yield the preferred "oxy"
R units in the following manner.
i) Substituting more preferred R3 into -(CH2CH2O)xR3(OCH2CH2)x- yields -(CH2CH2O)xCH2CHOHCH2(OCH2CH2)x-.
ii) Substituting preferred R1 and R2 into -(CH2CH(OR2)CH2O)z-(R1O)yR1O(CH2CH(OR2)CH2)w- yields -(CH2CH(OH)CH2O)z-(CH2CH2O)yCH2CH2O(CH2CH(OH)CH2)w-.
iii) Substituting preferred R2 into -CH2CH(OR2)CH2- yields -CHZCH(OH)CHZ-.
E units are selected from the group consisting of -(CH2)pCO2M, -(CH2)q-SO3M, -CH(CH2CO2M)CO2M, -(CH2)pPO3M, -(R1O)xB, preferably -(R1O)xB, -(CH2)pCO2M, -(CH2)qSO3M, CH(CH2CO2M)CO2M, more preferably -(R10)xB. When no modification or substitution is made on a nitrogen then hydrogen atom will remain as the moiety representing E.
E units do not comprise hydrogen atom when the V, W or Z units are oxidized, that is the nitrogens are N-oxides. For example, the backbone chain or branching chains do not comprise units of the following structure:
t t t -N-R or H-N-R or -N-H
I I I
H H H
B is hydrogen, -(CH2)pCO2M, -(CH2)qSO3M, -(CH2)qCH(SO3M)-CH2SO3M, -(CH2)qCH(SO2M)CH2SO3M, -(CH2)pPO3M, -PO3M, preferably hydrogen, -(CH2)qSO3M, -(CH2)qCH(SO3M)CH2SO3M, -(CH2)qCH(SO2M)-CH2SO3M, more preferably hydrogen or -(CH2)qSO3M.
M is hydrogen or a water soluble cation in sufficient amount to satisfy charge balance.
For example, a sodium cation equally satisfies -(CH2)pCO2M, and -(CH2)qSO3M, thereby resulting in -(CH2)pCO2Na, and -(CH2)qSO3Na moieties. More than one monovalent cation, (sodium, potassium, etc.) can be combined to satisfy the required chemical charge balance.
However, more than one anionic group may be charge balanced by a divalent cation, or more than one mono-valent cation may be necessary to satisfy the charge requirements of a poly-anionic radical. For example, a-(CH2)pPO3M moiety substituted with sodium atoms has the formula -(CH2)pPO3Na2. Divalent cations such as calcium (Ca2+) or magnesium (Mg2+) may be substituted for or combined with other suitable mono-valent water soluble cations. Preferred cations are sodium and potassium, more preferred is sodium.
X is a water soluble anion such as chlorine (Cl-), bromine (Br-) and iodine (I-) or X can be any negatively charged radical such as sulfate (S042-), methosulfate (CH30S03-), and methanesulfonate (CH3SO3-).
The formula indices have the following values: p has the value from 1 to 6; q has the value from 0 to 6; r has the value 0 or 1; w has the value 0 or 1; x has the value from 1 to 100; y has the value from 0 to 100; z has the value 0 or 1; k has the value from 0 to about 20; m has the value from 4 to about 400; n has the value from 0 to about 200; preferably m +
n has the value of at least 5.
The preferred cotton soil release agents of the present invention comprise polyamine backbones wherein less than about 100% of the R groups comprise "oxy" R units, preferably less than about 50% , more preferably less than 30%, most preferably less than about 20% of the R
units comprise "oxy" R units.
I I I
H H H
B is hydrogen, -(CH2)pCO2M, -(CH2)qSO3M, -(CH2)qCH(SO3M)-CH2SO3M, -(CH2)qCH(SO2M)CH2SO3M, -(CH2)pPO3M, -PO3M, preferably hydrogen, -(CH2)qSO3M, -(CH2)qCH(SO3M)CH2SO3M, -(CH2)qCH(SO2M)-CH2SO3M, more preferably hydrogen or -(CH2)qSO3M.
M is hydrogen or a water soluble cation in sufficient amount to satisfy charge balance.
For example, a sodium cation equally satisfies -(CH2)pCO2M, and -(CH2)qSO3M, thereby resulting in -(CH2)pCO2Na, and -(CH2)qSO3Na moieties. More than one monovalent cation, (sodium, potassium, etc.) can be combined to satisfy the required chemical charge balance.
However, more than one anionic group may be charge balanced by a divalent cation, or more than one mono-valent cation may be necessary to satisfy the charge requirements of a poly-anionic radical. For example, a-(CH2)pPO3M moiety substituted with sodium atoms has the formula -(CH2)pPO3Na2. Divalent cations such as calcium (Ca2+) or magnesium (Mg2+) may be substituted for or combined with other suitable mono-valent water soluble cations. Preferred cations are sodium and potassium, more preferred is sodium.
X is a water soluble anion such as chlorine (Cl-), bromine (Br-) and iodine (I-) or X can be any negatively charged radical such as sulfate (S042-), methosulfate (CH30S03-), and methanesulfonate (CH3SO3-).
The formula indices have the following values: p has the value from 1 to 6; q has the value from 0 to 6; r has the value 0 or 1; w has the value 0 or 1; x has the value from 1 to 100; y has the value from 0 to 100; z has the value 0 or 1; k has the value from 0 to about 20; m has the value from 4 to about 400; n has the value from 0 to about 200; preferably m +
n has the value of at least 5.
The preferred cotton soil release agents of the present invention comprise polyamine backbones wherein less than about 100% of the R groups comprise "oxy" R units, preferably less than about 50% , more preferably less than 30%, most preferably less than about 20% of the R
units comprise "oxy" R units.
The preferred cotton soil release agents of the present invention comprise polyamine backbones wherein less than 50% of the "hydrocarbyl" R groups comprise more than 3 carbon atoms. For example, ethylene, 1,2-propylene, and 1,3-propylene comprise 3 or less carbon atoms and are the preferred "hydrocarbyl" R units. That is when backbone R units are C2-C12 alkylene, preferred is C2-C3 alkylene, most preferred is ethylene.
The cotton soil release agents of the present invention comprise modified non-homogeneous polyamine backbones, wherein 100% or less of the -NH units are modified. For the purpose of the present invention the term "homogeneous polyamine backbone"
is defined as a polyamine backbone having R units that are the same (i.e., all ethylene).
However, this sameness definition does not exclude polyamines that comprise other extraneous units comprising the polymer backbone which are present due to an artifact of the chosen method of chemical synthesis. For example, it is known to those skilled in the art that ethanolamine may be used as an "initiator" in the synthesis of polyethyleneimines, therefore a sample of polyethyleneimine that comprises one hydroxyethyl moiety resulting from the polymerization "initiator" would be considered to comprise a homogeneous polyamine backbone for the purposes of the present invention.
For the purposes of the present invention the term "non-homogeneous polymer backbone"
refers to polyamine backbones that are a composite of various R unit lengths and R unit types.
The proper manipulation of these "R unit chain lengths" provides the formulator with the ability to modify the solubility and fabric substantivity of the cotton soil release agents of the present invention.
An example of a polyamine backbone according to the present invention prior to modification has the formula H H OH H H
N~~N~-~NH2 NH2 H2N~/ H
wherein 8 R units comprise ethylene units and 1 R unit comprises a -CH2CH(OH)CH2O(R1O)yR1OCH2CH(OH)CH2-moiety wherein R1 is ethylene and y is equal to 1.
A further example of a polyamine backbone prior to modification that is suitable for use as a cotton soil release agent according to the present invention has the formula H H OH H H
I H2N~~~NI I
~NH2 H=N__-~N__~NH2 H2N___N----NH2 ~
wherein 12 R units comprise ethylene units and 1 R unit comprises a -CH2CH(OH)CH2O(R1O)yR1OCH2CH(OH)CH2-moiety wherein R1 is ethylene and y is equal to 1. Structures similar to these two examples given above are for the purposes of the present invention commonly referred to as "blocks". Typically several blocks are combined to form the final backbone prior to modification.
As in the examples above, polyethyleneimines (PEI's) and polyethyleneamines (PEA's) of low molecular weight, typically below 600 daltons, are linked together using the "oxy" R units which serve as convenient coupling agents. Depending on the desired properties of the final cotton soil release agent (e.g., solubility, fabric substantivity) a lesser or greater degree of "oxy" R
units will comprise the polyamine backbone.
It is more convenient for nitrogen modification to occur after complete assembly of the polyamine backbone. However the formulator may wish to have a polymer backbone with a high degree of unmodified nitrogen atoms. This can be accomplished by pre-modifying some or all or the polyalkyleneimine or polyalkyleneamine "hydrocarbyl" portion of the backbone prior to linking via "oxy" R units.
An example of a procedure that allows for a mixture of modified and unmodified blocks in the cotton soil release polymer, comprises the steps of i) modifying a polyethyleneimine having, for example, the formula:
~ H
HZN,,,,,--,,N-,-~N-_~N-,-~N---~NHZ
H ~
H
NI
NHZ
wherein the modification is a) substitution of the -NH hydrogen atom by an E unit;
5 b) quaternization;
c) oxidation to the N-oxide; or d) mixtures thereof;
resulting in an example modified polyethyleneimine having the formula:
NMod2 Mod H
M o d ZN"'^"N~~ NM o d I I
H
Mod NMod2 10 wherein Mod represents one or more modifications according to the present invention;
ii) the modified polyethyleneimine is coupled with a second molecule of the original unmodified polyethyleneimine through an -CH2CH(OH)CH2O(R1O)yR1OCH2CH(OH)CH2- moiety wherein R1 is ethylene and y is equal to 1, to form a polyamine cotton soil release agent having the formula:
NMod2 Mod H
M o d ZN N~~ N~~ N~~ N~~ NM o d I ~
Mod rN
`
OH NMod2 O
O
) H H
'1~~~
NHZ
H
~1N
H ~
NHZ
Once this process is completed, the above unit may be used "as is" or may be further coupled to one or more modified or un-modified blocks.
The preferred "blocks" of polyamines having "hydrocarbyl" R units that comprise the backbone of the compounds of the present invention are generally polyalkyleneamines (PAA's), polyalkyleneimines (PAI's), preferably polyethyleneamine (PEA's), polyethyleneimines (PEI's) units. An example of a polyalkyleneamine (PAA) is tetrabutylenepentamine.
PEA's are obtained by reactions involving ammonia and ethylene dichloride, followed by fractional distillation. The common PEA's obtained are triethylenetetramine (TETA) and teraethylenepentamine (TEPA).
Above the pentamines, i.e., the hexamines, heptamines, octamines and possibly nonamines, the cogenerically derived mixture does not appear to separate by distillation and can include other materials such as cyclic amines and particularly piperazines. There can also be present cyclic amines with side chains in which nitrogen atoms appear. See U.S. Patent 2,792,372, Dickinson, issued May 14, 1957, which describes the preparation of PEA's.
