CA2214615A1 - Machine dishwashing composition containing amphoteric polymers - Google Patents
Machine dishwashing composition containing amphoteric polymers Download PDFInfo
- Publication number
- CA2214615A1 CA2214615A1 CA002214615A CA2214615A CA2214615A1 CA 2214615 A1 CA2214615 A1 CA 2214615A1 CA 002214615 A CA002214615 A CA 002214615A CA 2214615 A CA2214615 A CA 2214615A CA 2214615 A1 CA2214615 A1 CA 2214615A1
- Authority
- CA
- Canada
- Prior art keywords
- acid
- group
- moiety
- mole
- alkyl
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Abandoned
Links
- 239000000203 mixture Substances 0.000 title claims abstract description 108
- 229920000642 polymer Polymers 0.000 title claims abstract description 54
- 238000004851 dishwashing Methods 0.000 title description 11
- 239000000344 soap Substances 0.000 claims abstract description 42
- 235000008733 Citrus aurantifolia Nutrition 0.000 claims abstract description 38
- 235000011941 Tilia x europaea Nutrition 0.000 claims abstract description 38
- 239000004571 lime Substances 0.000 claims abstract description 38
- 239000003599 detergent Substances 0.000 claims abstract description 26
- 102000004190 Enzymes Human genes 0.000 claims abstract description 24
- 108090000790 Enzymes Proteins 0.000 claims abstract description 24
- 238000000034 method Methods 0.000 claims abstract description 23
- 230000008021 deposition Effects 0.000 claims abstract description 22
- 230000002366 lipolytic effect Effects 0.000 claims abstract description 14
- -1 vinyl compound Chemical class 0.000 claims description 76
- 125000000217 alkyl group Chemical group 0.000 claims description 41
- 239000002253 acid Substances 0.000 claims description 31
- 239000000178 monomer Substances 0.000 claims description 29
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 claims description 28
- NIXOWILDQLNWCW-UHFFFAOYSA-N 2-Propenoic acid Natural products OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 claims description 28
- 150000001875 compounds Chemical class 0.000 claims description 24
- CERQOIWHTDAKMF-UHFFFAOYSA-N Methacrylic acid Chemical compound CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 claims description 23
- 150000007942 carboxylates Chemical group 0.000 claims description 23
- 125000000129 anionic group Chemical group 0.000 claims description 20
- 239000000463 material Substances 0.000 claims description 20
- JAHNSTQSQJOJLO-UHFFFAOYSA-N 2-(3-fluorophenyl)-1h-imidazole Chemical compound FC1=CC=CC(C=2NC=CN=2)=C1 JAHNSTQSQJOJLO-UHFFFAOYSA-N 0.000 claims description 19
- LVHBHZANLOWSRM-UHFFFAOYSA-N methylenebutanedioic acid Natural products OC(=O)CC(=C)C(O)=O LVHBHZANLOWSRM-UHFFFAOYSA-N 0.000 claims description 19
- 239000001257 hydrogen Substances 0.000 claims description 17
- 229910052739 hydrogen Inorganic materials 0.000 claims description 17
- 125000002091 cationic group Chemical group 0.000 claims description 16
- VZCYOOQTPOCHFL-UHFFFAOYSA-N trans-butenedioic acid Natural products OC(=O)C=CC(O)=O VZCYOOQTPOCHFL-UHFFFAOYSA-N 0.000 claims description 16
- VZCYOOQTPOCHFL-OWOJBTEDSA-N Fumaric acid Chemical compound OC(=O)\C=C\C(O)=O VZCYOOQTPOCHFL-OWOJBTEDSA-N 0.000 claims description 10
- VZCYOOQTPOCHFL-UPHRSURJSA-N maleic acid Chemical compound OC(=O)\C=C/C(O)=O VZCYOOQTPOCHFL-UPHRSURJSA-N 0.000 claims description 10
- 229910019142 PO4 Inorganic materials 0.000 claims description 9
- 229910052783 alkali metal Inorganic materials 0.000 claims description 8
- 229920001577 copolymer Polymers 0.000 claims description 8
- 239000010452 phosphate Substances 0.000 claims description 8
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 7
- OFOBLEOULBTSOW-UHFFFAOYSA-N Propanedioic acid Natural products OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 0.000 claims description 7
- 125000003118 aryl group Chemical group 0.000 claims description 7
- 150000002431 hydrogen Chemical class 0.000 claims description 7
- 239000011976 maleic acid Substances 0.000 claims description 7
- 229910052757 nitrogen Inorganic materials 0.000 claims description 7
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 claims description 7
- 238000010936 aqueous wash Methods 0.000 claims description 6
- 229910052760 oxygen Inorganic materials 0.000 claims description 6
- 229920001897 terpolymer Polymers 0.000 claims description 6
- PSZAEHPBBUYICS-UHFFFAOYSA-N 2-methylidenepropanedioic acid Chemical compound OC(=O)C(=C)C(O)=O PSZAEHPBBUYICS-UHFFFAOYSA-N 0.000 claims description 5
- 150000001340 alkali metals Chemical class 0.000 claims description 5
- PVEOYINWKBTPIZ-UHFFFAOYSA-N but-3-enoic acid Chemical compound OC(=O)CC=C PVEOYINWKBTPIZ-UHFFFAOYSA-N 0.000 claims description 5
- HNEGQIOMVPPMNR-IHWYPQMZSA-N citraconic acid Chemical compound OC(=O)C(/C)=C\C(O)=O HNEGQIOMVPPMNR-IHWYPQMZSA-N 0.000 claims description 5
- 229940018557 citraconic acid Drugs 0.000 claims description 5
- LDHQCZJRKDOVOX-NSCUHMNNSA-N crotonic acid Chemical compound C\C=C\C(O)=O LDHQCZJRKDOVOX-NSCUHMNNSA-N 0.000 claims description 5
- 239000001530 fumaric acid Substances 0.000 claims description 5
- HNEGQIOMVPPMNR-NSCUHMNNSA-N mesaconic acid Chemical compound OC(=O)C(/C)=C/C(O)=O HNEGQIOMVPPMNR-NSCUHMNNSA-N 0.000 claims description 5
- HNEGQIOMVPPMNR-UHFFFAOYSA-N methylfumaric acid Natural products OC(=O)C(C)=CC(O)=O HNEGQIOMVPPMNR-UHFFFAOYSA-N 0.000 claims description 5
- HVAMZGADVCBITI-UHFFFAOYSA-N pent-4-enoic acid Chemical compound OC(=O)CCC=C HVAMZGADVCBITI-UHFFFAOYSA-N 0.000 claims description 5
- LDHQCZJRKDOVOX-UHFFFAOYSA-N trans-crotonic acid Natural products CC=CC(O)=O LDHQCZJRKDOVOX-UHFFFAOYSA-N 0.000 claims description 5
- QTBSBXVTEAMEQO-UHFFFAOYSA-M Acetate Chemical compound CC([O-])=O QTBSBXVTEAMEQO-UHFFFAOYSA-M 0.000 claims description 4
- BDAGIHXWWSANSR-UHFFFAOYSA-M Formate Chemical compound [O-]C=O BDAGIHXWWSANSR-UHFFFAOYSA-M 0.000 claims description 4
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 claims description 4
- 150000003863 ammonium salts Chemical class 0.000 claims description 4
- GQOKIYDTHHZSCJ-UHFFFAOYSA-M dimethyl-bis(prop-2-enyl)azanium;chloride Chemical compound [Cl-].C=CC[N+](C)(C)CC=C GQOKIYDTHHZSCJ-UHFFFAOYSA-M 0.000 claims description 4
- 229910052736 halogen Inorganic materials 0.000 claims description 4
- 150000002367 halogens Chemical class 0.000 claims description 4
- XLYOFNOQVPJJNP-UHFFFAOYSA-M hydroxide Chemical compound [OH-] XLYOFNOQVPJJNP-UHFFFAOYSA-M 0.000 claims description 4
- IJGRMHOSHXDMSA-UHFFFAOYSA-N nitrogen Substances N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 4
- QJGQUHMNIGDVPM-UHFFFAOYSA-N nitrogen group Chemical group [N] QJGQUHMNIGDVPM-UHFFFAOYSA-N 0.000 claims description 4
- OEIXGLMQZVLOQX-UHFFFAOYSA-N trimethyl-[3-(prop-2-enoylamino)propyl]azanium;chloride Chemical compound [Cl-].C[N+](C)(C)CCCNC(=O)C=C OEIXGLMQZVLOQX-UHFFFAOYSA-N 0.000 claims description 4
- 108010065511 Amylases Proteins 0.000 claims description 3
- 102000013142 Amylases Human genes 0.000 claims description 3
- 108091005804 Peptidases Proteins 0.000 claims description 3
- 239000004365 Protease Substances 0.000 claims description 3
- 235000019418 amylase Nutrition 0.000 claims description 3
- 239000007864 aqueous solution Substances 0.000 claims description 3
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims description 3
- 239000004382 Amylase Substances 0.000 claims description 2
- 102100037486 Reverse transcriptase/ribonuclease H Human genes 0.000 claims description 2
- 125000000623 heterocyclic group Chemical group 0.000 claims description 2
- 229920002554 vinyl polymer Polymers 0.000 claims 5
- 125000006273 (C1-C3) alkyl group Chemical group 0.000 claims 2
- UYMKPFRHYYNDTL-UHFFFAOYSA-N ethenamine Chemical compound NC=C UYMKPFRHYYNDTL-UHFFFAOYSA-N 0.000 claims 1
- 125000004005 formimidoyl group Chemical group [H]\N=C(/[H])* 0.000 claims 1
- 239000004367 Lipase Substances 0.000 description 36
- 108090001060 Lipase Proteins 0.000 description 36
- 102000004882 Lipase Human genes 0.000 description 36
- 235000019421 lipase Nutrition 0.000 description 36
- 125000004432 carbon atom Chemical group C* 0.000 description 29
- 229940088598 enzyme Drugs 0.000 description 21
- 235000002639 sodium chloride Nutrition 0.000 description 16
- 239000002270 dispersing agent Substances 0.000 description 15
- 239000002585 base Substances 0.000 description 14
- 239000007844 bleaching agent Substances 0.000 description 14
- 239000002689 soil Substances 0.000 description 14
- 239000004094 surface-active agent Substances 0.000 description 14
- 150000003839 salts Chemical class 0.000 description 13
- 238000009472 formulation Methods 0.000 description 11
- 229910052500 inorganic mineral Inorganic materials 0.000 description 11
- 235000010755 mineral Nutrition 0.000 description 11
- 239000011707 mineral Substances 0.000 description 11
- 239000002562 thickening agent Substances 0.000 description 11
- 239000000194 fatty acid Substances 0.000 description 10
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 10
- 239000004698 Polyethylene Substances 0.000 description 9
- 239000000460 chlorine Substances 0.000 description 9