The PEI blocks which comprise the preferred backbones of the polyamines of the present invention 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 PEI's are disclosed in U.S. Patent 2,182,306, Ulrich et al., issued December 5, 1939; U.S. Patent 3,033,746, Mayle et al., issued May 8, 1962; U.S. Patent 2,208,095, Esselmann et al., issued July 16, 1940;
U.S. Patent 2,806,839, Crowther, issued September 17, 1957; and U.S. Patent 2,553,696, Wilson, issued May 21, 1951 (all herein incorporated by reference). In addition to the linear and branched PEI's, the present invention also includes the cyclic amines that are typically formed as artifacts of synthesis. The presence of these materials may be increased or decreased depending on the conditions chosen by the formulator.
However, polyamine backbones of the present invention may comprise 100% "oxy"
moieties, for example, a polyamine backbone prior to modification comprising -CH2CH(OH)CH2O(R1O)yR1OCH2CH(OH)CH2- R units wherein R1 is ethylene and y is equal to 1, has the formula OH
H OH
o OH n+ ~
OH m OH
I Jn OH
An example of a soil release agent according to the present invention has the formula:
OH
OH OH OH OH
OH
~ ~ 1OH Or f f O O O O O
O
H Ol C1 CN 3 ~,NNU \~NN~~+
Cl OHCH3 ~3 O rOHCA ~ ?
J O OH 1NO IN) HO + ~ O OH O N OH
J O O COO
OH HO-_,N
~ O~ OH OH
CH
(T +N`;~O"'~OH
HO-*"~O~~ ~'O~~OH
CI O
- r HO_,,~O,,-,iNO~~OH OH
wherein R units are ethylene and -CHZCH[(CHZCHZO)ZH]CHZ- and the E units are -(CHZCHZO)ZH and -CH3.
Preferred, but non-limiting, examples of polyamine-based polymers of the present invention are shown below - PE1600(EO)10(PO)7 and PE1600(EO)2o, respectively.
-N N
1 ,f o ...
~
~J U ~ ~1_ to ta ~' li~ ~~ \l ~v LL ~i tr, ~`!!
~ ~-~
+OCHzCH+N---CHzCHzOH
H -H`! ~N
r0 2p Oy2 C~y r 2~ y(;HzCHzOH
N
OG~ y H
2p/O H
Ch HN
H
N ~v I v N" v N v N" v N v NCHzCHzO+2 GZ''L TAx 4- L CHZCHZO~H
G~2 = = 20 x O = N =
o H
H I J ~ I
H r a Cy H
H-i-OCHzCH2'~'N X
The cotton soil release agents of the present invention comprise modified non-homogeneous polyamine backbones, wherein 100% or less of the -NH units are modified. For the purpose of the present invention the term "homogeneous polyamine backbone"
is defined as a polyamine backbone having R units that are the same (i.e., all ethylene).
However, this sameness definition does not exclude polyamines that comprise other extraneous units comprising the polymer backbone which are present due to an artifact of the chosen method of chemical synthesis. For example, it is known to those skilled in the art that ethanolamine may be used as an "initiator" in the synthesis of polyethyleneimines, therefore a sample of polyethyleneimine that comprises one hydroxyethyl moiety resulting from the polymerization "initiator" would be considered to comprise a homogeneous polyamine backbone for the purposes of the present invention.
For the purposes of the present invention the term "non-homogeneous polymer backbone"
refers to polyamine backbones that are a composite of various R unit lengths and R unit types.
The proper manipulation of these "R unit chain lengths" provides the formulator with the ability to modify the solubility and fabric substantivity of the cotton soil release agents of the present invention.
An example of a polyamine backbone according to the present invention prior to modification has the formula H H OH H H
N~~N~-~NH2 NH2 H2N~/ H
wherein 8 R units comprise ethylene units and 1 R unit comprises a -CH2CH(OH)CH2O(R1O)yR1OCH2CH(OH)CH2-moiety wherein R1 is ethylene and y is equal to 1.
A further example of a polyamine backbone prior to modification that is suitable for use as a cotton soil release agent according to the present invention has the formula H H OH H H
I H2N~~~NI I
~NH2 H=N__-~N__~NH2 H2N___N----NH2 ~
wherein 12 R units comprise ethylene units and 1 R unit comprises a -CH2CH(OH)CH2O(R1O)yR1OCH2CH(OH)CH2-moiety wherein R1 is ethylene and y is equal to 1. Structures similar to these two examples given above are for the purposes of the present invention commonly referred to as "blocks". Typically several blocks are combined to form the final backbone prior to modification.
As in the examples above, polyethyleneimines (PEI's) and polyethyleneamines (PEA's) of low molecular weight, typically below 600 daltons, are linked together using the "oxy" R units which serve as convenient coupling agents. Depending on the desired properties of the final cotton soil release agent (e.g., solubility, fabric substantivity) a lesser or greater degree of "oxy" R
units will comprise the polyamine backbone.
It is more convenient for nitrogen modification to occur after complete assembly of the polyamine backbone. However the formulator may wish to have a polymer backbone with a high degree of unmodified nitrogen atoms. This can be accomplished by pre-modifying some or all or the polyalkyleneimine or polyalkyleneamine "hydrocarbyl" portion of the backbone prior to linking via "oxy" R units.
An example of a procedure that allows for a mixture of modified and unmodified blocks in the cotton soil release polymer, comprises the steps of i) modifying a polyethyleneimine having, for example, the formula:
~ H
HZN,,,,,--,,N-,-~N-_~N-,-~N---~NHZ
H ~
H
NI
NHZ
wherein the modification is a) substitution of the -NH hydrogen atom by an E unit;
5 b) quaternization;
c) oxidation to the N-oxide; or d) mixtures thereof;
resulting in an example modified polyethyleneimine having the formula:
NMod2 Mod H
M o d ZN"'^"N~~ NM o d I I
H
Mod NMod2 10 wherein Mod represents one or more modifications according to the present invention;
ii) the modified polyethyleneimine is coupled with a second molecule of the original unmodified polyethyleneimine through an -CH2CH(OH)CH2O(R1O)yR1OCH2CH(OH)CH2- moiety wherein R1 is ethylene and y is equal to 1, to form a polyamine cotton soil release agent having the formula:
NMod2 Mod H
M o d ZN N~~ N~~ N~~ N~~ NM o d I ~
Mod rN
`
OH NMod2 O
O
) H H
'1~~~
NHZ
H
~1N
H ~
NHZ
Once this process is completed, the above unit may be used "as is" or may be further coupled to one or more modified or un-modified blocks.
The preferred "blocks" of polyamines having "hydrocarbyl" R units that comprise the backbone of the compounds of the present invention are generally polyalkyleneamines (PAA's), polyalkyleneimines (PAI's), preferably polyethyleneamine (PEA's), polyethyleneimines (PEI's) units. An example of a polyalkyleneamine (PAA) is tetrabutylenepentamine.
PEA's are obtained by reactions involving ammonia and ethylene dichloride, followed by fractional distillation. The common PEA's obtained are triethylenetetramine (TETA) and teraethylenepentamine (TEPA).
Above the pentamines, i.e., the hexamines, heptamines, octamines and possibly nonamines, the cogenerically derived mixture does not appear to separate by distillation and can include other materials such as cyclic amines and particularly piperazines. There can also be present cyclic amines with side chains in which nitrogen atoms appear. See U.S. Patent 2,792,372, Dickinson, issued May 14, 1957, which describes the preparation of PEA's.
The PEI blocks which comprise the preferred backbones of the polyamines of the present invention 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 PEI's are disclosed in U.S. Patent 2,182,306, Ulrich et al., issued December 5, 1939; U.S. Patent 3,033,746, Mayle et al., issued May 8, 1962; U.S. Patent 2,208,095, Esselmann et al., issued July 16, 1940;
U.S. Patent 2,806,839, Crowther, issued September 17, 1957; and U.S. Patent 2,553,696, Wilson, issued May 21, 1951 (all herein incorporated by reference). In addition to the linear and branched PEI's, the present invention also includes the cyclic amines that are typically formed as artifacts of synthesis. The presence of these materials may be increased or decreased depending on the conditions chosen by the formulator.
However, polyamine backbones of the present invention may comprise 100% "oxy"
moieties, for example, a polyamine backbone prior to modification comprising -CH2CH(OH)CH2O(R1O)yR1OCH2CH(OH)CH2- R units wherein R1 is ethylene and y is equal to 1, has the formula OH
H OH
o OH n+ ~
OH m OH
I Jn OH
An example of a soil release agent according to the present invention has the formula:
OH
OH OH OH OH
OH
~ ~ 1OH Or f f O O O O O
O
H Ol C1 CN 3 ~,NNU \~NN~~+
Cl OHCH3 ~3 O rOHCA ~ ?
J O OH 1NO IN) HO + ~ O OH O N OH
J O O COO
OH HO-_,N
~ O~ OH OH
CH
(T +N`;~O"'~OH
HO-*"~O~~ ~'O~~OH
CI O
- r HO_,,~O,,-,iNO~~OH OH
wherein R units are ethylene and -CHZCH[(CHZCHZO)ZH]CHZ- and the E units are -(CHZCHZO)ZH and -CH3.
Preferred, but non-limiting, examples of polyamine-based polymers of the present invention are shown below - PE1600(EO)10(PO)7 and PE1600(EO)2o, respectively.
-N N
1 ,f o ...
~
~J U ~ ~1_ to ta ~' li~ ~~ \l ~v LL ~i tr, ~`!!
~ ~-~
+OCHzCH+N---CHzCHzOH
H -H`! ~N
r0 2p Oy2 C~y r 2~ y(;HzCHzOH
N
OG~ y H
2p/O H
Ch HN
H
N ~v I v N" v N v N" v N v NCHzCHzO+2 GZ''L TAx 4- L CHZCHZO~H
G~2 = = 20 x O = N =
o H
H I J ~ I
H r a Cy H
H-i-OCHzCH2'~'N X
H~OCHzCH2~'-N
20 I-CHzCHzO--H
The polyacrylic acid based polymers of the present invention may also be beneficially 5 combined with zwitterionic polyamine additives disclosed in U.S. 6,660,711.
These zwitterionic polyamines of the present invention have the formula:
[J-R]n-J
wherein the [J-R] units represent the amino units which comprise the main backbone and any branching chains. Preferably the zwitterionic polyamines prior to modification, inter alia, 10 quaternization, substitution of an amino unit hydrogen with an alkyleneoxy unit, have backbones which comprise from 2 to about 100 amino units. The index n which describes the number of backbone units present is further described herein below.
J units are the backbone amino units, said units are selected from the group consisting of:
15 i) primary amino units having the formula:
(Ri)zN.
ii) secondary amino units having the formula:
-RiN.
iii) tertiary amino units having the formula:
B
-N=
iv) primary quaternary amino units having the formula:
(Ri)2N
Q;
v) secondary quaternary amino units having the formula:
RiN
5 Q;
vi) tertiary quaternary amino units having the formula:
B
- N+
I
Q;
vii) primary N-oxide amino units having the formula:
(RI)2N
O=
10 viii) secondary N-oxide amino units having the formula:
- RiN
ix) tertiary N-oxide amino units having the formula:
B
- N
O=
x) and mixtures thereof.
15 B units which have the formula:
[J- R]
represent a continuation of the zwitterionic polyamine backbone by branching.
The number of B
units present, as well as, any further amino units which comprise the branches are reflected in the total value of the index n.
20 The backbone amino units of the zwitterionic polymers are connected by one or more R
units, said R units are selected from the group consisting of:
i) C2-Ci2 linear alkylene, C3-Ci2 branched alkylene, or mixtures thereof;
preferably C3-C6 alkylene. When two adjacent nitrogens of the polyamine backbone are N-oxides, preferably the alkylene backbone unit which separates said units are units or greater.
ii) alkyleneoxyalkylene units having the formula:
- (R2O)w(R3)-wherein R2 is selected from the group consisting of ethylene, 1,2-propylene, 1,3-propylene, 1,2-butylene, 1,4-butylene, and mixtures thereof; R3 is C2-C8 linear alkylene, C3-C8 branched alkylene, phenylene, substituted phenylene, and mixtures thereof; the index w is from 0 to about 25. R2 and R3 units may also comprise other backbone units. When comprising alkyleneoxyalkylene units, in one embodiment R2 and R3 units are each preferably ethylene or mixtures of ethylene, propylene and butylene, more preferably ethylene; in another embodiment R2 and R3 units are preferably mixtures of ethylene, propylene and butylene; the index w is from 1, preferably from about 2 to about 10, preferably to about 6.
iii) hydroxyalkylene units having the formula:
-(CHz),(CH)y(CHz)z wherein R4 is hydrogen, Ci-C6 alkyl, -(CH2)õ(R2O)r(CH2)õY, and mixtures thereof.
When R units comprise hydroxyalkylene units, R4 is preferably hydrogen or -(CH2)õ(R2O)r(CH2)õY wherein the index t is greater than 0, preferably from 10 to 30; the index u is from 0 to 6; and Y is preferably hydrogen or an anionic unit, more preferably -SO3M. The indices x, y, and z are each independently from 1 to 6, preferably the indices are each equal to 1 and R4 is hydrogen (2-hydroxypropylene unit) or (R2O)rY, or for polyhydroxy units y is preferably 2 or 3.
A preferred hydroxyalkylene unit is the 2-hydroxypropylene unit which can, for example, be suitably formed from glycidyl ether forming reagents, inter alia, epihalohydrin.
iv) hydroxyalkylene/oxyalkylene units having the formula:
(CH2)x(CH)y(CH2)z(X)r R20)w (CH2)x(CH)y(CH2)z(X)r j k wherein R2 , R4, and the indices w, x, y, and z are the same as defined herein above. X is oxygen or the amino unit -NR4-, the index r is 0 or 1. The indices j and k are each independently from 1 to 20. When alkyleneoxy units are absent the index w is 0. Non-limiting examples of preferred hydroxyalkylene/oxyalkylene units have the formula:
OH OH
I I
-CH2CHCH2O-(CH2CH2CH2O)2 CH2CHCH2 -OH OH OH
CH2CHCH2O-(CH2CH2O)3 CH2CHCH2O CH2CHCH2 OH OH
CH2CHCH2O- (CH2CH2O) CH2CHCH2 OH OH
CH2CHCH2O- (CH2CH2CH2O)4 CH2CHCH2 v) carboxyalkyleneoxy units having the formula:
- (R30)w(R3)w(X)r- II C- (X)r- R3 II
- (X)r- C- (X)r(R3)w(OR3)w-.
wherein R2 , R3, X, r, and w are the same as defined herein above. Non-limiting examples of preferred carboxyalkyleneoxy units include:
II II
- CHz C- O- CHzCHzCHzCHz O- C- CHz .
I
O O
~I --,a I I
CHz C- NH NH- C- CHz O O
-(CH2CH2CH2O)4 C C-(OCH2CH2CH2)4 vi) backbone branching units having the formula:
(CH2)x( ~ )y(CH2)z(~')r (R20)w (CH2)x( ~ )y(CH2)z(~')r i k wherein R4 is hydrogen, Ci-C6 alkyl, -(CH2)õ(R2O)r(CH2)õY, and mixtures thereof.
When R units comprise backbone branching units, R4 is preferably hydrogen or -(CH2)õ(R2O)r-(CH2)õY wherein the index t is greater than 0, preferably from 10 to 30; the index u is from 0 to 6; and Y is hydrogen, Ci-C4 linear alkyl, -N(Ri)2, an anionic unit, and mixtures thereof; preferably Y is hydrogen, or - N(Ri)2. A
preferred embodiment of backbone branching units comprises R4 equal to -(R2O)rH. The indices x, y, and z are each independently from 0 to 6.
vii) The formulator may suitably combine any of the above described R units to make a zwitterionic polyamine having a greater or lesser degree of hydrophilic character.
Ri units are the units which are attached to the backbone nitrogens. Ri units are selected from the group consisting of:
i) hydrogen; which is the unit typically present prior to any backbone modification.
ii) Ci-C22 alkyl, preferably Ci-C4 alkyl, more preferably methyl or ethyl, most preferably methyl. A preferred embodiment of the present invention in the instance wherein Ri units are attached to quaternary units (iv) or (v), Ri is the same unit as quaternizing unit Q. For example a J unit having the formula:
+
(CH3)2N
iii) C7-C22 arylalkyl, preferably benzyl.
iv) -[CH2CH(OR4)CH2O]s(R2O)rY; wherein R2 and R4 are the same as defined herein above, preferably when Ri units comprise R2 units, R2 is preferably ethylene.
The value of the index s is from 0 to 5. For the purposes of the present invention the index t is expressed as an average value, said average value from about 0.5 to about 100. The formulator may lightly alkyleneoxylate the backbone nitrogens in a manner wherein not every nitrogen atom comprises an Ri unit which is an alkyleneoxy unit thereby rendering the value of the index t less than 1.
v) Anionic units as described herein below.
vi) The formulator may suitably combine one or more of the above described Ri units when substituting the backbone of the zwitterionic polymers of the present invention.
Q is a quaternizing unit selected from the group consisting of Ci-C4 linear alkyl, benzyl, and mixtures thereof, preferably methyl. As described herein above, preferably Q is the same as Ri when Ri comprises an alkyl unit. For each backbone N+ unit (quaternary nitrogen) there will be an anion to provide charge neutrality. The anionic groups of the present invention include both units which are covalently attached to the polymer, as well as, external anions which are present to achieve charge neutrality. Non-limiting examples of anions suitable for use include halogen, inter alia, chloride; methyl sulfate; hydrogen sulfate, and sulfate.
The formulator will recognize by the herein described examples that the anion will typically be a unit which is part of the quaternizing reagent, inter alia, methyl chloride, dimethyl sulfate, benzyl bromide.
X is oxygen, -NR4-, and mixtures thereof, preferably oxygen.
Y is hydrogen, Ci-C4 linear alkyl, -N(Ri)2, or an anionic unit. Y is -N(Ri)2 preferably when Y is part of an R unit which is a backbone branching unit. Anionic units are defined herein as "units or moieties which are capable of having a negative charge". For example, a carboxylic acid unit, -CO2H, is neutral, however upon de-protonation the unit becomes an anionic unit, -C02 , the unit is therefore, "capable of having a negative charge. Non-limiting examples of anionic Y units include -(CH2)fCO2M, -C(O)(CH2)fCO2M, -(CH2)fPO3M, -(CH2)fOPO3M, -(CH2)fSO3M, -CH2(CHSO3M)-(CH2)fSO3M, -CH2(CHSO2M)(CH2)fSO3M, -C(O)CH2CH(SO3M)CO2M, -C(O)CH2CH(CO2M)NHCH(CO2M)CH2CO2M, -C(O)CH2CH(CO2M)NHCH2CO2M, -CH2CH(OZ)CH2O(RiO)rZ, -(CH2)fCH[O(R2O)rZ]-CHfO(R20)rZ, and mixtures thereof, wherein Z is hydrogen or an anionic unit non-limiting examples of which include -(CH2)fCO2M, -C(O)(CH2)fCO2M, -(CH2)fPO3M, -(CH2)fOPO3M, -(CH2)fSO3M, -CH2(CHSO3M)-(CH2)fSO3M, -CH2(CHSO2M)(CH2)fSO3M, -C(O)CH2CH(SO3M)CO2M, -C(O)CH2CH(CO2M)NHCH(CO2M)CH2CO2M, and mixtures thereof, M is a cation which provides charge neutrality.
5 Y units may also be oligomeric or polymeric, for example, the anionic Y unit having the formula:
OH i S03Na -CHzCHCHzO-CHzCHCHzSO3Na may be oligomerized or polymerized to form units having the general formula:
r O H
iO3Na CHzCHCHzO-CHzCHCHzS03Na n 10 wherein the index n represents a number greater than 1.
Further non-limiting examples of Y units which can be suitably oligomerized or polymerized include:
OH i S02Na -CHzCHCHzO-CHzCHCHzSO3Na and OH
15 -CH2CHCH2O-CH2CH2CH2SO3Na and OSO3Na - CHzCHCHzO- CHzCHzCHzOS O3Na As described herein above that a variety of factors, inter alia, the overall polymer structure, the nature of the formulation, the wash conditions, and the intended target cleaning 20 benefit, all can influence the formulator's optimal values for Qr , AQ, and Q(+).
For liquid laundry detergent compositions preferably less than about 90%, more preferably less than 75%, yet more preferably less than 50%, most preferably less than 40% of said Y units comprise an anionic moiety, inter alia, -SO3M comprising units.
The number of Y
units which comprise an anionic unit will vary from embodiment to embodiment.
M is hydrogen, 25 a water soluble cation, and mixtures thereof; the index f is from 0 to 6.
The index n represents the number of backbone units wherein the number of amino units in the backbone is equal to n + 1. For the purposes of the present invention the index n is from 1 to about 99. Branching units B are included in the total number of backbone units.
The following non-limiting examples indicate the manner in which the backbones of the present polyamines are assembled and defined.
The following is an non-limiting example of a backbone according to the present invention prior to quatrernization:
OH
OH
O~N,,,^,,O11_~N~~O
O H OH
O
OH
which has an index n equal to 4.
The following is also a non-limiting example of a backbone according to the present invention prior to quatrernization:
O
H2N N_,~ O~O~~N NH2 I
O
which has an index n equal to 4.
The following is a non-limiting example of a polyamine backbone which is fully quaternized.
+ N(CH3)3 OH
OH
O~~O N(CH3)3 O
O~C~~O CH
N~'O
O
OH
+N(CH3)3 The following is a non-limiting example of a polyamine backbone which is fully quaternized.
N(CH3)3 O
+ rf I CH3 +( 3 + N~~ O~~ I NCH)3 (CHAN CH O
The following is a non-limiting example of a final zwitterionic polyamine according to the present invention.