- 235000014113 dietary fatty acids Nutrition 0.000 description 9
- 229930195729 fatty acid Natural products 0.000 description 9
- 239000011521 glass Substances 0.000 description 9
- 239000002736 nonionic surfactant Substances 0.000 description 9
- 229920000573 polyethylene Polymers 0.000 description 9
- 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 8
- 229920002125 Sokalan® Polymers 0.000 description 8
- 239000002738 chelating agent Substances 0.000 description 8
- 238000004140 cleaning Methods 0.000 description 8
- 150000002148 esters Chemical class 0.000 description 8
- 230000002209 hydrophobic effect Effects 0.000 description 8
- 239000011734 sodium Substances 0.000 description 8
- 229910052708 sodium Inorganic materials 0.000 description 8
- 125000001931 aliphatic group Chemical group 0.000 description 7
- 150000001768 cations Chemical class 0.000 description 7
- 235000021317 phosphate Nutrition 0.000 description 7
- 244000060011 Cocos nucifera Species 0.000 description 6
- 235000013162 Cocos nucifera Nutrition 0.000 description 6
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 6
- IAYPIBMASNFSPL-UHFFFAOYSA-N Ethylene oxide Chemical compound C1CO1 IAYPIBMASNFSPL-UHFFFAOYSA-N 0.000 description 6
- 229920003171 Poly (ethylene oxide) Polymers 0.000 description 6
- 150000007513 acids Chemical class 0.000 description 6
- 239000011575 calcium Substances 0.000 description 6
- 239000002243 precursor Substances 0.000 description 6
- 230000003381 solubilizing effect Effects 0.000 description 6
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 5
- 125000002947 alkylene group Chemical group 0.000 description 5
- 230000015572 biosynthetic process Effects 0.000 description 5
- 229910052801 chlorine Inorganic materials 0.000 description 5
- 238000009826 distribution Methods 0.000 description 5
- 150000004665 fatty acids Chemical class 0.000 description 5
- 150000002191 fatty alcohols Chemical class 0.000 description 5
- 239000000945 filler Substances 0.000 description 5
- 239000000499 gel Substances 0.000 description 5
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 5
- 229920000058 polyacrylate Polymers 0.000 description 5
- 239000000047 product Substances 0.000 description 5
- 150000003254 radicals Chemical class 0.000 description 5
- 239000003381 stabilizer Substances 0.000 description 5
- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 description 4
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 description 4
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 description 4
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 description 4
- IMROMDMJAWUWLK-UHFFFAOYSA-N Ethenol Chemical compound OC=C IMROMDMJAWUWLK-UHFFFAOYSA-N 0.000 description 4
- ABLZXFCXXLZCGV-UHFFFAOYSA-N Phosphorous acid Chemical class OP(O)=O ABLZXFCXXLZCGV-UHFFFAOYSA-N 0.000 description 4
- GOOHAUXETOMSMM-UHFFFAOYSA-N Propylene oxide Chemical group CC1CO1 GOOHAUXETOMSMM-UHFFFAOYSA-N 0.000 description 4
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 4
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 description 4
- 239000003945 anionic surfactant Substances 0.000 description 4
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 4
- 230000008901 benefit Effects 0.000 description 4
- 239000013530 defoamer Substances 0.000 description 4
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 4
- 229930195733 hydrocarbon Natural products 0.000 description 4
- 239000001301 oxygen Substances 0.000 description 4
- 239000004584 polyacrylic acid Substances 0.000 description 4
- 229920001451 polypropylene glycol Polymers 0.000 description 4
- 150000004760 silicates Chemical class 0.000 description 4
- 125000004178 (C1-C4) alkyl group Chemical group 0.000 description 3
- 239000004215 Carbon black (E152) Substances 0.000 description 3
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 3
- BGRWYDHXPHLNKA-UHFFFAOYSA-N Tetraacetylethylenediamine Chemical compound CC(=O)N(C(C)=O)CCN(C(C)=O)C(C)=O BGRWYDHXPHLNKA-UHFFFAOYSA-N 0.000 description 3
- 230000009471 action Effects 0.000 description 3
- 150000001298 alcohols Chemical class 0.000 description 3
- 125000003342 alkenyl group Chemical group 0.000 description 3
- 229910000019 calcium carbonate Inorganic materials 0.000 description 3
- GUJOJGAPFQRJSV-UHFFFAOYSA-N dialuminum;dioxosilane;oxygen(2-);hydrate Chemical compound O.[O-2].[O-2].[O-2].[Al+3].[Al+3].O=[Si]=O.O=[Si]=O.O=[Si]=O.O=[Si]=O GUJOJGAPFQRJSV-UHFFFAOYSA-N 0.000 description 3
- GSPKZYJPUDYKPI-UHFFFAOYSA-N diethoxy sulfate Chemical compound CCOOS(=O)(=O)OOCC GSPKZYJPUDYKPI-UHFFFAOYSA-N 0.000 description 3
- 150000002194 fatty esters Chemical class 0.000 description 3
- 239000012634 fragment Substances 0.000 description 3
- 239000004615 ingredient Substances 0.000 description 3
- 229940094522 laponite Drugs 0.000 description 3
- 239000007788 liquid Substances 0.000 description 3
- XCOBTUNSZUJCDH-UHFFFAOYSA-B lithium magnesium sodium silicate Chemical compound [Li+].[Li+].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[Na+].[Na+].[Mg+2].[Mg+2].[Mg+2].[Mg+2].[Mg+2].[Mg+2].[Mg+2].[Mg+2].[Mg+2].[Mg+2].[Mg+2].[Mg+2].[Mg+2].[Mg+2].[Mg+2].[Mg+2].O1[Si](O2)([O-])O[Si]3([O-])O[Si]1([O-])O[Si]2([O-])O3.O1[Si](O2)([O-])O[Si]3([O-])O[Si]1([O-])O[Si]2([O-])O3.O1[Si](O2)([O-])O[Si]3([O-])O[Si]1([O-])O[Si]2([O-])O3.O1[Si](O2)([O-])O[Si]3([O-])O[Si]1([O-])O[Si]2([O-])O3.O1[Si](O2)([O-])O[Si]3([O-])O[Si]1([O-])O[Si]2([O-])O3.O1[Si](O2)([O-])O[Si]3([O-])O[Si]1([O-])O[Si]2([O-])O3 XCOBTUNSZUJCDH-UHFFFAOYSA-B 0.000 description 3
- 229910052751 metal Inorganic materials 0.000 description 3
- 239000002184 metal Substances 0.000 description 3
- MGFYIUFZLHCRTH-UHFFFAOYSA-N nitrilotriacetic acid Chemical class OC(=O)CN(CC(O)=O)CC(O)=O MGFYIUFZLHCRTH-UHFFFAOYSA-N 0.000 description 3
- 229920005646 polycarboxylate Polymers 0.000 description 3
- 229920006395 saturated elastomer Polymers 0.000 description 3
- QSKQNALVHFTOQX-UHFFFAOYSA-M sodium nonanoyloxybenzenesulfonate Chemical compound [Na+].CCCCCCCCC(=O)OC1=CC=CC=C1S([O-])(=O)=O QSKQNALVHFTOQX-UHFFFAOYSA-M 0.000 description 3
- 235000019832 sodium triphosphate Nutrition 0.000 description 3
- 239000000243 solution Substances 0.000 description 3
- 239000000271 synthetic detergent Substances 0.000 description 3
- UFTFJSFQGQCHQW-UHFFFAOYSA-N triformin Chemical compound O=COCC(OC=O)COC=O UFTFJSFQGQCHQW-UHFFFAOYSA-N 0.000 description 3
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 description 3
- 238000005406 washing Methods 0.000 description 3
- JNYAEWCLZODPBN-JGWLITMVSA-N (2r,3r,4s)-2-[(1r)-1,2-dihydroxyethyl]oxolane-3,4-diol Chemical class OC[C@@H](O)[C@H]1OC[C@H](O)[C@H]1O JNYAEWCLZODPBN-JGWLITMVSA-N 0.000 description 2
- MPJQXAIKMSKXBI-UHFFFAOYSA-N 2,7,9,14-tetraoxa-1,8-diazabicyclo[6.6.2]hexadecane-3,6,10,13-tetrone Chemical compound C1CN2OC(=O)CCC(=O)ON1OC(=O)CCC(=O)O2 MPJQXAIKMSKXBI-UHFFFAOYSA-N 0.000 description 2
- CFPOJWPDQWJEMO-UHFFFAOYSA-N 2-(1,2-dicarboxyethoxy)butanedioic acid Chemical class OC(=O)CC(C(O)=O)OC(C(O)=O)CC(O)=O CFPOJWPDQWJEMO-UHFFFAOYSA-N 0.000 description 2
- CZUSWJYAWTXIIZ-UHFFFAOYSA-N 2-carboxyoxybenzenesulfonic acid Chemical compound OC(=O)OC1=CC=CC=C1S(O)(=O)=O CZUSWJYAWTXIIZ-UHFFFAOYSA-N 0.000 description 2
- HRPVXLWXLXDGHG-UHFFFAOYSA-N Acrylamide Chemical compound NC(=O)C=C HRPVXLWXLXDGHG-UHFFFAOYSA-N 0.000 description 2
- FERIUCNNQQJTOY-UHFFFAOYSA-N Butyric acid Chemical compound CCCC(O)=O FERIUCNNQQJTOY-UHFFFAOYSA-N 0.000 description 2
- 125000002853 C1-C4 hydroxyalkyl group Chemical group 0.000 description 2
- KXDHJXZQYSOELW-UHFFFAOYSA-N Carbamic acid Chemical class NC(O)=O KXDHJXZQYSOELW-UHFFFAOYSA-N 0.000 description 2
- WQZGKKKJIJFFOK-GASJEMHNSA-N Glucose Natural products OC[C@H]1OC(O)[C@H](O)[C@@H](O)[C@@H]1O WQZGKKKJIJFFOK-GASJEMHNSA-N 0.000 description 2
- IMQLKJBTEOYOSI-GPIVLXJGSA-N Inositol-hexakisphosphate Chemical compound OP(O)(=O)O[C@H]1[C@H](OP(O)(O)=O)[C@@H](OP(O)(O)=O)[C@H](OP(O)(O)=O)[C@H](OP(O)(O)=O)[C@@H]1OP(O)(O)=O IMQLKJBTEOYOSI-GPIVLXJGSA-N 0.000 description 2
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 2
- JLVVSXFLKOJNIY-UHFFFAOYSA-N Magnesium ion Chemical compound [Mg+2] JLVVSXFLKOJNIY-UHFFFAOYSA-N 0.000 description 2
- BCXBKOQDEOJNRH-UHFFFAOYSA-N NOP(O)=O Chemical class NOP(O)=O BCXBKOQDEOJNRH-UHFFFAOYSA-N 0.000 description 2
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 2
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 2
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 description 2
- WCUXLLCKKVVCTQ-UHFFFAOYSA-M Potassium chloride Chemical compound [Cl-].[K+] WCUXLLCKKVVCTQ-UHFFFAOYSA-M 0.000 description 2
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 2
- PMZURENOXWZQFD-UHFFFAOYSA-L Sodium Sulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=O PMZURENOXWZQFD-UHFFFAOYSA-L 0.000 description 2
- BCKXLBQYZLBQEK-KVVVOXFISA-M Sodium oleate Chemical compound [Na+].CCCCCCCC\C=C/CCCCCCCC([O-])=O BCKXLBQYZLBQEK-KVVVOXFISA-M 0.000 description 2
- UYXTWWCETRIEDR-UHFFFAOYSA-N Tributyrin Chemical compound CCCC(=O)OCC(OC(=O)CCC)COC(=O)CCC UYXTWWCETRIEDR-UHFFFAOYSA-N 0.000 description 2
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Chemical compound NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 description 2
- XTXRWKRVRITETP-UHFFFAOYSA-N Vinyl acetate Chemical compound CC(=O)OC=C XTXRWKRVRITETP-UHFFFAOYSA-N 0.000 description 2
- NVANJYGRGNEULT-BDZGGURLSA-N [(3s,4r,5r)-4-hexadecanoyloxy-5-[(1r)-1-hexadecanoyloxy-2-hydroxyethyl]oxolan-3-yl] hexadecanoate Chemical compound CCCCCCCCCCCCCCCC(=O)O[C@H](CO)[C@H]1OC[C@H](OC(=O)CCCCCCCCCCCCCCC)[C@H]1OC(=O)CCCCCCCCCCCCCCC NVANJYGRGNEULT-BDZGGURLSA-N 0.000 description 2
- 150000003926 acrylamides Chemical class 0.000 description 2
- 150000004808 allyl alcohols Chemical class 0.000 description 2
- 229910000323 aluminium silicate Inorganic materials 0.000 description 2
- 150000001412 amines Chemical class 0.000 description 2
- 239000000440 bentonite Substances 0.000 description 2
- 229910000278 bentonite Inorganic materials 0.000 description 2
- SVPXDRXYRYOSEX-UHFFFAOYSA-N bentoquatam Chemical compound O.O=[Si]=O.O=[Al]O[Al]=O SVPXDRXYRYOSEX-UHFFFAOYSA-N 0.000 description 2
- 229920001400 block copolymer Polymers 0.000 description 2
- 229910052791 calcium Inorganic materials 0.000 description 2
- 235000010216 calcium carbonate Nutrition 0.000 description 2
- 229910001424 calcium ion Inorganic materials 0.000 description 2
- 150000001735 carboxylic acids Chemical class 0.000 description 2
- 239000003054 catalyst Substances 0.000 description 2
- 239000000919 ceramic Substances 0.000 description 2
- 239000003795 chemical substances by application Substances 0.000 description 2
- OEYIOHPDSNJKLS-UHFFFAOYSA-N choline Chemical compound C[N+](C)(C)CCO OEYIOHPDSNJKLS-UHFFFAOYSA-N 0.000 description 2
- 229960001231 choline Drugs 0.000 description 2
- 239000004927 clay Substances 0.000 description 2
- 230000009849 deactivation Effects 0.000 description 2
- 239000012933 diacyl peroxide Substances 0.000 description 2
- 150000004985 diamines Chemical class 0.000 description 2
- 235000011180 diphosphates Nutrition 0.000 description 2
- POULHZVOKOAJMA-UHFFFAOYSA-N dodecanoic acid Chemical compound CCCCCCCCCCCC(O)=O POULHZVOKOAJMA-UHFFFAOYSA-N 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 238000005538 encapsulation Methods 0.000 description 2
- 229940071087 ethylenediamine disuccinate Drugs 0.000 description 2
- 238000001704 evaporation Methods 0.000 description 2
- 230000008020 evaporation Effects 0.000 description 2
- 239000008103 glucose Substances 0.000 description 2
- IPCSVZSSVZVIGE-UHFFFAOYSA-N hexadecanoic acid Chemical compound CCCCCCCCCCCCCCCC(O)=O IPCSVZSSVZVIGE-UHFFFAOYSA-N 0.000 description 2
- 230000002401 inhibitory effect Effects 0.000 description 2
- 229910052742 iron Inorganic materials 0.000 description 2
- ZFSLODLOARCGLH-UHFFFAOYSA-N isocyanuric acid Chemical compound OC1=NC(O)=NC(O)=N1 ZFSLODLOARCGLH-UHFFFAOYSA-N 0.000 description 2
- 239000012669 liquid formulation Substances 0.000 description 2
- 229910001425 magnesium ion Inorganic materials 0.000 description 2
- 229910052748 manganese Inorganic materials 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- XJRBAMWJDBPFIM-UHFFFAOYSA-N methyl vinyl ether Chemical compound COC=C XJRBAMWJDBPFIM-UHFFFAOYSA-N 0.000 description 2
- 108010020132 microbial serine proteinases Proteins 0.000 description 2
- 150000004682 monohydrates Chemical class 0.000 description 2
- HWGNBUXHKFFFIH-UHFFFAOYSA-I pentasodium;[oxido(phosphonatooxy)phosphoryl] phosphate Chemical compound [Na+].[Na+].[Na+].[Na+].[Na+].[O-]P([O-])(=O)OP([O-])(=O)OP([O-])([O-])=O HWGNBUXHKFFFIH-UHFFFAOYSA-I 0.000 description 2
- XCRBXWCUXJNEFX-UHFFFAOYSA-N peroxybenzoic acid Chemical compound OOC(=O)C1=CC=CC=C1 XCRBXWCUXJNEFX-UHFFFAOYSA-N 0.000 description 2
- 125000001476 phosphono group Chemical group [H]OP(*)(=O)O[H] 0.000 description 2
- 150000003014 phosphoric acid esters Chemical class 0.000 description 2
- 229910052698 phosphorus Inorganic materials 0.000 description 2
- 239000011574 phosphorus Substances 0.000 description 2
- 235000002949 phytic acid Nutrition 0.000 description 2
- 229920003023 plastic Polymers 0.000 description 2
- 239000004033 plastic Substances 0.000 description 2
- 239000011591 potassium Substances 0.000 description 2
- 229910052700 potassium Inorganic materials 0.000 description 2
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Chemical compound [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 description 2
- 230000008569 process Effects 0.000 description 2
- 108090000623 proteins and genes Proteins 0.000 description 2
- 229910021647 smectite Inorganic materials 0.000 description 2
- 239000011780 sodium chloride Substances 0.000 description 2
- NTHWMYGWWRZVTN-UHFFFAOYSA-N sodium silicate Chemical compound [Na+].[Na+].[O-][Si]([O-])=O NTHWMYGWWRZVTN-UHFFFAOYSA-N 0.000 description 2
- 229910052938 sodium sulfate Inorganic materials 0.000 description 2
- 235000011152 sodium sulphate Nutrition 0.000 description 2
- MWNQXXOSWHCCOZ-UHFFFAOYSA-L sodium;oxido carbonate Chemical compound [Na+].[O-]OC([O-])=O MWNQXXOSWHCCOZ-UHFFFAOYSA-L 0.000 description 2
- 235000000346 sugar Nutrition 0.000 description 2
- 150000008163 sugars Chemical class 0.000 description 2
- 239000003760 tallow Substances 0.000 description 2
- 108010075550 termamyl Proteins 0.000 description 2
- 238000010998 test method Methods 0.000 description 2
- HLZKNKRTKFSKGZ-UHFFFAOYSA-N tetradecan-1-ol Chemical compound CCCCCCCCCCCCCCO HLZKNKRTKFSKGZ-UHFFFAOYSA-N 0.000 description 2
- UZNHKBFIBYXPDV-UHFFFAOYSA-N trimethyl-[3-(2-methylprop-2-enoylamino)propyl]azanium;chloride Chemical compound [Cl-].CC(=C)C(=O)NCCC[N+](C)(C)C UZNHKBFIBYXPDV-UHFFFAOYSA-N 0.000 description 2
- PNBOBRKDXRJMTL-UHFFFAOYSA-N (2-nitrophenyl) benzoate Chemical compound [O-][N+](=O)C1=CC=CC=C1OC(=O)C1=CC=CC=C1 PNBOBRKDXRJMTL-UHFFFAOYSA-N 0.000 description 1
- OHWWOZGHMUITKG-UHFFFAOYSA-N (4-bromophenyl) benzoate Chemical compound C1=CC(Br)=CC=C1OC(=O)C1=CC=CC=C1 OHWWOZGHMUITKG-UHFFFAOYSA-N 0.000 description 1
- ALSTYHKOOCGGFT-KTKRTIGZSA-N (9Z)-octadecen-1-ol Chemical compound CCCCCCCC\C=C/CCCCCCCCO ALSTYHKOOCGGFT-KTKRTIGZSA-N 0.000 description 1
- ZPKJJNNXJWJAKV-UHFFFAOYSA-N (dodecan-2-ylamino) propane-1-sulfonate;sodium Chemical compound [Na].CCCCCCCCCCC(C)NOS(=O)(=O)CCC ZPKJJNNXJWJAKV-UHFFFAOYSA-N 0.000 description 1
- ZGFFRBOJKCLILZ-UHFFFAOYSA-N (dodecan-3-ylamino) propanoate;sodium Chemical compound [Na].CCCCCCCCCC(CC)NOC(=O)CC ZGFFRBOJKCLILZ-UHFFFAOYSA-N 0.000 description 1
- ZORQXIQZAOLNGE-UHFFFAOYSA-N 1,1-difluorocyclohexane Chemical compound FC1(F)CCCCC1 ZORQXIQZAOLNGE-UHFFFAOYSA-N 0.000 description 1
- KEQGZUUPPQEDPF-UHFFFAOYSA-N 1,3-dichloro-5,5-dimethylimidazolidine-2,4-dione Chemical compound CC1(C)N(Cl)C(=O)N(Cl)C1=O KEQGZUUPPQEDPF-UHFFFAOYSA-N 0.000 description 1
- NOGFHTGYPKWWRX-UHFFFAOYSA-N 2,2,6,6-tetramethyloxan-4-one Chemical compound CC1(C)CC(=O)CC(C)(C)O1 NOGFHTGYPKWWRX-UHFFFAOYSA-N 0.000 description 1
- LSZBMXCYIZBZPD-UHFFFAOYSA-N 2-[(1-hydroperoxy-1-oxohexan-2-yl)carbamoyl]benzoic acid Chemical compound CCCCC(C(=O)OO)NC(=O)C1=CC=CC=C1C(O)=O LSZBMXCYIZBZPD-UHFFFAOYSA-N 0.000 description 1
- QSOVSKMNRYAVJR-UHFFFAOYSA-N 2-benzoyloxybenzoic acid Chemical compound OC(=O)C1=CC=CC=C1OC(=O)C1=CC=CC=C1 QSOVSKMNRYAVJR-UHFFFAOYSA-N 0.000 description 1
- WREFNFTVBQKRGZ-UHFFFAOYSA-N 2-decylbutanediperoxoic acid Chemical compound CCCCCCCCCCC(C(=O)OO)CC(=O)OO WREFNFTVBQKRGZ-UHFFFAOYSA-N 0.000 description 1
- CJAZCKUGLFWINJ-UHFFFAOYSA-N 3,4-dihydroxybenzene-1,2-disulfonic acid Chemical class OC1=CC=C(S(O)(=O)=O)C(S(O)(=O)=O)=C1O CJAZCKUGLFWINJ-UHFFFAOYSA-N 0.000 description 1
- TYKPJLVEPXWTFW-UHFFFAOYSA-N 3,7,9-trichloro-1-isocyanopurine-2,6,8-trione Chemical compound ClN1C(=O)N([N+]#[C-])C(=O)C2=C1N(Cl)C(=O)N2Cl TYKPJLVEPXWTFW-UHFFFAOYSA-N 0.000 description 1
- JBNHKYQZNSPSOR-UHFFFAOYSA-N 4-(carboxymethylperoxy)-4-oxobutanoic acid Chemical class OC(=O)CCC(=O)OOCC(O)=O JBNHKYQZNSPSOR-UHFFFAOYSA-N 0.000 description 1
- 244000215068 Acacia senegal Species 0.000 description 1
- 241000228212 Aspergillus Species 0.000 description 1
- 240000006439 Aspergillus oryzae Species 0.000 description 1
- 241000894006 Bacteria Species 0.000 description 1
- OMPJBNCRMGITSC-UHFFFAOYSA-N Benzoylperoxide Chemical compound C=1C=CC=CC=1C(=O)OOC(=O)C1=CC=CC=C1 OMPJBNCRMGITSC-UHFFFAOYSA-N 0.000 description 1
- 235000018185 Betula X alpestris Nutrition 0.000 description 1
- 235000018212 Betula X uliginosa Nutrition 0.000 description 1
- BVKZGUZCCUSVTD-UHFFFAOYSA-M Bicarbonate Chemical class OC([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-M 0.000 description 1
- LSNNMFCWUKXFEE-UHFFFAOYSA-M Bisulfite Chemical compound OS([O-])=O LSNNMFCWUKXFEE-UHFFFAOYSA-M 0.000 description 1
- BTBUEUYNUDRHOZ-UHFFFAOYSA-N Borate Chemical compound [O-]B([O-])[O-] BTBUEUYNUDRHOZ-UHFFFAOYSA-N 0.000 description 1
- KNMZUYRTYPXGDH-UHFFFAOYSA-N BrC12NC(NC1(NC(N(C2=O)[N+]#[C-])=O)Br)=O Chemical compound BrC12NC(NC1(NC(N(C2=O)[N+]#[C-])=O)Br)=O KNMZUYRTYPXGDH-UHFFFAOYSA-N 0.000 description 1
- LRRDOTYFRDWULQ-UHFFFAOYSA-N BrN1C(N(C=2N(C(N(C(C1=2)=O)[N+]#[C-])=O)Br)Br)=O Chemical compound BrN1C(N(C=2N(C(N(C(C1=2)=O)[N+]#[C-])=O)Br)Br)=O LRRDOTYFRDWULQ-UHFFFAOYSA-N 0.000 description 1