+
OH CH3- N[(CH2CH2O)2OS03M]2 N[(CH2CH2O)2OSO3M]2 OH
O +N Ci H3 ~
O OH
O [(CH2CH2O)2OS03M]
OH
+
N[(CH2CH2O)2OS03M]2 The following is a non-limiting example of a final zwitterionic polyamine according to the present invention.
N[(CH2CH2O)20SO3M]2 +N OI 0~~, NH3 N[(CH2CH20)20S03M]2 CH3-IN CH3 + I CH3 [(CH2CH20)20S03M]2 0 [(CH2CH2O)20S03M]2 Preferred zwitterionic polymers of the present invention have the formula:
r 1(R2O)fY
+ +I +
[Y(OR2)f]2 N-R N-R N-[(R2O)fY]2 Q L Q Q
m wherein R units have the formula -(R2O)WR3- wherein R2 and R3 are each independently selected from the group consisting of C2-C8 linear alkylene, C3-C8 branched alkylene, phenylene, substituted phenylene, and mixtures thereof. The R2 units of the formula above, which comprise -(R2O)rY units, are each ethylene; Y is hydrogen, -SO3M, and mixtures thereof, the index t is from 15 to 25; the index m is from 0 to 20, preferably from 0 to 10, more preferably from 0 to 4, yet more preferably from 0 to 3, most preferably from 0 to 2; the index w is from 1, preferably from about 2 to about 10, preferably to about 6.
Non-limiting examples of backbones according to the present invention include 1,9-diamino-3,7-dioxanonane; 1,10-diamino-3,8-dioxadecane; 1,12-diamino-3,10-dioxadodecane;
1,14-diamino-3,12-dioxatetradecane. However, backbones which comprise more than two nitrogens may comprise one or more repeating units having the formula:
H2N- [R-NH] -for example a unit having the formula:
H2N- [CH2CH2OCH2CH2NH] -is described herein as 1,5-diamino-3-oxapentane. A backbone which comprises two 1,5-diamino-3-oxapentane units has the formula:
H2NCH2CH2OCH2CH2NHCH2CH2OCH2CH2NH2.
Further suitable repeating units include 1,8-diamino-3,6-diaxaoctane; 1,11-diamino-3,6,9-trioxaundecane; 1,5-diamino-1,4-dimethyl-3-oxaheptane; 1,8-diamino-1,4,7-trimethyl-3,6-dioxaoctane; 1,9-diamino-5-oxanonane; 1,14-diamino-5,10-dioxatetradecane.
The zwitterionic polymers of the present invention preferably comprise polyamine backbone which are derivatives of two types of backbone units:
i) normal oligomers which comprise R units of type (i), which are preferably polyamines having the formula:
HzN-(CHz)~n+l [NH-(CHz)~m [NB-(CHz)~n NH2 wherein B is a continuation of the polyamine chain by branching, n is preferably 0, m is from 0 to 3, x is 2 to 8, preferably from 3 to 6; and ii) hydrophilic oligomers which comprise R units of type (ii), which are preferably polyamines having the formula:
HzN-[(CHz)XO]y(CHz)~-[NH-[(CHz),,O]y(CHz)jm NH2 wherein m is from 0 to 3; each x is independently from 2 to 8, preferably from 2 to 6; y is preferably from 1 to 8.
Depending upon the degree of hydrophilic character needed in the zwitterionic backbones, the formulator may assemble higher oligomers from these constituent parts by using R units of types (iii), (iv), and (v). Non-limiting examples include the epihalohydrin condensate having the formula:
H H OH H H
H2N-(CH2)6-N-(CH2)6-N-CH2CHCH27N-(CHz)6--N-(CHz)6---NHz or the hybrid oligomer having the formula:
OH OH
H2N(CH2)3O(CH2)4O(CH2)3N-CH2CHCH2O-(CH2)40-CH2CHCH2- N(CH2)3O(CH2)4O(CH2)3NH2 wherein each backbone comprises a mixture of R units.
As described herein before, the formulator may form zwitterionic polymers which have an excess of charge (Qr less than 1 or greater than 1) or an equivalent amount of charge type (Qr equal to 1). An example of a preferred zwitterionic polyamine according to the present invention which has an excess of anionic charged units, Qr equal to 2, has the formula:
[CH2CH2O]20S03 I + [CH2CH2O]20S03 CH3 N~O ~ I
I O +N-CH3 [CH2CH2O]20S03 I
[CH2CH2O]20S03 wherein R is a 1,3-propyleneoxy-1,4-butyleneoxy-1,3-propylene unit, w is 2; Ri is -(R'O)rY, wherein R2 is ethylene, each Y is -S03, Q is methyl, m is 0, n is 0, t is 20.
For zwitterionic polyamines of the present invention, it will be recognized by the formulator that not every Ri unit will have a-S03- moiety capping said Ri unit. For the above example, the final zwitterionic 5 polyamine mixture comprises at least about 90% Y units which are -S03-units.
As described herein before, the formulator may form zwitterionic polymers which have an excess of charge or an equivalent amount of charge type. An example of a preferred zwitterionic polyamine according to the present invention which has an excess of backbone quaternized units, has the formula:
+ ~CHZCH20)Z0H +N HZCH2O)ZOH ~CHZCH20)Z0H
H3C-N ICH + N-CH3 (CH2CH2O)20S03M
(CH2CH20)20S03M 3 wherein R is a 1,5-hexamethylene, w is 2; Ri is -(R2O)rY, wherein R2 is ethylene, Y is hydrogen or -SO3M, Q is methyl, m is 1, t is 20. For zwitterionic polyamines of the present invention, it will be recognized by the formulator that not every Ri unit will have a-SO3 moiety capping said Ri unit. For the above example, the final zwitterionic polyamine mixture comprises at least about 40% Y units which are -S03- units.
The liquid detergent compositions herein are in the form of an aqueous solution or uniform dispersion or suspension of surfactant, polymer, and optional other ingredients, some of which may normally be in solid form, that have been combined with the normally liquid components of the composition, such as the non-aminofunctional surfactant and any other normally liquid optional ingredients. Such a solution, dispersion or suspension will be acceptably phase stable and will typically have a viscosity which ranges from about 100 to 600 cps, more preferably from about 150 to 400 cps. For purposes of this invention, viscosity is measured with a Brookfield LVDV-II+ viscometer apparatus using a #21 spindle.
The liquid detergent compositions herein can be prepared by combining the components thereof in any convenient order and by mixing, e.g., agitating, the resulting component combination to form a phase stable liquid detergent composition. In a preferred process for preparing such compositions, a liquid matrix is formed containing at least a major proportion, and preferably substantially all, of the liquid components, e.g., nonionic surfactant, the non-surface active liquid carriers and other optional liquid components, with the liquid components being thoroughly admixed by imparting shear agitation to this liquid combination.
For example, rapid stirring with a mechanical stirrer may usefully be employed. While shear agitation is maintained, substantially all of any anionic surfactants and the solid form ingredients can be added. Agitation of the mixture is continued, and if necessary, can be increased at this point to form a solution or a uniform dispersion of insoluble solid phase particulates within the liquid phase. After some or all of the solid-form materials have been added to this agitated mixture, particles of any enzyme material to be included, e.g., enzyme prills, are incorporated. As a variation of the composition preparation procedure hereinbefore described, one or more of the solid components may be added to the agitated mixture as a solution or slurry of particles premixed with a minor portion of one or more of the liquid components. After addition of all of the composition components, agitation of the mixture is continued for a period of time sufficient to form compositions having the requisite viscosity and phase stability characteristics. Frequently this will involve agitation for a period of from about 30 to 60 minutes.
The compositions of this invention, prepared as hereinbefore described, can be used to form aqueous washing solutions for use in the laundering of fabrics.
Generally, an effective amount of such compositions is added to water, preferably in a conventional fabric laundering automatic washing machine, to form such aqueous laundering solutions. The aqueous washing solution so formed is then contacted, preferably under agitation, with the fabrics to be laundered therewith. An effective amount of the liquid detergent compositions herein added to water to form aqueous laundering solutions can comprise amounts sufficient to form from about 500 to 7,000 ppm of composition in aqueous washing solution. More preferably, from about 1,000 to 3,000 ppm of the detergent compositions herein will be provided in aqueous washing solution.
EXAMPLES
The following examples illustrate the compositions of the present invention but are not necessarily meant to limit or otherwise define the scope of the invention herein.
Example 1 The following liquid formulas are within the scope of the present invention.
Ingredient la lb 1c 1d le wt % wt % wt % wt % wt %
Sodium alkyl ether sulfate 20.5% 20.5 20.5 branched alcohol sulfate 5.8% 5.8 5.8 linear alkylbenzene sulfonic acid 2.5% 2.5 2.5 alkyl ethoxylate 0.8% 0.8 0.8 amine oxide citric acid 3.5% 3.5 3.5 fatty acid 2.0% 2.0 2.0 Protease 0.7% 0.7 0.7 Amylase 0.37% 0.37 0.37 Lipase Borax 3.0% 3.0 3.0 Calcium and sodium formate 0.22% 0.22 0.22 formic acid amine ethoxylate polymers 1.2% 1.2 1.2 zwitterionic amine ethoxylate 1.6% 1.6 1.6 polymer Sodium polyacrylatei 0.6%
Sodium polyacrylate copolymer2 0.6 Sodium polyacrylate copolymer3 1.6 DTPA4 0.25%
fluorescent whitening agent 0.2%
Ethanol 2.9%
Propanediol 5.0%
diethylene glycol 2.56%
polyethylene glyco14000 0.11%
Ethanolamine 2.7%
Sodium hydroxide 3.67%
Sodium cumene sulfonate Silicone suds suppressor 0.01%
Perfume 0.5%
Acid Blue 75 0.01%
opacifier6 Water balance balance balance balance balance 100.0% 100.0% 100.0% 100.0% 100.0%
"Sodium salt of polyacrylic acid, Mn = 1000-4000 amu, PD < 5.
2, Sodium salt of 90:10 polyacrylic acid-ethylene copolymer, Mn = 1000-4000 amu, PD < 5.
3. Sodium salt of 90:10 polyacrylic acid-polyethyleneglycol acrylate copolymer, Mn = 1000-4000 amu, PD < 5.
4 diethylenetriaminepentaacetic acid, sodium salt s a non-tinting dye used to adjust formula color 6 Acusol OP 301 All documents cited in the Detailed Description of the Invention are, are, in relevant part, incorporated herein by reference; the citation of any document is not to be construed as an admission that it is prior art with respect to the present invention.
While particular embodiments of the present invention have been illustrated and described, it would be obvious to those skilled in the art that various other changes and modifications can be made without departing from the spirit and scope of the invention. It is therefore intended to cover in the appended claims all such changes and modifications that are within the scope of this invention.
20 I-CHzCHzO--H
The polyacrylic acid based polymers of the present invention may also be beneficially 5 combined with zwitterionic polyamine additives disclosed in U.S. 6,660,711.