- WKBOTKDWSSQWDR-UHFFFAOYSA-N Bromine atom Chemical compound [Br] WKBOTKDWSSQWDR-UHFFFAOYSA-N 0.000 description 1
- 229910021532 Calcite Inorganic materials 0.000 description 1
- BHPQYMZQTOCNFJ-UHFFFAOYSA-N Calcium cation Chemical compound [Ca+2] BHPQYMZQTOCNFJ-UHFFFAOYSA-N 0.000 description 1
- XXAXVMUWHZHZMJ-UHFFFAOYSA-N Chymopapain Chemical compound OC1=CC(S(O)(=O)=O)=CC(S(O)(=O)=O)=C1O XXAXVMUWHZHZMJ-UHFFFAOYSA-N 0.000 description 1
- FBPFZTCFMRRESA-FSIIMWSLSA-N D-Glucitol Natural products OC[C@H](O)[C@H](O)[C@@H](O)[C@H](O)CO FBPFZTCFMRRESA-FSIIMWSLSA-N 0.000 description 1
- FBPFZTCFMRRESA-JGWLITMVSA-N D-glucitol Chemical compound OC[C@H](O)[C@@H](O)[C@H](O)[C@H](O)CO FBPFZTCFMRRESA-JGWLITMVSA-N 0.000 description 1
- WQZGKKKJIJFFOK-QTVWNMPRSA-N D-mannopyranose Chemical compound OC[C@H]1OC(O)[C@@H](O)[C@@H](O)[C@@H]1O WQZGKKKJIJFFOK-QTVWNMPRSA-N 0.000 description 1
- QEVGZEDELICMKH-UHFFFAOYSA-N Diglycolic acid Chemical class OC(=O)COCC(O)=O QEVGZEDELICMKH-UHFFFAOYSA-N 0.000 description 1
- RWSOTUBLDIXVET-UHFFFAOYSA-N Dihydrogen sulfide Chemical class S RWSOTUBLDIXVET-UHFFFAOYSA-N 0.000 description 1
- KCXVZYZYPLLWCC-UHFFFAOYSA-N EDTA Chemical class OC(=O)CN(CC(O)=O)CCN(CC(O)=O)CC(O)=O KCXVZYZYPLLWCC-UHFFFAOYSA-N 0.000 description 1
- 241000196324 Embryophyta Species 0.000 description 1
- PIICEJLVQHRZGT-UHFFFAOYSA-N Ethylenediamine Chemical compound NCCN PIICEJLVQHRZGT-UHFFFAOYSA-N 0.000 description 1
- WSFSSNUMVMOOMR-UHFFFAOYSA-N Formaldehyde Chemical compound O=C WSFSSNUMVMOOMR-UHFFFAOYSA-N 0.000 description 1
- 241000233866 Fungi Species 0.000 description 1
- 229920000084 Gum arabic Polymers 0.000 description 1
- 239000005639 Lauric acid Substances 0.000 description 1
- 229920000877 Melamine resin Polymers 0.000 description 1
- CERQOIWHTDAKMF-UHFFFAOYSA-M Methacrylate Chemical compound CC(=C)C([O-])=O CERQOIWHTDAKMF-UHFFFAOYSA-M 0.000 description 1
- 241000187479 Mycobacterium tuberculosis Species 0.000 description 1
- 244000218514 Opuntia robusta Species 0.000 description 1
- 235000003166 Opuntia robusta Nutrition 0.000 description 1
- 235000021314 Palmitic acid Nutrition 0.000 description 1
- 102000019280 Pancreatic lipases Human genes 0.000 description 1
- 108050006759 Pancreatic lipases Proteins 0.000 description 1
- 102000035195 Peptidases Human genes 0.000 description 1
- IMQLKJBTEOYOSI-UHFFFAOYSA-N Phytic acid Natural products OP(O)(=O)OC1C(OP(O)(O)=O)C(OP(O)(O)=O)C(OP(O)(O)=O)C(OP(O)(O)=O)C1OP(O)(O)=O IMQLKJBTEOYOSI-UHFFFAOYSA-N 0.000 description 1
- 229920002257 Plurafac® Polymers 0.000 description 1
- 229920002004 Pluronic® R Polymers 0.000 description 1
- 229930182556 Polyacetal Natural products 0.000 description 1
- 229920000388 Polyphosphate Polymers 0.000 description 1
- 101710194948 Protein phosphatase PhpP Proteins 0.000 description 1
- 241000589516 Pseudomonas Species 0.000 description 1
- UDQKLVFQAFYISR-UHFFFAOYSA-N S(=O)(=O)(O)C(COC(O)=O)C1=CC=CC=C1.[Na] Chemical compound S(=O)(=O)(O)C(COC(O)=O)C1=CC=CC=C1.[Na] UDQKLVFQAFYISR-UHFFFAOYSA-N 0.000 description 1
- 241000221662 Sclerotinia Species 0.000 description 1
- 239000004115 Sodium Silicate Substances 0.000 description 1
- DWAQJAXMDSEUJJ-UHFFFAOYSA-M Sodium bisulfite Chemical compound [Na+].OS([O-])=O DWAQJAXMDSEUJJ-UHFFFAOYSA-M 0.000 description 1
- IYFATESGLOUGBX-YVNJGZBMSA-N Sorbitan monopalmitate Chemical compound CCCCCCCCCCCCCCCC(=O)OC[C@@H](O)[C@H]1OC[C@H](O)[C@H]1O IYFATESGLOUGBX-YVNJGZBMSA-N 0.000 description 1
- HVUMOYIDDBPOLL-XWVZOOPGSA-N Sorbitan monostearate Chemical compound CCCCCCCCCCCCCCCCCC(=O)OC[C@@H](O)[C@H]1OC[C@H](O)[C@H]1O HVUMOYIDDBPOLL-XWVZOOPGSA-N 0.000 description 1
- 239000004147 Sorbitan trioleate Substances 0.000 description 1
- PRXRUNOAOLTIEF-ADSICKODSA-N Sorbitan trioleate Chemical compound CCCCCCCC\C=C/CCCCCCCC(=O)OC[C@@H](OC(=O)CCCCCCC\C=C/CCCCCCCC)[C@H]1OC[C@H](O)[C@H]1OC(=O)CCCCCCC\C=C/CCCCCCCC PRXRUNOAOLTIEF-ADSICKODSA-N 0.000 description 1
- 241000519995 Stachys sylvatica Species 0.000 description 1
- 241000191940 Staphylococcus Species 0.000 description 1
- 235000021355 Stearic acid Nutrition 0.000 description 1
- 108010056079 Subtilisins Proteins 0.000 description 1
- 102000005158 Subtilisins Human genes 0.000 description 1
- 244000269722 Thea sinensis Species 0.000 description 1
- 241000223258 Thermomyces lanuginosus Species 0.000 description 1
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 1
- 241000235015 Yarrowia lipolytica Species 0.000 description 1
- NCHJGQKLPRTMAO-XWVZOOPGSA-N [(2R)-2-[(2R,3R,4S)-3,4-dihydroxyoxolan-2-yl]-2-hydroxyethyl] 16-methylheptadecanoate Chemical compound CC(C)CCCCCCCCCCCCCCC(=O)OC[C@@H](O)[C@H]1OC[C@H](O)[C@H]1O NCHJGQKLPRTMAO-XWVZOOPGSA-N 0.000 description 1
- YHGREDQDBYVEOS-UHFFFAOYSA-N [acetyloxy-[2-(diacetyloxyamino)ethyl]amino] acetate Chemical class CC(=O)ON(OC(C)=O)CCN(OC(C)=O)OC(C)=O YHGREDQDBYVEOS-UHFFFAOYSA-N 0.000 description 1
- 239000000205 acacia gum Substances 0.000 description 1
- 235000010489 acacia gum Nutrition 0.000 description 1
- ZXXMRXJZFTUYQE-UHFFFAOYSA-N acetic acid 2,3-dihydroxybutanedioic acid Chemical class C(C)(=O)O.C(C)(=O)O.C(=O)(O)C(O)C(O)C(=O)O ZXXMRXJZFTUYQE-UHFFFAOYSA-N 0.000 description 1
- LMESJJCHPWBJHQ-UHFFFAOYSA-N acetic acid;2,3-dihydroxybutanedioic acid Chemical class CC(O)=O.OC(=O)C(O)C(O)C(O)=O LMESJJCHPWBJHQ-UHFFFAOYSA-N 0.000 description 1
- 150000007933 aliphatic carboxylic acids Chemical class 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- 229910000288 alkali metal carbonate Inorganic materials 0.000 description 1
- 150000008041 alkali metal carbonates Chemical class 0.000 description 1
- 229910052784 alkaline earth metal Inorganic materials 0.000 description 1
- 150000001342 alkaline earth metals Chemical class 0.000 description 1
- 125000005024 alkenyl aryl group Chemical group 0.000 description 1
- 150000004703 alkoxides Chemical class 0.000 description 1
- 125000003282 alkyl amino group Chemical group 0.000 description 1
- 125000005210 alkyl ammonium group Chemical group 0.000 description 1
- 125000002877 alkyl aryl group Chemical group 0.000 description 1
- 150000004996 alkyl benzenes Chemical class 0.000 description 1
- 125000005907 alkyl ester group Chemical group 0.000 description 1
- 150000008051 alkyl sulfates Chemical class 0.000 description 1
- 125000005263 alkylenediamine group Polymers 0.000 description 1
- RMRFFCXPLWYOOY-UHFFFAOYSA-N allyl radical Chemical compound [CH2]C=C RMRFFCXPLWYOOY-UHFFFAOYSA-N 0.000 description 1
- WQZGKKKJIJFFOK-PHYPRBDBSA-N alpha-D-galactose Chemical compound OC[C@H]1O[C@H](O)[C@H](O)[C@@H](O)[C@H]1O WQZGKKKJIJFFOK-PHYPRBDBSA-N 0.000 description 1
- 230000004075 alteration Effects 0.000 description 1
- AZDRQVAHHNSJOQ-UHFFFAOYSA-N alumane Chemical class [AlH3] AZDRQVAHHNSJOQ-UHFFFAOYSA-N 0.000 description 1
- 229940025131 amylases Drugs 0.000 description 1
- 150000001449 anionic compounds Chemical class 0.000 description 1
- 239000002518 antifoaming agent Substances 0.000 description 1
- 125000005018 aryl alkenyl group Chemical group 0.000 description 1
- 125000003710 aryl alkyl group Chemical group 0.000 description 1
- 125000004429 atom Chemical group 0.000 description 1
- YVUMSUIENBQZTE-UHFFFAOYSA-N benzenesulfonyl benzenecarboperoxoate;potassium Chemical compound [K].C=1C=CC=CC=1C(=O)OOS(=O)(=O)C1=CC=CC=C1 YVUMSUIENBQZTE-UHFFFAOYSA-N 0.000 description 1
- QRUDEWIWKLJBPS-UHFFFAOYSA-N benzotriazole Chemical compound C1=CC=C2N[N][N]C2=C1 QRUDEWIWKLJBPS-UHFFFAOYSA-N 0.000 description 1
- 239000012964 benzotriazole Substances 0.000 description 1
- 235000019400 benzoyl peroxide Nutrition 0.000 description 1
- 210000001124 body fluid Anatomy 0.000 description 1
- 239000010839 body fluid Substances 0.000 description 1
- 150000001642 boronic acid derivatives Chemical class 0.000 description 1
- FNXLCIKXHOPCKH-UHFFFAOYSA-N bromamine Chemical class BrN FNXLCIKXHOPCKH-UHFFFAOYSA-N 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
- CMFFZBGFNICZIS-UHFFFAOYSA-N butanedioic acid;2,3-dihydroxybutanedioic acid Chemical class OC(=O)CCC(O)=O.OC(=O)CCC(O)=O.OC(=O)C(O)C(O)C(O)=O CMFFZBGFNICZIS-UHFFFAOYSA-N 0.000 description 1
- HXDRSFFFXJISME-UHFFFAOYSA-N butanedioic acid;2,3-dihydroxybutanedioic acid Chemical class OC(=O)CCC(O)=O.OC(=O)C(O)C(O)C(O)=O HXDRSFFFXJISME-UHFFFAOYSA-N 0.000 description 1
- 239000002775 capsule Substances 0.000 description 1
- 239000004202 carbamide Substances 0.000 description 1
- 150000001720 carbohydrates Chemical class 0.000 description 1
- 150000001732 carboxylic acid derivatives Chemical class 0.000 description 1
- 230000015556 catabolic process Effects 0.000 description 1
- 239000007795 chemical reaction product Substances 0.000 description 1
- 125000001309 chloro group Chemical group Cl* 0.000 description 1
- 238000010367 cloning Methods 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 235000019864 coconut oil Nutrition 0.000 description 1
- 239000003240 coconut oil Substances 0.000 description 1
- 239000003086 colorant Substances 0.000 description 1
- 238000002485 combustion reaction Methods 0.000 description 1
- 238000009833 condensation Methods 0.000 description 1
- 230000005494 condensation Effects 0.000 description 1
- 229910052802 copper Inorganic materials 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 238000006731 degradation reaction Methods 0.000 description 1
- 230000001419 dependent effect Effects 0.000 description 1
- CEJLBZWIKQJOAT-UHFFFAOYSA-N dichloroisocyanuric acid Chemical class ClN1C(=O)NC(=O)N(Cl)C1=O CEJLBZWIKQJOAT-UHFFFAOYSA-N 0.000 description 1
- FRXGWNKDEMTFPL-UHFFFAOYSA-N dioctadecyl hydrogen phosphate Chemical compound CCCCCCCCCCCCCCCCCCOP(O)(=O)OCCCCCCCCCCCCCCCCCC FRXGWNKDEMTFPL-UHFFFAOYSA-N 0.000 description 1
- HNPSIPDUKPIQMN-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Al]O[Al]=O HNPSIPDUKPIQMN-UHFFFAOYSA-N 0.000 description 1
- VTIIJXUACCWYHX-UHFFFAOYSA-L disodium;carboxylatooxy carbonate Chemical compound [Na+].[Na+].[O-]C(=O)OOC([O-])=O VTIIJXUACCWYHX-UHFFFAOYSA-L 0.000 description 1
- 238000004090 dissolution Methods 0.000 description 1
- LQZZUXJYWNFBMV-UHFFFAOYSA-N dodecan-1-ol Chemical compound CCCCCCCCCCCCO LQZZUXJYWNFBMV-UHFFFAOYSA-N 0.000 description 1
- BRDYCNFHFWUBCZ-UHFFFAOYSA-N dodecaneperoxoic acid Chemical compound CCCCCCCCCCCC(=O)OO BRDYCNFHFWUBCZ-UHFFFAOYSA-N 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 239000000839 emulsion Substances 0.000 description 1
- RTZKZFJDLAIYFH-UHFFFAOYSA-N ether Substances CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 1
- 238000007046 ethoxylation reaction Methods 0.000 description 1
- 239000003925 fat Substances 0.000 description 1
- 235000019197 fats Nutrition 0.000 description 1
- 239000006260 foam Substances 0.000 description 1
- 235000013305 food Nutrition 0.000 description 1
- 235000019256 formaldehyde Nutrition 0.000 description 1
- 238000005194 fractionation Methods 0.000 description 1
- 239000013538 functional additive Substances 0.000 description 1
- 125000000524 functional group Chemical group 0.000 description 1
- 229930182830 galactose Natural products 0.000 description 1
- 150000004676 glycans Chemical class 0.000 description 1
- 125000001046 glycoluril group Chemical group [H]C12N(*)C(=O)N(*)C1([H])N(*)C(=O)N2* 0.000 description 1
- 229930182470 glycoside Natural products 0.000 description 1
- KWLMIXQRALPRBC-UHFFFAOYSA-L hectorite Chemical compound [Li+].[OH-].[OH-].[Na+].[Mg+2].O1[Si]2([O-])O[Si]1([O-])O[Si]([O-])(O1)O[Si]1([O-])O2 KWLMIXQRALPRBC-UHFFFAOYSA-L 0.000 description 1
- 229910000271 hectorite Inorganic materials 0.000 description 1
- 150000001469 hydantoins Chemical class 0.000 description 1
- BHEPBYXIRTUNPN-UHFFFAOYSA-N hydridophosphorus(.) (triplet) Chemical compound [PH] BHEPBYXIRTUNPN-UHFFFAOYSA-N 0.000 description 1
- 125000001165 hydrophobic group Chemical group 0.000 description 1
- 230000005661 hydrophobic surface Effects 0.000 description 1
- 239000003752 hydrotrope Substances 0.000 description 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- 125000005020 hydroxyalkenyl group Chemical group 0.000 description 1
- 125000002768 hydroxyalkyl group Chemical group 0.000 description 1
- 238000010348 incorporation Methods 0.000 description 1
- 230000005764 inhibitory process Effects 0.000 description 1
- 150000002484 inorganic compounds Chemical class 0.000 description 1
- 239000011256 inorganic filler Substances 0.000 description 1
- 229910003475 inorganic filler Inorganic materials 0.000 description 1
- 229910010272 inorganic material Inorganic materials 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 230000000670 limiting effect Effects 0.000 description 1
- 239000011777 magnesium Substances 0.000 description 1
- USSBDBZGEDUBHE-UHFFFAOYSA-L magnesium;2-oxidooxycarbonylbenzoate Chemical compound [Mg+2].[O-]OC(=O)C1=CC=CC=C1C([O-])=O USSBDBZGEDUBHE-UHFFFAOYSA-L 0.000 description 1
- 150000002690 malonic acid derivatives Chemical class 0.000 description 1
- 235000013310 margarine Nutrition 0.000 description 1
- 239000003264 margarine Substances 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- JDSHMPZPIAZGSV-UHFFFAOYSA-N melamine Chemical compound NC1=NC(N)=NC(N)=N1 JDSHMPZPIAZGSV-UHFFFAOYSA-N 0.000 description 1
- 230000008018 melting Effects 0.000 description 1
- 238000002844 melting Methods 0.000 description 1
- 108010003855 mesentericopeptidase Proteins 0.000 description 1
- 229910044991 metal oxide Inorganic materials 0.000 description 1
- 150000004706 metal oxides Chemical class 0.000 description 1
- 230000002906 microbiologic effect Effects 0.000 description 1
- 244000005700 microbiome Species 0.000 description 1
- 239000002480 mineral oil Substances 0.000 description 1
- 235000010446 mineral oil Nutrition 0.000 description 1
- 229910052901 montmorillonite Inorganic materials 0.000 description 1
- 229940043348 myristyl alcohol Drugs 0.000 description 1
- WQEPLUUGTLDZJY-UHFFFAOYSA-N n-Pentadecanoic acid Natural products CCCCCCCCCCCCCCC(O)=O WQEPLUUGTLDZJY-UHFFFAOYSA-N 0.000 description 1
- 229920001206 natural gum Polymers 0.000 description 1
- QIQXTHQIDYTFRH-UHFFFAOYSA-N octadecanoic acid Chemical compound CCCCCCCCCCCCCCCCCC(O)=O QIQXTHQIDYTFRH-UHFFFAOYSA-N 0.000 description 1
- OQCDKBAXFALNLD-UHFFFAOYSA-N octadecanoic acid Natural products CCCCCCCC(C)CCCCCCCCC(O)=O OQCDKBAXFALNLD-UHFFFAOYSA-N 0.000 description 1
- UHGIMQLJWRAPLT-UHFFFAOYSA-N octadecyl dihydrogen phosphate Chemical compound CCCCCCCCCCCCCCCCCCOP(O)(O)=O UHGIMQLJWRAPLT-UHFFFAOYSA-N 0.000 description 1
- 239000003921 oil Substances 0.000 description 1
- 235000019198 oils Nutrition 0.000 description 1
- 229940055577 oleyl alcohol Drugs 0.000 description 1
- XMLQWXUVTXCDDL-UHFFFAOYSA-N oleyl alcohol Natural products CCCCCCC=CCCCCCCCCCCO XMLQWXUVTXCDDL-UHFFFAOYSA-N 0.000 description 1
- 239000003605 opacifier Substances 0.000 description 1
- 210000000056 organ Anatomy 0.000 description 1
- 150000002894 organic compounds Chemical class 0.000 description 1
- 239000012766 organic filler Substances 0.000 description 1
- 150000004967 organic peroxy acids Chemical class 0.000 description 1
- 125000001741 organic sulfur group Chemical group 0.000 description 1
- 230000001590 oxidative effect Effects 0.000 description 1
- 235000013808 oxidized starch Nutrition 0.000 description 1
- 239000012188 paraffin wax Substances 0.000 description 1
- 239000002304 perfume Substances 0.000 description 1
- 150000004965 peroxy acids Chemical class 0.000 description 1
- 125000000864 peroxy group Chemical group O(O*)* 0.000 description 1
- LUSSRKMAXZEBEC-UHFFFAOYSA-N phenyl 4-nitrobenzoate Chemical compound C1=CC([N+](=O)[O-])=CC=C1C(=O)OC1=CC=CC=C1 LUSSRKMAXZEBEC-UHFFFAOYSA-N 0.000 description 1
- FCJSHPDYVMKCHI-UHFFFAOYSA-N phenyl benzoate Chemical compound C=1C=CC=CC=1C(=O)OC1=CC=CC=C1 FCJSHPDYVMKCHI-UHFFFAOYSA-N 0.000 description 1
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 1
- XYFCBTPGUUZFHI-UHFFFAOYSA-O phosphonium Chemical compound [PH4+] XYFCBTPGUUZFHI-UHFFFAOYSA-O 0.000 description 1
- PTMHPRAIXMAOOB-UHFFFAOYSA-N phosphoramidic acid Chemical class NP(O)(O)=O PTMHPRAIXMAOOB-UHFFFAOYSA-N 0.000 description 1
- 125000003703 phosphorus containing inorganic group Chemical group 0.000 description 1
- 229940068041 phytic acid Drugs 0.000 description 1
- 239000000467 phytic acid Substances 0.000 description 1
- 229920001983 poloxamer Polymers 0.000 description 1
- 238000006116 polymerization reaction Methods 0.000 description 1
- 230000000379 polymerizing effect Effects 0.000 description 1
- 229920000193 polymethacrylate Polymers 0.000 description 1
- 229920002503 polyoxyethylene-polyoxypropylene Polymers 0.000 description 1
- 229920006324 polyoxymethylene Polymers 0.000 description 1
- 239000001205 polyphosphate Substances 0.000 description 1
- 235000011176 polyphosphates Nutrition 0.000 description 1
- 229920001282 polysaccharide Polymers 0.000 description 1
- 239000005017 polysaccharide Substances 0.000 description 1
- 235000015497 potassium bicarbonate Nutrition 0.000 description 1
- 229910000027 potassium carbonate Inorganic materials 0.000 description 1
- 235000011181 potassium carbonates Nutrition 0.000 description 1
- 239000001103 potassium chloride Substances 0.000 description 1
- 235000011164 potassium chloride Nutrition 0.000 description 1
- TYJJADVDDVDEDZ-UHFFFAOYSA-M potassium hydrogencarbonate Chemical class [K+].OC([O-])=O TYJJADVDDVDEDZ-UHFFFAOYSA-M 0.000 description 1
- 235000008476 powdered milk Nutrition 0.000 description 1
- 239000002244 precipitate Substances 0.000 description 1
- 238000001556 precipitation Methods 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 230000002829 reductive effect Effects 0.000 description 1
- 229920005989 resin Polymers 0.000 description 1
- 239000011347 resin Substances 0.000 description 1
- 230000000717 retained effect Effects 0.000 description 1
- 238000000518 rheometry Methods 0.000 description 1
- 239000008237 rinsing water Substances 0.000 description 1
- 229910000275 saponite Inorganic materials 0.000 description 1
- 239000003352 sequestering agent Substances 0.000 description 1
- 239000000741 silica gel Substances 0.000 description 1
- 229910002027 silica gel Inorganic materials 0.000 description 1