These zwitterionic polyamines of the present invention have the formula:
[J-R]n-J
wherein the [J-R] units represent the amino units which comprise the main backbone and any branching chains. Preferably the zwitterionic polyamines prior to modification, inter alia, 10 quaternization, substitution of an amino unit hydrogen with an alkyleneoxy unit, have backbones which comprise from 2 to about 100 amino units. The index n which describes the number of backbone units present is further described herein below.
J units are the backbone amino units, said units are selected from the group consisting of:
15 i) primary amino units having the formula:
(Ri)zN.
ii) secondary amino units having the formula:
-RiN.
iii) tertiary amino units having the formula:
B
-N=
iv) primary quaternary amino units having the formula:
(Ri)2N
Q;
v) secondary quaternary amino units having the formula:
RiN
5 Q;
vi) tertiary quaternary amino units having the formula:
B
- N+
I
Q;
vii) primary N-oxide amino units having the formula:
(RI)2N
O=
10 viii) secondary N-oxide amino units having the formula:
- RiN
ix) tertiary N-oxide amino units having the formula:
B
- N
O=
x) and mixtures thereof.
15 B units which have the formula:
[J- R]
represent a continuation of the zwitterionic polyamine backbone by branching.
The number of B
units present, as well as, any further amino units which comprise the branches are reflected in the total value of the index n.
20 The backbone amino units of the zwitterionic polymers are connected by one or more R
units, said R units are selected from the group consisting of:
i) C2-Ci2 linear alkylene, C3-Ci2 branched alkylene, or mixtures thereof;
preferably C3-C6 alkylene. When two adjacent nitrogens of the polyamine backbone are N-oxides, preferably the alkylene backbone unit which separates said units are units or greater.
ii) alkyleneoxyalkylene units having the formula:
- (R2O)w(R3)-wherein R2 is selected from the group consisting of ethylene, 1,2-propylene, 1,3-propylene, 1,2-butylene, 1,4-butylene, and mixtures thereof; R3 is C2-C8 linear alkylene, C3-C8 branched alkylene, phenylene, substituted phenylene, and mixtures thereof; the index w is from 0 to about 25. R2 and R3 units may also comprise other backbone units. When comprising alkyleneoxyalkylene units, in one embodiment R2 and R3 units are each preferably ethylene or mixtures of ethylene, propylene and butylene, more preferably ethylene; in another embodiment R2 and R3 units are preferably mixtures of ethylene, propylene and butylene; the index w is from 1, preferably from about 2 to about 10, preferably to about 6.
iii) hydroxyalkylene units having the formula:
-(CHz),(CH)y(CHz)z wherein R4 is hydrogen, Ci-C6 alkyl, -(CH2)õ(R2O)r(CH2)õY, and mixtures thereof.
When R units comprise hydroxyalkylene units, R4 is preferably hydrogen or -(CH2)õ(R2O)r(CH2)õY wherein the index t is greater than 0, preferably from 10 to 30; the index u is from 0 to 6; and Y is preferably hydrogen or an anionic unit, more preferably -SO3M. The indices x, y, and z are each independently from 1 to 6, preferably the indices are each equal to 1 and R4 is hydrogen (2-hydroxypropylene unit) or (R2O)rY, or for polyhydroxy units y is preferably 2 or 3.
A preferred hydroxyalkylene unit is the 2-hydroxypropylene unit which can, for example, be suitably formed from glycidyl ether forming reagents, inter alia, epihalohydrin.
iv) hydroxyalkylene/oxyalkylene units having the formula:
(CH2)x(CH)y(CH2)z(X)r R20)w (CH2)x(CH)y(CH2)z(X)r j k wherein R2 , R4, and the indices w, x, y, and z are the same as defined herein above. X is oxygen or the amino unit -NR4-, the index r is 0 or 1. The indices j and k are each independently from 1 to 20. When alkyleneoxy units are absent the index w is 0. Non-limiting examples of preferred hydroxyalkylene/oxyalkylene units have the formula:
OH OH
I I
-CH2CHCH2O-(CH2CH2CH2O)2 CH2CHCH2 -OH OH OH
CH2CHCH2O-(CH2CH2O)3 CH2CHCH2O CH2CHCH2 OH OH
CH2CHCH2O- (CH2CH2O) CH2CHCH2 OH OH
CH2CHCH2O- (CH2CH2CH2O)4 CH2CHCH2 v) carboxyalkyleneoxy units having the formula:
- (R30)w(R3)w(X)r- II C- (X)r- R3 II
- (X)r- C- (X)r(R3)w(OR3)w-.
wherein R2 , R3, X, r, and w are the same as defined herein above. Non-limiting examples of preferred carboxyalkyleneoxy units include:
II II
- CHz C- O- CHzCHzCHzCHz O- C- CHz .
I
O O
~I --,a I I
CHz C- NH NH- C- CHz O O
-(CH2CH2CH2O)4 C C-(OCH2CH2CH2)4 vi) backbone branching units having the formula:
(CH2)x( ~ )y(CH2)z(~')r (R20)w (CH2)x( ~ )y(CH2)z(~')r i k wherein R4 is hydrogen, Ci-C6 alkyl, -(CH2)õ(R2O)r(CH2)õY, and mixtures thereof.
When R units comprise backbone branching units, R4 is preferably hydrogen or -(CH2)õ(R2O)r-(CH2)õY wherein the index t is greater than 0, preferably from 10 to 30; the index u is from 0 to 6; and Y is hydrogen, Ci-C4 linear alkyl, -N(Ri)2, an anionic unit, and mixtures thereof; preferably Y is hydrogen, or - N(Ri)2. A
preferred embodiment of backbone branching units comprises R4 equal to -(R2O)rH. The indices x, y, and z are each independently from 0 to 6.
vii) The formulator may suitably combine any of the above described R units to make a zwitterionic polyamine having a greater or lesser degree of hydrophilic character.
Ri units are the units which are attached to the backbone nitrogens. Ri units are selected from the group consisting of:
i) hydrogen; which is the unit typically present prior to any backbone modification.
ii) Ci-C22 alkyl, preferably Ci-C4 alkyl, more preferably methyl or ethyl, most preferably methyl. A preferred embodiment of the present invention in the instance wherein Ri units are attached to quaternary units (iv) or (v), Ri is the same unit as quaternizing unit Q. For example a J unit having the formula:
+
(CH3)2N
iii) C7-C22 arylalkyl, preferably benzyl.
iv) -[CH2CH(OR4)CH2O]s(R2O)rY; wherein R2 and R4 are the same as defined herein above, preferably when Ri units comprise R2 units, R2 is preferably ethylene.
The value of the index s is from 0 to 5. For the purposes of the present invention the index t is expressed as an average value, said average value from about 0.5 to about 100. The formulator may lightly alkyleneoxylate the backbone nitrogens in a manner wherein not every nitrogen atom comprises an Ri unit which is an alkyleneoxy unit thereby rendering the value of the index t less than 1.
v) Anionic units as described herein below.
vi) The formulator may suitably combine one or more of the above described Ri units when substituting the backbone of the zwitterionic polymers of the present invention.
Q is a quaternizing unit selected from the group consisting of Ci-C4 linear alkyl, benzyl, and mixtures thereof, preferably methyl. As described herein above, preferably Q is the same as Ri when Ri comprises an alkyl unit. For each backbone N+ unit (quaternary nitrogen) there will be an anion to provide charge neutrality. The anionic groups of the present invention include both units which are covalently attached to the polymer, as well as, external anions which are present to achieve charge neutrality. Non-limiting examples of anions suitable for use include halogen, inter alia, chloride; methyl sulfate; hydrogen sulfate, and sulfate.
The formulator will recognize by the herein described examples that the anion will typically be a unit which is part of the quaternizing reagent, inter alia, methyl chloride, dimethyl sulfate, benzyl bromide.
X is oxygen, -NR4-, and mixtures thereof, preferably oxygen.
Y is hydrogen, Ci-C4 linear alkyl, -N(Ri)2, or an anionic unit. Y is -N(Ri)2 preferably when Y is part of an R unit which is a backbone branching unit. Anionic units are defined herein as "units or moieties which are capable of having a negative charge". For example, a carboxylic acid unit, -CO2H, is neutral, however upon de-protonation the unit becomes an anionic unit, -C02 , the unit is therefore, "capable of having a negative charge. Non-limiting examples of anionic Y units include -(CH2)fCO2M, -C(O)(CH2)fCO2M, -(CH2)fPO3M, -(CH2)fOPO3M, -(CH2)fSO3M, -CH2(CHSO3M)-(CH2)fSO3M, -CH2(CHSO2M)(CH2)fSO3M, -C(O)CH2CH(SO3M)CO2M, -C(O)CH2CH(CO2M)NHCH(CO2M)CH2CO2M, -C(O)CH2CH(CO2M)NHCH2CO2M, -CH2CH(OZ)CH2O(RiO)rZ, -(CH2)fCH[O(R2O)rZ]-CHfO(R20)rZ, and mixtures thereof, wherein Z is hydrogen or an anionic unit non-limiting examples of which include -(CH2)fCO2M, -C(O)(CH2)fCO2M, -(CH2)fPO3M, -(CH2)fOPO3M, -(CH2)fSO3M, -CH2(CHSO3M)-(CH2)fSO3M, -CH2(CHSO2M)(CH2)fSO3M, -C(O)CH2CH(SO3M)CO2M, -C(O)CH2CH(CO2M)NHCH(CO2M)CH2CO2M, and mixtures thereof, M is a cation which provides charge neutrality.
5 Y units may also be oligomeric or polymeric, for example, the anionic Y unit having the formula:
OH i S03Na -CHzCHCHzO-CHzCHCHzSO3Na may be oligomerized or polymerized to form units having the general formula:
r O H
iO3Na CHzCHCHzO-CHzCHCHzS03Na n 10 wherein the index n represents a number greater than 1.
Further non-limiting examples of Y units which can be suitably oligomerized or polymerized include:
OH i S02Na -CHzCHCHzO-CHzCHCHzSO3Na and OH
15 -CH2CHCH2O-CH2CH2CH2SO3Na and OSO3Na - CHzCHCHzO- CHzCHzCHzOS O3Na As described herein above that a variety of factors, inter alia, the overall polymer structure, the nature of the formulation, the wash conditions, and the intended target cleaning 20 benefit, all can influence the formulator's optimal values for Qr , AQ, and Q(+).
For liquid laundry detergent compositions preferably less than about 90%, more preferably less than 75%, yet more preferably less than 50%, most preferably less than 40% of said Y units comprise an anionic moiety, inter alia, -SO3M comprising units.
The number of Y
units which comprise an anionic unit will vary from embodiment to embodiment.
M is hydrogen, 25 a water soluble cation, and mixtures thereof; the index f is from 0 to 6.
The index n represents the number of backbone units wherein the number of amino units in the backbone is equal to n + 1. For the purposes of the present invention the index n is from 1 to about 99. Branching units B are included in the total number of backbone units.
The following non-limiting examples indicate the manner in which the backbones of the present polyamines are assembled and defined.