- 239000000377 silicon dioxide Substances 0.000 description 1
- 229920002545 silicone oil Polymers 0.000 description 1
- 235000017557 sodium bicarbonate Nutrition 0.000 description 1
- 229910000029 sodium carbonate Inorganic materials 0.000 description 1
- 235000010267 sodium hydrogen sulphite Nutrition 0.000 description 1
- 229940045872 sodium percarbonate Drugs 0.000 description 1
- 229910052911 sodium silicate Inorganic materials 0.000 description 1
- OVONNAXAHAIEDF-UHFFFAOYSA-M sodium;4-benzoyloxybenzenesulfonate Chemical compound [Na+].C1=CC(S(=O)(=O)[O-])=CC=C1OC(=O)C1=CC=CC=C1 OVONNAXAHAIEDF-UHFFFAOYSA-M 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 239000001593 sorbitan monooleate Substances 0.000 description 1
- 235000011069 sorbitan monooleate Nutrition 0.000 description 1
- 229940035049 sorbitan monooleate Drugs 0.000 description 1
- 235000011071 sorbitan monopalmitate Nutrition 0.000 description 1
- 239000001570 sorbitan monopalmitate Substances 0.000 description 1
- 229940031953 sorbitan monopalmitate Drugs 0.000 description 1
- 239000001587 sorbitan monostearate Substances 0.000 description 1
- 235000011076 sorbitan monostearate Nutrition 0.000 description 1
- 229940035048 sorbitan monostearate Drugs 0.000 description 1
- 235000019337 sorbitan trioleate Nutrition 0.000 description 1
- 229960000391 sorbitan trioleate Drugs 0.000 description 1
- 239000000600 sorbitol Substances 0.000 description 1
- 241000894007 species Species 0.000 description 1
- 230000007480 spreading Effects 0.000 description 1
- 238000003892 spreading Methods 0.000 description 1
- 229910001220 stainless steel Inorganic materials 0.000 description 1
- 239000010935 stainless steel Substances 0.000 description 1
- 239000008117 stearic acid Substances 0.000 description 1
- 125000001424 substituent group Chemical group 0.000 description 1
- 239000000758 substrate Substances 0.000 description 1
- 150000003890 succinate salts Chemical class 0.000 description 1
- 150000003445 sucroses Chemical class 0.000 description 1
- BDHFUVZGWQCTTF-UHFFFAOYSA-M sulfonate Chemical compound [O-]S(=O)=O BDHFUVZGWQCTTF-UHFFFAOYSA-M 0.000 description 1
- QAOWNCQODCNURD-UHFFFAOYSA-N sulfuric acid Substances OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 1
- 150000003467 sulfuric acid derivatives Chemical class 0.000 description 1
- 239000000375 suspending agent Substances 0.000 description 1
- 150000003512 tertiary amines Chemical class 0.000 description 1
- TUNFSRHWOTWDNC-HKGQFRNVSA-N tetradecanoic acid Chemical compound CCCCCCCCCCCCC[14C](O)=O TUNFSRHWOTWDNC-HKGQFRNVSA-N 0.000 description 1
- 150000004685 tetrahydrates Chemical class 0.000 description 1
- 125000000383 tetramethylene group Chemical group [H]C([H])([*:1])C([H])([H])C([H])([H])C([H])([H])[*:2] 0.000 description 1
- 230000009974 thixotropic effect Effects 0.000 description 1
- 229910052719 titanium Inorganic materials 0.000 description 1
- 239000010936 titanium Substances 0.000 description 1
- 239000003053 toxin Substances 0.000 description 1
- 231100000765 toxin Toxicity 0.000 description 1
- 108700012359 toxins Proteins 0.000 description 1
- 229910052723 transition metal Inorganic materials 0.000 description 1
- 229910001428 transition metal ion Inorganic materials 0.000 description 1
- 150000003624 transition metals Chemical class 0.000 description 1
- 150000003626 triacylglycerols Chemical class 0.000 description 1
- 125000005208 trialkylammonium group Chemical group 0.000 description 1
- 230000000007 visual effect Effects 0.000 description 1
- 239000001993 wax Substances 0.000 description 1
- GDJZZWYLFXAGFH-UHFFFAOYSA-M xylenesulfonate group Chemical group C1(C(C=CC=C1)C)(C)S(=O)(=O)[O-] GDJZZWYLFXAGFH-UHFFFAOYSA-M 0.000 description 1
- 239000010457 zeolite 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
- C11D3/3796—Amphoteric polymers or zwitterionic polymers
-
- 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
- C11D3/3769—(Co)polymerised monomers containing nitrogen, e.g. carbonamides, nitriles or amines
- C11D3/3773—(Co)polymerised monomers containing nitrogen, e.g. carbonamides, nitriles or amines 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
- C11D3/38—Products with no well-defined composition, e.g. natural products
- C11D3/386—Preparations containing enzymes, e.g. protease or amylase
- C11D3/38627—Preparations containing enzymes, e.g. protease or amylase containing lipase
-
- C11D2111/14—
Abstract
A composition and method of preventing lime soap deposition on tableware cleaned in a machine dishwasher are described. The detergent composition contains an effective amount of an amphoteric polymer and a lipolytic enzyme as described.
Description
CA 0221461~ 1997-09-03 C 6a~;2 (-V) ,.. .
Machine Dishwashinq Compo~ition ContAi n; n~ Am~hoteric PolYmers Field of Invention The invention relates to detergent compositions containing amphoteric polymers to control the deposition of lime soap, particularly machine dishwashing compositions containing lipolytic enzymes.
Backqround of the Invention A critical criteria for an effective machine dishwashing composition is the appearance of both the washed glassware and plastic articles to the consumer. Spotting and filming of such tableware, when washed with commercial products, generally results from mineral deposition during the evaporation of undrained wash solution in the drying step.
The deposited minerals are from many sources, including salts of ingredients in the product formulations, calcium carbonate from temporary water hardness, and suspended 20 soil.
The deposition on the surfaces of the washed articles make them look dull due to the presence of spots, streaks or surface covering film. The most intense spotting problems are related to the deposition of hydrophobic soil fragments. In the final rinse stage, this hydrophobic soil is thought to break-up the water film, leaving droplets ~ehind on the tableware which result in mineral deposits observed as white spots upon evaporation of the water component.
A prior art solution to the removal of these white mineral spots has been the addition of a rinse aid composition to the rinsing water of the machine cycle. Although the visual appearance of the washed tableware is improved, some CA 0221461~ 1997-09-03 C 6-~62 ~v) spotting, but especially mineral film formation has still been observed even with the use of this additional product.
Moreover, use of a rinse aid is inconvenient to the consumer.
The major fraction of the hydrophobic soil fragments that are present on washed tableware is believed to be triglyceride and fatty ester soil. Consequently, machine dishwashing and rinse aid compositions incorporating lipolytic enzymes which assist in breaking down these soiIs have been described in EP-A-346,136 and EP-A-271,155. Although lipolytic enzymes can reduce the formation of mineral spots due to hydrophobic soil fragments, the enzymes can also cause a different type of white deposits to build up on hydrophobic surfaces such as plastics. These fatty deposits are due to precipitation of lime soaps which are formed from the mixture of calcium and magnesium ions in the wash water with fatty acids, which are liberated from the triglyceride and fatty ester soils by the action of the lipolytic enzymes. The higher the level of fatty soil present in the dishwasher, the worse the problem of lime soap deposition.
Prior art solutions to these problems include formulations of machine dishwashing compositions incorporating certain lime soap dispersants with lipolytic enzymes as described in W0-94/07984 and W0-94/07985 (Proctor & Gamble). Tableware washed with compositions containing lipases and these lime soap dispersants have been observed to have low lime soap film scores (i.e. little to no filming is observed).
However, a large number of white mineral spots on the washed articles have been observed. It is thus believed that the lime soap dispersants described in these publications actually inhibit the action of the lipase.
CA 0221461~ 1997-09-03 C 6-~62 (.V) Hydrophobically modified copolymers, of especially acrylic acid, have been described in copending Gordon et al.; U.S.
Serial No. 08/457,690 for incorporation in machine dishwashing compositions. Calcium soap deposition is reduced by the presence of these polymers.
US-A-4,891,149 describes polymeric lime soap dispersants which consist of copolymers and water soluble salts of copolymers of acrylic acid, methacrylic acid and mixtures thereof and acrylamide, alkyl or alkylol substituted acrylamide, or mixture of said acrylamides. Optionally, enzymes may also be added to the formulations.
US-A-5,308,532 (Rohm & Haas) describes aminoacryloyl -containing terpolymers which are useful for reducing mineral spotting and filming of tableware. Thus, the detergent formulation acts by preventing hydrophobic deposits on glassware and does not address the issue of preventing lime soap deposition. The use of lipolytic enzymes in combination with such terpolymers to control the deposition of lime soaps is neither taught nor suggested.
It is therefore an object of the present invention to provide machine dishwashing compositions and methods of using them to prevent lime soap deposition on washed tableware.
Another object of the invention is to selectively combine lipolytic enzymes with particular amphoteric polymers in a detergent composition to control lime soap deposition and virtually prevent spotting and lime soap filming on cleaned tableware.
Summary of the Invention CA 0221461~ 1997-09-03 C 6.362 (V) Accordingly, the present invention provides a machine washing composition comprising:
(a) an effective amount of a amphoteric polymer wherein in a 1~ aqueous wash liquor having a pH of about 7 or greater, positive charges on the polymer comprise between 1~ and 50~, preferably between 2~ and 20~, most preferably between 5 and 15~ of the total charges on the polymer having a formula selected from:
i) AXByCz where in a 1~ aqueous wash liquor pH
A is an anionic moiety, B is a cationic moiety and C is an anionic, cationic, amphoteric or uncharged moiety and mixtures thereof, x, y, and z refer to mole percentages, x is 50-99~, preferably 80-98~, most preferably 85-95~, and y is 1-50~, preferably 2-20~, most preferably 5-15~ and z is 0 to 25~, preferably 0 to 18~;
or ii) DdEf where at the wash pH D is an amphoteric moiety, E is an anionic, cationic, or uncharged moiety and mixture thereof, d and f refer to mole percentages, and d is 1-100~ and f is 0-99~ provided the above stated charge distribution is satisfied;
(b) 0.01~ to about 4 wt. ~ of a lipolytic enzyme; and (c) about 1 to about 75~ by wt. of a builder material.
A bleaching agent is optionally included.
Detailed DescriPtion of Preferred Embodiments The amphoteric polymers incorporated in the compositions of the invention are present in an effective amount, preferably about 0.1 to about 25~, more preferably from CA 022l46l~ l997-09-03 C 6362 (V) about 1 to about 15~, most preferably from about 2 to about 10~ by wt.
Wash pH is defined as the measured pH of a 1~ aqueous solution of dishwasher water in the main wash cycle after addition and dissolution of the detergent composition. At a wash pH preferably between about 7 and about 12, most preferably between about 8 and about 11, positive charges on the polymer comprise between 1~ and 50~, preferably between 2~ and 20~, most preferably between 5 and 15~ of the total charges on the polymer.
The amphoteric polymers are addition polymers which may be prepared by (1) copolymerizing selected monomers which are anionic at the wash pH with selected monomers which are cationic at the wash pH, or (2) by polymerizing selected amphoteric monomers.
A first means of preparing the amphoteric polymers which are useful in the invention consists of copolymerizing from about 50 to about 99~ , preferably from about 80 to about 98~, most preferably from about 85 to about 98% by wt. of the anionic monomer (A) with about 1 to about 50~, preferably from about 2 to about 20~, most preferably from about 2 to about 15~ by wt. of the cationic monomer.
Optionally, a charged or uncharged moiety (C) is also copolymerized.
The monomers (A) used to prepare the amphoteric polymers are substituted vinyl compounds which have anionic character at wash pH. Preferred monomers are substituted vinyl compounds of formula l CA 0221461~ 1997-09-03 C 6 ~62 (V) (I) Rl R2 wherein R1, R2, and R3 are independently a hydrogen, C1 to C3 alkyl, a carboxylate group or a carboxylate group substituted with a C1 to C30 straight or branched alkyl, aromatic heterocycle or a polyalkylamine oxide with the requirement that at least one of R1, R2, or R3 must be a carboxylate or substituted carboxylate;
Preferred monomers include acrylic acid, methacrylic acid, maleic acid, ~-ethacrylic acid, ~,~,-dimethacrylic acid, methylenemalonic acid, vinylacetic acid, allylacetic acid, ethylidineacetic acid, propylidineacitic acid, crotonic acid, fumaric acid, itaconic acid, citraconic acid, mesaconic acid and the like. Most preferred monomers include acrylic acid, methacrylic acid, and maleic acid.
The monomers (B) used to form the amphoteric polymers of the invention which have cationic character at wash pH are substituted vinyl compounds of formula ll I I ~) wherein R4 is a hydrogen, aromatic, heterocycle or a polyalkylamine oxide; Rs is a hydrogen or a Cl to C30 straight or branched alkyl; and Q i8 a nitrogen-containing organic radical, said radical having a pKa value of ~ 7.
CA 0221461~ 1997-09-03 C 6~62 (~) methacrylate, dialkylaminoalkyl acrylate, dialkylaminoalkyl methacrylamide and dialkylaminoalkyl acrylamide.
The monomers of formula II are preferably quaternized wherein Q is preferably selected from the group consisting of formula 111 --CH2N (CH3)~,CH2CH=CH2 X (III) wherein X~ is any suitable counterion such as halogen, hydroxide, sulfate, hydrosulfate, phosphate, formate and lS acetate or, a compound of formula lV
-Z-CH2-CR6R7(CH2)mN ' R8R9R'0 (IV) wherein Z is selected from the group consisting of O, COO
and CONR11 in which R11 is a hydrogen or a C1 to C3 alkyl group; R6 and R7 are each independently selected from the group consisting of hydrogen, C1 to C4 alkyl or R6 and R7 taken together form a C3 to C7 aliphatic heterocycle; m is 0 to 2 provided that when m is 0 a C-N bond is present in lieu of the (CH2)m group and R8, R9, and R10are each independently selected from a group consisting of hydrogen or a Cl to C~ alkyl; or R8 and R9 are taken together with the nitrogen to which they are attached to form a 3 to 7 membered non-aromatic nitrogen heterocycle; and X is any suitable counterion such as a halogen, hydroxide, sulfate, hydrosulfate, phosphate, formate and acetate.
CA 0221461~ 1997-09-03 C 6362 (V.) Preferred examples of the quaternized monomers are (3-acrylamidopropyl) trimethylammonium chloride (APTAC), (3-methacrylamidopropyl) trimethylammonium chloride (MAPTAC), and dimethyldiallylammonium chloride (DMDAC). Other suitable examples include such materials as vinylbenzyltrialkylammonium salts and the like.
Monomers (C) which are anionic or cationic are selected from compounds of formula I or II, respectively.
Amphoteric monomers (C) may be selected from compounds of formula V described below.
/ IRl3 \ IRl~ 1~l t R ~ Rl6 Y
wherein, Rl2 is a C3 to C6 monoethylenically unsaturated carboxylate; Rl3 and Rl~ each independently represent hydrogen or a Cl to C3 alkyl; Rls and Rl6 each independently represent a hydrogen or a Cl to C3 alkyl; x is 1 to 3; and y is 1 to 3.
Suitable carboxylates represented by Rl2 include, but are not limited to, acrylic acid, methacrylic acid, ~-ethacrylic acid, ~,~,-dimethacrylic acid, methylenemalonic acid, vinylacetic acid, allylacetic acid, ethylidineacetic acid, propylidineacitic acid, crotonic acid, maleic acid, fumaric acid, itaconic acid, citraconic acid, mesaconic acid, and alkali metal and ammonium salts thereof.
CA 0221461~ 1997-09-03 C 6362 (V) Preferably, the unsaturated carboxylic acid is acrylic or methacrylic acid.
Uncharged monomers (C) are selected from C1-Cs alkyl esters of acrylic acid, methacrylic acid, and itaconic acid; C1C4 hydroxyalkyl esters of acrylic acid, methacrylic acid, and itaconic acid, alkylene oxide esters of acrylic acid, methacrylic acid, and itaconic acid having 1-20 alkylene oxide repeat units; and Cl-C20 EO1-EO20 ethoxyalkyl esters of acrylic acid, methacrylic acid, and itaconic acid;
styrene; vinyl alcohol; vinyl acetate; methyl vinyl ether;
and allyl alcohols. Preferably the uncharged monomer is C1-C4 alkyl ester of acrylic acid, methacrylic acid, or itaconic acid, C1-C4 hydroxyalkyl ester of acrylic acid, methacrylic acid, or itaconic acid, or C1-C20 EO1-EO20 ethoxyalkyl ester of acrylilc acid, methacrylic acid, or itaconic acid.
If these optional monomers (C) are present they should be present only in an amount of less than 25~ of the total monomer distribution.
Preferably the amphoteric polymers (AXByCz wherein z is 0) produced from the monomers of formulas l and ll are formed of monomers of acrylic acid polymerized with quaternized basic monomers.
A second means of obtaining amphoteric polymers useful in the invention is the polymerization of an amphoteric monomer (D) having a formula (V) as described above.
The amphoteric monomers of formula (V) may be homopolymerized or copolymerized with non-amphoteric polymerizable monomers (E) in an amount from about 0 to about 99~ by wt., preferably from 0 to about 75~ by wt., 3 5 with the requirement that the previously defined polymer charge distribution be satisfied.
CA 0221461~ 1997-09-03 C 6362 (~) Suitable anionic, and cationic monomers from which the moiety E is selected are represented by formulas I and II.
Uncharged monomers are selected from C1-C4 alkyl esters of acrylic acid, methacrylic acid, and itaconic acid; C1-C4 hydroxyalkyl esters of acrylic acid, methacrylic acid, and itaconic acid, alkylene oxide esters of acrylic acid, methacrylic acid, and itaconic acid having 1-20 alkylene oxide repeat units; and Cl-C20 EO1-EO20 ethoxyalkyl esters of acrylic acid, methacrylic acid, and itaconic acid;
styrene; vinyl alcohol; vinyl acetate; methyl vinyl ether;
and allyl alcohols. Preferably the uncharged monomer is C1-C4 alkyl ester of acrylic acid, methacrylic acid, or itaconic acid, C1-C4 hydroxyalkyl ester of acrylic acid, methacrylic acid, or itaconic acid, or C1-C20 EO1-EO20 ethoxyalkyl ester of acrylilc acid, methacrylic acid, or itaconic acid.
Suitable examples of amphoteric polymers include, but are not limited to, a copolymer of acrylic acid and 3-acrylamidopropyl trimethylammonium chloride as described inEP-A- 560, 519 Rohm and Haas, and EXP-2072 and EXP-2075 (terpolymers of acrylic acid, dimethyldiallylammonium chloride and C14-20 EO 20 itaconate ester available from Alco). Preferably, the polymers are the copolymers of acrylic acid and 3-acrylamido-propyl trimethylammonium chloride.
LiPolYtic EnzYmes Li~olytic enzymes are an essential component of the machine washing compositions of the invention. They are present at levels of active enzyme of from 0.01 to 4% by wt., preferably 0.01~ to 3% by wt., most preferably from 0.05%
to 1.5% by wt. of the composition, based on lipolytic activity of 100 LU/mg. Lipolytic activity is commonly defined by the amount of titratable fatty acid liberated from triglyceride under specified conditions. One lipase CA 0221461~ 1997-09-03 C 6362 (v) unit (LU) of activity is equivalent to liberation of one micromole of butyric acid per minute from an emulsion of tributyrin and gum arabic in the presence of Ca++ and NaCl at 30 Deg. C and pH 7.
Lipases facilitate the degradation or alteration of soils and stains comprising triglycerides or fatty esters.
Lipases suitable for use herein include those of animal, plant and microbiological origin. Suitable lipases are also found in many strains of bacteria and fungi. For example, lipases suitable for use herein can be obtained from Pseudomonas, Aspergillus, Staphylococcus, Toxins, Mycobacterium Tuberculosis, Mycotorula Lipolytica and Sclerotinia microorganisms. Lipases from chemically or genetically modified mutants are also included herein.