The following is an non-limiting example of a backbone according to the present invention prior to quatrernization:
OH
OH
O~N,,,^,,O11_~N~~O
O H OH
O
OH
which has an index n equal to 4.
The following is also a non-limiting example of a backbone according to the present invention prior to quatrernization:
O
H2N N_,~ O~O~~N NH2 I
O
which has an index n equal to 4.
The following is a non-limiting example of a polyamine backbone which is fully quaternized.
+ N(CH3)3 OH
OH
O~~O N(CH3)3 O
O~C~~O CH
N~'O
O
OH
+N(CH3)3 The following is a non-limiting example of a polyamine backbone which is fully quaternized.
N(CH3)3 O
+ rf I CH3 +( 3 + N~~ O~~ I NCH)3 (CHAN CH O
The following is a non-limiting example of a final zwitterionic polyamine according to the present invention.
+
OH CH3- N[(CH2CH2O)2OS03M]2 N[(CH2CH2O)2OSO3M]2 OH
O +N Ci H3 ~
O OH
O [(CH2CH2O)2OS03M]
OH
+
N[(CH2CH2O)2OS03M]2 The following is a non-limiting example of a final zwitterionic polyamine according to the present invention.
N[(CH2CH2O)20SO3M]2 +N OI 0~~, NH3 N[(CH2CH20)20S03M]2 CH3-IN CH3 + I CH3 [(CH2CH20)20S03M]2 0 [(CH2CH2O)20S03M]2 Preferred zwitterionic polymers of the present invention have the formula:
r 1(R2O)fY
+ +I +
[Y(OR2)f]2 N-R N-R N-[(R2O)fY]2 Q L Q Q
m wherein R units have the formula -(R2O)WR3- wherein R2 and R3 are each independently selected from the group consisting of C2-C8 linear alkylene, C3-C8 branched alkylene, phenylene, substituted phenylene, and mixtures thereof. The R2 units of the formula above, which comprise -(R2O)rY units, are each ethylene; Y is hydrogen, -SO3M, and mixtures thereof, the index t is from 15 to 25; the index m is from 0 to 20, preferably from 0 to 10, more preferably from 0 to 4, yet more preferably from 0 to 3, most preferably from 0 to 2; the index w is from 1, preferably from about 2 to about 10, preferably to about 6.
Non-limiting examples of backbones according to the present invention include 1,9-diamino-3,7-dioxanonane; 1,10-diamino-3,8-dioxadecane; 1,12-diamino-3,10-dioxadodecane;
1,14-diamino-3,12-dioxatetradecane. However, backbones which comprise more than two nitrogens may comprise one or more repeating units having the formula:
H2N- [R-NH] -for example a unit having the formula:
H2N- [CH2CH2OCH2CH2NH] -is described herein as 1,5-diamino-3-oxapentane. A backbone which comprises two 1,5-diamino-3-oxapentane units has the formula:
H2NCH2CH2OCH2CH2NHCH2CH2OCH2CH2NH2.
Further suitable repeating units include 1,8-diamino-3,6-diaxaoctane; 1,11-diamino-3,6,9-trioxaundecane; 1,5-diamino-1,4-dimethyl-3-oxaheptane; 1,8-diamino-1,4,7-trimethyl-3,6-dioxaoctane; 1,9-diamino-5-oxanonane; 1,14-diamino-5,10-dioxatetradecane.
The zwitterionic polymers of the present invention preferably comprise polyamine backbone which are derivatives of two types of backbone units:
i) normal oligomers which comprise R units of type (i), which are preferably polyamines having the formula:
HzN-(CHz)~n+l [NH-(CHz)~m [NB-(CHz)~n NH2 wherein B is a continuation of the polyamine chain by branching, n is preferably 0, m is from 0 to 3, x is 2 to 8, preferably from 3 to 6; and ii) hydrophilic oligomers which comprise R units of type (ii), which are preferably polyamines having the formula:
HzN-[(CHz)XO]y(CHz)~-[NH-[(CHz),,O]y(CHz)jm NH2 wherein m is from 0 to 3; each x is independently from 2 to 8, preferably from 2 to 6; y is preferably from 1 to 8.
Depending upon the degree of hydrophilic character needed in the zwitterionic backbones, the formulator may assemble higher oligomers from these constituent parts by using R units of types (iii), (iv), and (v). Non-limiting examples include the epihalohydrin condensate having the formula:
H H OH H H
H2N-(CH2)6-N-(CH2)6-N-CH2CHCH27N-(CHz)6--N-(CHz)6---NHz or the hybrid oligomer having the formula:
OH OH
H2N(CH2)3O(CH2)4O(CH2)3N-CH2CHCH2O-(CH2)40-CH2CHCH2- N(CH2)3O(CH2)4O(CH2)3NH2 wherein each backbone comprises a mixture of R units.
As described herein before, the formulator may form zwitterionic polymers which have an excess of charge (Qr less than 1 or greater than 1) or an equivalent amount of charge type (Qr equal to 1). An example of a preferred zwitterionic polyamine according to the present invention which has an excess of anionic charged units, Qr equal to 2, has the formula:
[CH2CH2O]20S03 I + [CH2CH2O]20S03 CH3 N~O ~ I
I O +N-CH3 [CH2CH2O]20S03 I
[CH2CH2O]20S03 wherein R is a 1,3-propyleneoxy-1,4-butyleneoxy-1,3-propylene unit, w is 2; Ri is -(R'O)rY, wherein R2 is ethylene, each Y is -S03, Q is methyl, m is 0, n is 0, t is 20.
For zwitterionic polyamines of the present invention, it will be recognized by the formulator that not every Ri unit will have a-S03- moiety capping said Ri unit. For the above example, the final zwitterionic 5 polyamine mixture comprises at least about 90% Y units which are -S03-units.
As described herein before, the formulator may form zwitterionic polymers which have an excess of charge or an equivalent amount of charge type. An example of a preferred zwitterionic polyamine according to the present invention which has an excess of backbone quaternized units, has the formula:
+ ~CHZCH20)Z0H +N HZCH2O)ZOH ~CHZCH20)Z0H
H3C-N ICH + N-CH3 (CH2CH2O)20S03M
(CH2CH20)20S03M 3 wherein R is a 1,5-hexamethylene, w is 2; Ri is -(R2O)rY, wherein R2 is ethylene, Y is hydrogen or -SO3M, Q is methyl, m is 1, t is 20. For zwitterionic polyamines of the present invention, it will be recognized by the formulator that not every Ri unit will have a-SO3 moiety capping said Ri unit. For the above example, the final zwitterionic polyamine mixture comprises at least about 40% Y units which are -S03- units.
The liquid detergent compositions herein are in the form of an aqueous solution or uniform dispersion or suspension of surfactant, polymer, and optional other ingredients, some of which may normally be in solid form, that have been combined with the normally liquid components of the composition, such as the non-aminofunctional surfactant and any other normally liquid optional ingredients. Such a solution, dispersion or suspension will be acceptably phase stable and will typically have a viscosity which ranges from about 100 to 600 cps, more preferably from about 150 to 400 cps. For purposes of this invention, viscosity is measured with a Brookfield LVDV-II+ viscometer apparatus using a #21 spindle.
The liquid detergent compositions herein can be prepared by combining the components thereof in any convenient order and by mixing, e.g., agitating, the resulting component combination to form a phase stable liquid detergent composition. In a preferred process for preparing such compositions, a liquid matrix is formed containing at least a major proportion, and preferably substantially all, of the liquid components, e.g., nonionic surfactant, the non-surface active liquid carriers and other optional liquid components, with the liquid components being thoroughly admixed by imparting shear agitation to this liquid combination.
For example, rapid stirring with a mechanical stirrer may usefully be employed. While shear agitation is maintained, substantially all of any anionic surfactants and the solid form ingredients can be added. Agitation of the mixture is continued, and if necessary, can be increased at this point to form a solution or a uniform dispersion of insoluble solid phase particulates within the liquid phase. After some or all of the solid-form materials have been added to this agitated mixture, particles of any enzyme material to be included, e.g., enzyme prills, are incorporated. As a variation of the composition preparation procedure hereinbefore described, one or more of the solid components may be added to the agitated mixture as a solution or slurry of particles premixed with a minor portion of one or more of the liquid components. After addition of all of the composition components, agitation of the mixture is continued for a period of time sufficient to form compositions having the requisite viscosity and phase stability characteristics. Frequently this will involve agitation for a period of from about 30 to 60 minutes.
The compositions of this invention, prepared as hereinbefore described, can be used to form aqueous washing solutions for use in the laundering of fabrics.
Generally, an effective amount of such compositions is added to water, preferably in a conventional fabric laundering automatic washing machine, to form such aqueous laundering solutions. The aqueous washing solution so formed is then contacted, preferably under agitation, with the fabrics to be laundered therewith. An effective amount of the liquid detergent compositions herein added to water to form aqueous laundering solutions can comprise amounts sufficient to form from about 500 to 7,000 ppm of composition in aqueous washing solution. More preferably, from about 1,000 to 3,000 ppm of the detergent compositions herein will be provided in aqueous washing solution.
EXAMPLES
The following examples illustrate the compositions of the present invention but are not necessarily meant to limit or otherwise define the scope of the invention herein.
Example 1 The following liquid formulas are within the scope of the present invention.
Ingredient la lb 1c 1d le wt % wt % wt % wt % wt %
Sodium alkyl ether sulfate 20.5% 20.5 20.5 branched alcohol sulfate 5.8% 5.8 5.8 linear alkylbenzene sulfonic acid 2.5% 2.5 2.5 alkyl ethoxylate 0.8% 0.8 0.8 amine oxide citric acid 3.5% 3.5 3.5 fatty acid 2.0% 2.0 2.0 Protease 0.7% 0.7 0.7 Amylase 0.37% 0.37 0.37 Lipase Borax 3.0% 3.0 3.0 Calcium and sodium formate 0.22% 0.22 0.22 formic acid amine ethoxylate polymers 1.2% 1.2 1.2 zwitterionic amine ethoxylate 1.6% 1.6 1.6 polymer Sodium polyacrylatei 0.6%
Sodium polyacrylate copolymer2 0.6 Sodium polyacrylate copolymer3 1.6 DTPA4 0.25%
fluorescent whitening agent 0.2%
Ethanol 2.9%
Propanediol 5.0%
diethylene glycol 2.56%
polyethylene glyco14000 0.11%
Ethanolamine 2.7%
Sodium hydroxide 3.67%
Sodium cumene sulfonate Silicone suds suppressor 0.01%
Perfume 0.5%
Acid Blue 75 0.01%
opacifier6 Water balance balance balance balance balance 100.0% 100.0% 100.0% 100.0% 100.0%
"Sodium salt of polyacrylic acid, Mn = 1000-4000 amu, PD < 5.
2, Sodium salt of 90:10 polyacrylic acid-ethylene copolymer, Mn = 1000-4000 amu, PD < 5.
3. Sodium salt of 90:10 polyacrylic acid-polyethyleneglycol acrylate copolymer, Mn = 1000-4000 amu, PD < 5.
4 diethylenetriaminepentaacetic acid, sodium salt s a non-tinting dye used to adjust formula color 6 Acusol OP 301 All documents cited in the Detailed Description of the Invention are, are, in relevant part, incorporated herein by reference; the citation of any document is not to be construed as an admission that it is prior art with respect to the present invention.
While particular embodiments of the present invention have been illustrated and described, it would be obvious to those skilled in the art that various other changes and modifications can be made without departing from the spirit and scope of the invention. It is therefore intended to cover in the appended claims all such changes and modifications that are within the scope of this invention.
Claims (10)
1. A liquid detergent composition comprising a polymer comprising polyacrylic acid monomers characterized in that the polyacrylic acid monomers have a number average molecular weight of from 1000 to 10,000 amu and a polydispersity of less than 5, and wherein the liquid detergent comprises less than 50%, preferably less than 40%, of any non-aminofunctional solvent.
2. A liquid detergent composition according to Claim 1 wherein the polymer is a homopolymer of polyacrylic acid monomer, preferably where the polyacrylic acid homopolymer has a number average molecular weight of from 1000 to 4000 amu, preferably from 1100 to 3000 amu.
3. A liquid detergent composition according to Claim 1 wherein the polymer is a copolymer comprising a mixture of acrylic acid monomers and hydrophilic monomers, preferably selected from the group consisting of polyethylene glycol acrylates, dicarboxylates, sulfonated monomers and mixtures thereof, the copolymer having a number average molecular weight of from 1000 to 4000 amu and a polydispersity of less than 3.5.
4. A liquid detergent composition according to Claim 1 wherein the copolymer comprises a mixture of acrylic acid monomers and hydrophobic monomers, preferably selected from the group consisting of alkyl, aryl, silicone, propoxy, butoxy monomers and mixures thereof, the copolymer having a number average molecular weight of from 1000 to 10,000 amu and a polydispersity of less than 5Ø
5. A liquid detergent composition comprising a polymer comprising polyacrylic acid monomers having a number average molecular weight of from 1000 to 10,000 amu and a polydispersity of less than 5 and a water-soluble or dispersible, modified polyamine compound.
6. A liquid detergent composition according to Claim 5 wherein the water-soluble or dispersible, modified polyamine compound comprises a polyamine backbone corresponding to the formula:
having a modified polyamine formula V(n+1)W m Y n Z, or a polyamine backbone corresponding to the formula:
having a modified polyamine formula V(n-k+1)W m Y n Y' k Z, wherein k is less than or equal to n, said polyamine backbone prior to modification has a molecular weight greater than 200 daltons, wherein i) V units are terminal units having the formula:
ii) W units are backbone units having the formula:
iii) Y units are branching units having the formula:
; and iv) Z units are terminal units having the formula:
wherein backbone linking R units are selected from the group consisting of C2-C12 alkylene, -(R1O)x R3(OR1)x-, -(CH2CH(OR2)CH2O)z(R1O)y R1(OCH2CH(OR2)CH2)w-, CH2CH(OR2)CH2- and mixtures thereof; provided that when R comprises C1-C12 alkylene R
also comprises at least one -(R1O)x R3(OR1)x-, -(CH2CH(OR2)CH2O)z(R1O)y R1-(OCH2CH(OR2)CH2)w-, or -CH2CH(OR2)CH2-unit; R1 is C2-C6 alkylene and mixtures thereof;
R2 is hydrogen, -(R1O)x B, and mixtures thereof;
R3 is C1-C12 alkylene, C3-C12 hydroxyalkylene, C4-C12 dihydroxy-alkylene, C8-dialkylarylene, -C(O)-, -C(O)NHR5NHC(O)-, -C(O)(R4)r C(O)-, -CH2CH(OH)CH20-(R1O)y R1OCH2CH(OH)CH2-, and mixtures thereof;
R4 is C1-C12 alkylene, C4-C12 alkenylene, C8-C12 arylalkylene, C6-C10 arylene, and mixtures thereof;
R5 is C2-C12 alkylene or C6-C12 arylene;
E units are selected from the group consisting of hydrogen, -(CH2)p-CO2M, -(CH2)q SO3M, -CH(CH2CO2M)CO2M, -(CH2)p PO3M, -(R1O)x B, and mixtures thereof; provided that when any E unit of a nitrogen is a hydrogen, said nitrogen is not also an N-oxide;
B is hydrogen, -(CH2)q SO3M, -(CH2)p CO2M, -(CH2)q CH(SO3M)-CH2SO3M, -(CH2)q CH(SO2M)CH2SO3M, -(CH2)p PO3M, -PO3M, and mixtures thereof;
M is hydrogen or a water soluble cation in sufficient amount to satisfy charge balance;
X is a water soluble anion; k has the value from 0 to 20; m has the value from 4 to 400; n has the value from 0 to 200; p has the value from 1 to 6, q has the value from 0 to 6;
r has the value 0 or 1; w has the value 0 or 1; x has the value from 1 to 100; y has the value from 0 to 100; and z has the value 0 or 1.
having a modified polyamine formula V(n+1)W m Y n Z, or a polyamine backbone corresponding to the formula:
having a modified polyamine formula V(n-k+1)W m Y n Y' k Z, wherein k is less than or equal to n, said polyamine backbone prior to modification has a molecular weight greater than 200 daltons, wherein i) V units are terminal units having the formula:
ii) W units are backbone units having the formula:
iii) Y units are branching units having the formula:
; and iv) Z units are terminal units having the formula:
wherein backbone linking R units are selected from the group consisting of C2-C12 alkylene, -(R1O)x R3(OR1)x-, -(CH2CH(OR2)CH2O)z(R1O)y R1(OCH2CH(OR2)CH2)w-, CH2CH(OR2)CH2- and mixtures thereof; provided that when R comprises C1-C12 alkylene R
also comprises at least one -(R1O)x R3(OR1)x-, -(CH2CH(OR2)CH2O)z(R1O)y R1-(OCH2CH(OR2)CH2)w-, or -CH2CH(OR2)CH2-unit; R1 is C2-C6 alkylene and mixtures thereof;
R2 is hydrogen, -(R1O)x B, and mixtures thereof;
R3 is C1-C12 alkylene, C3-C12 hydroxyalkylene, C4-C12 dihydroxy-alkylene, C8-dialkylarylene, -C(O)-, -C(O)NHR5NHC(O)-, -C(O)(R4)r C(O)-, -CH2CH(OH)CH20-(R1O)y R1OCH2CH(OH)CH2-, and mixtures thereof;
R4 is C1-C12 alkylene, C4-C12 alkenylene, C8-C12 arylalkylene, C6-C10 arylene, and mixtures thereof;
R5 is C2-C12 alkylene or C6-C12 arylene;
E units are selected from the group consisting of hydrogen, -(CH2)p-CO2M, -(CH2)q SO3M, -CH(CH2CO2M)CO2M, -(CH2)p PO3M, -(R1O)x B, and mixtures thereof; provided that when any E unit of a nitrogen is a hydrogen, said nitrogen is not also an N-oxide;
B is hydrogen, -(CH2)q SO3M, -(CH2)p CO2M, -(CH2)q CH(SO3M)-CH2SO3M, -(CH2)q CH(SO2M)CH2SO3M, -(CH2)p PO3M, -PO3M, and mixtures thereof;
M is hydrogen or a water soluble cation in sufficient amount to satisfy charge balance;
X is a water soluble anion; k has the value from 0 to 20; m has the value from 4 to 400; n has the value from 0 to 200; p has the value from 1 to 6, q has the value from 0 to 6;
r has the value 0 or 1; w has the value 0 or 1; x has the value from 1 to 100; y has the value from 0 to 100; and z has the value 0 or 1.
7. A liquid detergent composition according to Claim 6 wherein the modified polyamine compound is selected from the group consisting of compounds having the formulas and mixtures thereof.
8. A liquid detergent composition comprising a polymer comprising polyacrylic acid monomers having a number average molecular weight of from 1000 to 10,000 amu and a polydispersity of less than and a zwitterionic polyamine, preferably wherein the zwitterionic polyamine has the formula:
[J~R]n~J
wherein J is selected from the group consisting of:
i) primary amino units having the formula:
(R1)2N;
ii) secondary amino units having the formula:
~R1N.
iii) tertiary amino units having the formula:
iv) primary quaternary amino units having the formula:
v) secondary quaternary amino units having the formula:
vi) tertiary quaternary amino units having the formula:
vii) primary N-oxide amino units having the formula:
viii) secondary N-oxide amino units having the formula:
ix) tertiary N-oxide amino units having the formula:
x) and mixtures thereof;
wherein B is a continuation of the backbone by branching having the formula:
[J~R]~;
R is a hydrophilic backbone unit selected from the group consisting of:
i) C2-C12 linear alkylene, C3-C12 branched alkylene, or mixtures thereof;
ii) alkyleneoxyalkylene units having the formula:
~(R2O)w(R3)~
iii) hydroxyalkylene units having the formula:
iv) hydroxyalkylene/oxyalkylene units having the formula:
v) carboxyalkyleneoxy units having the formula:
vi) and mixtures thereof;
R1 is selected from the group consisting of:
i) hydrogen;
ii) C1-C22 alkyl;
iii) C7-C22 arylalkyl;
iv) -[CH2CH(OR4)CH2O]s(R2O)t Y;
v) anionic units;
vi) and mixtures thereof;
R2 is selected from the group consisting of ethylene, 1,2-propylene, 1,3-propylene, 1,2-butylene, 1,4-butylene, and mixtures thereof;
R3 is C2-C8 linear alkylene, C3-C8 branched alkylene, phenylene, substituted phenylene, and mixtures thereof;
R4 is hydrogen, C1-C4 alkyl, -(R2O)t Y, and mixtures thereof;
Q is a quaternizing unit selected from the group consisting of C1-C4 linear alkyl, C1-C4 hydroxyalkyl, benzyl, (R2O)t Y, and mixtures thereof;
X is oxygen, -NR4-, and mixtures thereof;
Y is hydrogen, C1-C4 linear alkyl, an anionic unit, and mixtures thereof;
the index j is from 0 to 20; the index k is from 1 to 20; n is from 1 to 99;
the index r is 0 or 1; the index s is from 0 to 5; the index t has an average value of from 0.5 to 100; the index w is from 0 to 25; the indices x, y, and z are each independently from 0 to 6.
[J~R]n~J
wherein J is selected from the group consisting of:
i) primary amino units having the formula:
(R1)2N;
ii) secondary amino units having the formula:
~R1N.
iii) tertiary amino units having the formula:
iv) primary quaternary amino units having the formula:
v) secondary quaternary amino units having the formula:
vi) tertiary quaternary amino units having the formula:
vii) primary N-oxide amino units having the formula:
viii) secondary N-oxide amino units having the formula:
ix) tertiary N-oxide amino units having the formula:
x) and mixtures thereof;
wherein B is a continuation of the backbone by branching having the formula:
[J~R]~;
R is a hydrophilic backbone unit selected from the group consisting of:
i) C2-C12 linear alkylene, C3-C12 branched alkylene, or mixtures thereof;
ii) alkyleneoxyalkylene units having the formula:
~(R2O)w(R3)~
iii) hydroxyalkylene units having the formula:
iv) hydroxyalkylene/oxyalkylene units having the formula:
v) carboxyalkyleneoxy units having the formula:
vi) and mixtures thereof;
R1 is selected from the group consisting of:
i) hydrogen;
ii) C1-C22 alkyl;
iii) C7-C22 arylalkyl;
iv) -[CH2CH(OR4)CH2O]s(R2O)t Y;
v) anionic units;
vi) and mixtures thereof;
R2 is selected from the group consisting of ethylene, 1,2-propylene, 1,3-propylene, 1,2-butylene, 1,4-butylene, and mixtures thereof;
R3 is C2-C8 linear alkylene, C3-C8 branched alkylene, phenylene, substituted phenylene, and mixtures thereof;
R4 is hydrogen, C1-C4 alkyl, -(R2O)t Y, and mixtures thereof;
Q is a quaternizing unit selected from the group consisting of C1-C4 linear alkyl, C1-C4 hydroxyalkyl, benzyl, (R2O)t Y, and mixtures thereof;
X is oxygen, -NR4-, and mixtures thereof;
Y is hydrogen, C1-C4 linear alkyl, an anionic unit, and mixtures thereof;
the index j is from 0 to 20; the index k is from 1 to 20; n is from 1 to 99;
the index r is 0 or 1; the index s is from 0 to 5; the index t has an average value of from 0.5 to 100; the index w is from 0 to 25; the indices x, y, and z are each independently from 0 to 6.
9. A liquid detergent composition according to Claim 8 wherein the zwitterionic polyamine has the formula:
wherein R units have the formula -(R2O)w R3- wherein R2 and R3 are each independently selected from the group consisting of C2-C8 linear alkylene, C3-C8 branched alkylene, phenylene, substituted phenylene, and mixtures thereof; Y is an anionic unit selected from the group consisting of -(CH2)f CO2M, -C(O)(CH2)f CO2M, -(CH2)f PO3M, -(CH2)f OPO3M, -(CH2)f SO3M, -CH2(CHSO3M)(CH2)f SO3M, -CH2(CHSO2M)(CH2)f SO3M, and mixtures thereof; M is hydrogen, a water soluble cation, and mixtures thereof; the index f is from 0 to 10; Q
is a quaternizing unit selected from the group consisting of C1-C4 linear alkyl, C1-C4 hydroxyalkyl, benzyl, (R2O)t Y, and mixtures thereof; the index m is from 0 to 20; the index t is from 15 to 25.
wherein R units have the formula -(R2O)w R3- wherein R2 and R3 are each independently selected from the group consisting of C2-C8 linear alkylene, C3-C8 branched alkylene, phenylene, substituted phenylene, and mixtures thereof; Y is an anionic unit selected from the group consisting of -(CH2)f CO2M, -C(O)(CH2)f CO2M, -(CH2)f PO3M, -(CH2)f OPO3M, -(CH2)f SO3M, -CH2(CHSO3M)(CH2)f SO3M, -CH2(CHSO2M)(CH2)f SO3M, and mixtures thereof; M is hydrogen, a water soluble cation, and mixtures thereof; the index f is from 0 to 10; Q
is a quaternizing unit selected from the group consisting of C1-C4 linear alkyl, C1-C4 hydroxyalkyl, benzyl, (R2O)t Y, and mixtures thereof; the index m is from 0 to 20; the index t is from 15 to 25.
10. A liquid detergent composition according to Claim 8 further comprising a water-soluble or dispersible, modified polyamine compound.
Applications Claiming Priority (3)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
US81493806P | 2006-06-19 | 2006-06-19 | |
US60/814,938 | 2006-06-19 | ||
PCT/US2007/071441 WO2007149806A1 (en) | 2006-06-19 | 2007-06-18 | Liquid detergent compositions with low polydispersity polyacrylic acid based polymers |
Publications (1)
Publication Number | Publication Date |
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CA2652467A1 true CA2652467A1 (en) | 2007-12-27 |
Family
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Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
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CA002652467A Abandoned CA2652467A1 (en) | 2006-06-19 | 2007-06-18 | Liquid detergent compositions with low polydispersity polyacrylic acid based polymers |
Country Status (6)
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EP (1) | EP2029713A1 (en) |
JP (1) | JP2009542896A (en) |
BR (1) | BRPI0712934A2 (en) |
CA (1) | CA2652467A1 (en) |
MX (1) | MX2008016448A (en) |
WO (1) | WO2007149806A1 (en) |
Families Citing this family (28)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US9376648B2 (en) | 2008-04-07 | 2016-06-28 | The Procter & Gamble Company | Foam manipulation compositions containing fine particles |
CN104017789B (en) | 2008-06-06 | 2017-11-03 | 诺维信公司 | The xyloglucan enzyme variants of family 44 |
ES2720369T3 (en) | 2008-06-06 | 2019-07-19 | Procter & Gamble | Detergent composition comprising a variant of a family xyloglucanase 44 |
US20110150817A1 (en) * | 2009-12-17 | 2011-06-23 | Ricky Ah-Man Woo | Freshening compositions comprising malodor binding polymers and malodor control components |
US20120220513A1 (en) | 2009-12-29 | 2012-08-30 | Novozymes A/S | Polypeptides Having Detergency Enhancing Effect |
EP3892709A3 (en) | 2010-02-10 | 2022-01-19 | Novozymes A/S | Variants and compositions comprising variants with high stability in presence of a chelating agent |
EP2357220A1 (en) | 2010-02-10 | 2011-08-17 | The Procter & Gamble Company | Cleaning composition comprising amylase variants with high stability in the presence of a chelating agent |
JP5833576B2 (en) | 2010-02-25 | 2015-12-16 | ノボザイムス アクティーゼルスカブ | Variant of lysozyme and polynucleotide encoding the same |
US8492325B2 (en) * | 2010-03-01 | 2013-07-23 | The Procter & Gamble Company | Dual-usage liquid laundry detergents comprising a silicone anti-foam |
US20130266554A1 (en) | 2010-09-16 | 2013-10-10 | Novozymes A/S | Lysozymes |
EP2675884A1 (en) | 2011-02-16 | 2013-12-25 | Novozymes A/S | Detergent compositions comprising metalloproteases |
CN103476915A (en) | 2011-02-16 | 2013-12-25 | 诺维信公司 | Detergent compositions comprising metalloproteases |
MX2013009177A (en) | 2011-02-16 | 2013-08-29 | Novozymes As | Detergent compositions comprising m7 or m35 metalloproteases. |
EP2888358A1 (en) | 2012-08-22 | 2015-07-01 | Novozymes A/S | Detergent compositions comprising metalloproteases |
EP2888361A1 (en) | 2012-08-22 | 2015-07-01 | Novozymes A/S | Metalloprotease from exiguobacterium |
CN104603266B (en) | 2012-08-22 | 2017-11-10 | 诺维信公司 | Metalloproteinases from alicyclic acid bacillus |
DE102013216776A1 (en) * | 2013-08-23 | 2015-02-26 | Henkel Ag & Co. Kgaa | Detergents and cleaning agents with improved performance |
WO2016066369A1 (en) * | 2014-10-29 | 2016-05-06 | Unilever Plc | Reduction of colour damage during the laundry process |
EP3408386A1 (en) | 2016-01-29 | 2018-12-05 | Novozymes A/S | Beta-glucanase variants and polynucleotides encoding same |
WO2018224544A1 (en) | 2017-06-08 | 2018-12-13 | Novozymes A/S | Compositions comprising polypeptides having cellulase activity and amylase activity, and uses thereof in cleaning and detergent compositions |
EP3692148A1 (en) | 2017-10-02 | 2020-08-12 | Novozymes A/S | Polypeptides having mannanase activity and polynucleotides encoding same |
CN111417725A (en) | 2017-10-02 | 2020-07-14 | 诺维信公司 | Polypeptides having mannanase activity and polynucleotides encoding same |
US11866748B2 (en) | 2017-10-24 | 2024-01-09 | Novozymes A/S | Compositions comprising polypeptides having mannanase activity |
WO2020070199A1 (en) | 2018-10-03 | 2020-04-09 | Novozymes A/S | Polypeptides having alpha-mannan degrading activity and polynucleotides encoding same |
US20220169953A1 (en) | 2019-04-03 | 2022-06-02 | Novozymes A/S | Polypeptides having beta-glucanase activity, polynucleotides encoding same and uses thereof in cleaning and detergent compositions |
WO2021152123A1 (en) | 2020-01-31 | 2021-08-05 | Novozymes A/S | Mannanase variants and polynucleotides encoding same |
EP4097226A1 (en) | 2020-01-31 | 2022-12-07 | Novozymes A/S | Mannanase variants and polynucleotides encoding same |
WO2023247348A1 (en) | 2022-06-21 | 2023-12-28 | Novozymes A/S | Mannanase variants and polynucleotides encoding same |
Family Cites Families (5)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
AU581417B2 (en) * | 1984-11-16 | 1989-02-23 | Ciba Specialty Chemicals Water Treatments Limited | Water soluble polymers and dispersions containing them |
US6297336B1 (en) * | 1998-07-02 | 2001-10-02 | Nippon Shokubai Co., Ltd. | Detergent builder, production process therefor, and poly(meth)acrylic acid (or salt) polymer and use thereof |
US6794473B2 (en) * | 2001-05-01 | 2004-09-21 | Nippon Shokubai Co., Ltd. | Acrylic acid (salt) polymer, its production process and uses |
US7442749B2 (en) * | 2002-08-29 | 2008-10-28 | Nippon Shokubai Co., Ltd. | Sulfur-containing poly (unsaturated carboxylic acid) and its uses and production process |
EP1537198B2 (en) * | 2002-09-12 | 2011-11-16 | The Procter & Gamble Company | Polymer systems and cleaning compositions comprising same |
-
2007
- 2007-06-18 BR BRPI0712934-3A patent/BRPI0712934A2/en not_active IP Right Cessation
- 2007-06-18 WO PCT/US2007/071441 patent/WO2007149806A1/en active Application Filing
- 2007-06-18 EP EP07784463A patent/EP2029713A1/en not_active Ceased
- 2007-06-18 MX MX2008016448A patent/MX2008016448A/en unknown
- 2007-06-18 CA CA002652467A patent/CA2652467A1/en not_active Abandoned
- 2007-06-18 JP JP2009530711A patent/JP2009542896A/en not_active Withdrawn
Also Published As
Publication number | Publication date |
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EP2029713A1 (en) | 2009-03-04 |
WO2007149806A1 (en) | 2007-12-27 |
MX2008016448A (en) | 2009-01-22 |
JP2009542896A (en) | 2009-12-03 |
BRPI0712934A2 (en) | 2013-03-26 |
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