Mixtures of lipase from various strains are also included herein.
Suitable animal lipases are found in the body fluids and organs of many species. A preferred class of animal lipase herein are the pancreatic lipases.
A preferred lipase herein is obtained by cloning the gene from Humicola lanuginosa and expressing the gene in Aspergillus oryza, as host, as described in EP-A-0258068, which is commercially available from Novo Industri A/S, Denmark, under the tradename Lipolase.
Tradenames of other suitable lipases are Lipomax, ex. Gist Brocades (now Genencor), the Netherlands and Lipase G-1000, ex. Solvay Enzymes, USA.
Hypohalite Bleachinq Aqent Hypohalite may be used as long as the bleach is added to avoid deactivation of the enzymes of the formulation. A
preferred method of preventing enzyme deactivation is CA 0221461~ 1997-09-03 C 6362 (V) ~ .
encapsulation of the bleach is described in-US-A-5,200,236, herein incorporated by reference. In the patented method, the bleaching agent is encapsulated as a core in a paraffin wax material having a melting point from about 40~C to 50~C. The wax coating has a thickness of from 100 to 1500 mlcrons .
Suitable reactive chlorine or bromine oxidizing materials are chloro and bromo amides such as trichloroisocyanuric, tribromoisocyanuric, dibromoisocyanuric and dichloroisocyanuric acids, and salts thereof with water solubilizing cations such as potassium and sodium.
Hydantoin compounds such as 1,3-dichloro-5,5-dimethylhydantoin are also quite suitable.
PeroxY Bleachinq Aqents The oxygen bleaching agents of the compositions include organic peroxy acids and diacylperoxides. Typical monoperoxy acids useful herein include alkyl peroxy acids and aryl peroxy acids such as:
i) peroxybenzoic acid and ring-substituted peroxybenzoic acids, e.g., peroxy-alpha-naphthoic acid, and magnesium monoperoxyphthalate ii) aliphatic and substituted aliphatic monoperoxy acids, e.g., peroxylauric acid, epsilon-phthalimido-peroxyhexanoic acid and o-carboxybenzamido peroxyhexanoic acid, N-nonylamidoperadipic acid and N-nonylamidopersuccinic acid.
iii) Cationic peroxyacids such as those described in US-A-5,422,028, US-A-5,294,362; and US-A-5,292,447, Atty. Docket No. 95-0394-UNI; Case 7392, Oakes et al.; and U.S. S/N
08/210, 973, Oakes et al., herein incorporated by reference.
CA 0221461~ 1997-09-03 C 6362 (V) iv) Sulfonyl peroxyacids such as compounds described in US-A-5,039,447 (Monsanto Co.), herein incorporated by reference.
Typical diperoxy acids useful herein include alkyl diperoxy acids and aryl diperoxy acids, such as:
v) 1,12-diperoxydodecanedioic acid vi) 1,9-diperoxyazelaic acid vii) diperoxybrassylic acid; diperoxysecacic acid and diperoxy-isophthalic acid viii) 2-decyldiperoxybutan-1,4-dioic acid ix) N,N1-terephthaloyl-di(6-aminopercaproic acid).
A typical diacylperoxide useful herein includes dibenzoylperoxide.
Inorganic peroxygen compounds are also suitable for the present invention. Examples of these materials useful in the invention are salts of monopersulfate, perborate monohydrate, perborate tetrahydrate, and percarbonate.
Preferred oxygen bleaching agents include epsilon-phthalimido-peroxyhexanoic acid, o-carboxybenzaminoperoxyhexanoic acid, and mixtures thereof.
Most preferred bleaching agents include perborate monohydrate and percarbonate.
The oxygen bleaching agent is present in the composition in an amount from about of 1 to 20 weight percent, preferably 1 to 15 weight percent.
The oxygen bleaching agent may be incorporated directly into the formulation or may be encapsulated by any number of encapsulation techniques known in the art to produce stable capsules in alkaline liquid formulations.
CA 0221461~ 1997-09-03 C 6362 (V) Bleach Precursors Suitable peroxygen peracid precursors for peroxy bleach compounds have been amply described in the literature, including GB Nos. 836,988; 855,735; 907,356; 907;358;
907,950; 1,003,310 and 1,246,339; US-A-3,332,882 and US-A-4,128,494.
Typical examples of precursors are polyacylated alkylene diamines, such as N,N,N1,N1-tetraacetylethylene diamine (TAED) and N,N,N1,N1-tetraacetylmethylene diamine (TAMD);
acylated glycolurils, such as tetraacetylglycoluril (TAGU);
triacetylcyanurate, sodium sulfophenyl ethyl carbonic acid ester, sodium acetyloxybenene sulfonate (SABS), sodium nonanoyloxy benzene sulfonate (SNOBS) and choline sulfophenyl carbonate. Peroxybenzoic acid precursors are known in the art, e.g., as described in GB-A-836,988.
Examples of suitable precursors are phenylbenzoate; phenyl p-nitrobenzoate; o-nitrophenyl benzoate; o-carboxyphenyl benzoate; p-bromophenylbenzoate; sodium or potassium benzoyloxy benzene-sulfonate; and benzoic anhydride.
Preferred peroxygen bleach precursors are sodium p-benzoyloxybenzene sulfonate, N,N,N1,N1-tetraacetylethylene diamine, sodium nonanoyloxybenzene sulfonate and choline sulfophenyl carbonate.
Bleach catalysts which may also be used in the detergent compositions include maganese catalysts such as those described in US-A-5,246,621.
Deter~ent Builder Materials The compositions of this invention contains either organic builders, particularly carboxylates, or inorganic builders, particularly phosphorous containing compounds.
Phosphorus Cont~; n; n~ Builders CA 0221461~ 1997-09-03 C 6362 (V) Examples of phosphorus-containing inorganic builders include the water-soluble salts, especially alkali metal pyrophosphates, orthophosphates and polyphosphates, particularly ammonium and alkanol ammonium salts, and phosphonates. Particularly preferred phosphate builders include sodium and potassium tripolyphosphates, pyrophosphates, hexametaphosphates and trimetaphosphates.
When phosphate builders are incorporated into the formula, they are present in an amount of about 10 to about 75~ by wt., most preferably 15 to about 60 wt. ~.
NonPhosPhorus Inor~anic BuilderR
Non-phosphorus-containing inorganic builders may be additionally used such as water-soluble alkali metal carbonates, bicarbonates, sesquicarbonates, borates, silicates, layered silicates such as SKS-6 ex Hoechst, metasilicates, phytic acid, borate and crystalline and amorphous aluminosilicates. Specific examples include sodium carbonate (with or without calcite seeds), potassium carbonate, sodium and potassium bicarbonates, silicates, including layered silicates and zeolites.
Orqanic Builders Organic detergent builders useful in the present invention include a variety of polycarboxylate compounds. As used herein "polycarboxylate" refers to compounds having a plurality of carboxylate groups, preferably at least three (3) carboxylates. Monomeric or polymeric carboxylates are preferred. Examples of organic builders include alkali metal citrates, succinates, malonates, fatty acid sulfonates, fatty acid carboxylates, nitrilotriacetates, phytates, phosphonates, alkanehydroxyphosphonates, oxydisuccinates, alkyl and alkenyl disuccinates, oxydiacetates, carboxymethyloxy succinates, ethylenediamine tetraacetates, tartrate monosuccinates, tartrate disuccinates, tartrate monoacetates, tartrate diacetates, CA 0221461~ 1997-09-03 C 6362 (V) oxidized starches, oxidized heteropolymeric polysaccharides, and polyhydroxysulfonates.
Polycarboxylates include polyacrylates, polymaleates, polyacetates, polyhydroxyacrylates, polyacrylate/polymaleate and polyacrylate/ polymethacrylate copolymers, acrylate/maleate/vinyl alcohol terpolymers, aminopolycarboxylates and polyacetal carboxylates, and polyaspartates and mixtures thereof. Such carboxylates are described in US-A-4,144,226, US-A-4,146,495 and US-A-4,686,062, herein incorporated by reference.
Alkali metal citrates, nitrilotriacetates, oxydisuccinates, polyphosphonates and acrylate/maleate copolymers and acrylate/maleate/vinyl alcohol terpolymers are especially preferred organic builders.
When the builder is comprised primarily of either monomeric or polymeric carboxylates or mixtures thereof the builder should be present in an amount of 10 to 60 wt. ~, most preferably 15 to 50 wt. ~.
The foregoing detergent builders are meant to illustrate but not limit the types of builders that can be employed in the present invention.
EnzYmes Additional enzymes capable of facilitating the removal of soils from a substrate may also be present in an amount of up to about 10% by wt., preferably 1 to about 5 wt. ~.
Such enzymes include proteases (e.g., Alcalase~, Savinase~
and Esperase~ from Novo Industries A/S and Purafect OxP~, ex. Genencor) and amylases (e.g., Termamyl~ and Duramyl~
from Novo Industries and Purafect OxAm~, ex. Genencor).
CA 022l46l~ l997-09-03 C 6362 (V) ODtional Inqredients Minor amounts of various other components may optionally be present in the cleaning composition. These include filler, non-carboxylic thickening agents, defoamer, bleach 5 scavengers including but not limited to sodium bisulfite, reducing sugars, and short chain alcohols; solvents and hydrotropes such as ethanol, isopropanol and xylene sulfonates; enzyme stabilizing agents; soil suspending agents; antiredeposition agents; anti-corrosion agents, such as benzotriazole and isocyanuric acid described in US-A-5,374,369; ingredients to enhance decor care such as certain aluminum salts described in U.S. Serial No.
08/444,502 and 08/444,503, herein incorporated by reference; colorants; perfumes; opacifiers such as titanium 15 dioxide; and other functional additives.
Sequestrants The detergent compositions herein may also optionally contain one or more transition metal tsuch as Fe, Mn, or 20 Cu) chelating agents. Such chelating agents can be selected from the group consisting of amino carboxylates, amino phosphonates, polyfunctionally-substituted aromatic chelating agents and mixtures therein. Without intending to be bound by theory, it is believed that the benefit of 25 these materials is due in part to their exceptional ability to remove transition metal ions such as Fe, Mn, and Cu from washing ~olutions by formation of soluble chelates.
Amino carboxylates useful as optional chelating agents 30 include ethylenediaminetetraacetates; N-hydroxyethylethylenediaminetriacetates; nitrilotriacetates;
ethylenediamine tetraproprionates; triethylenetetraamine-hexaacetates; diethylenetriaminepentaacetates;
ethylenediamine disuccinate; ethanoldiglycines; alkali 35 metal, ammonium, and substituted ammonium salts therein and mixtures therein.
CA 0221461~ 1997-09-03 C 6362 (V) .
Phosphonates and amino phosphonates are also suitable for use as chelating agents in the compositions of the invention when at least low levels of total phosphorus are permitted in detergent compositions, and include ethylenediaminetetrakis (methylenephosphonates), nitrilotris (methylenephosphonates) and diethylenetriaminepentakis (methylenephosphonates).
Preferably, these phosphonates and aminophosphonates do not contain alkyl or alkenyl groups with more than about 6 carbon atoms.
Polyfunctionally-substituted aromatic chelating agents are also useful in the compositions herein. See US-A-3,812,044, Preferred compounds of this type in acid formare dihydroxydisulfobenzenes such as 1,2-dihydroxy-3,5-disulfobenzene.
If utilized, these chelating agents will generally comprise from about 0.1~ to about 10~ by weight of the detergent compositions herein. More preferably, if utilized, the chelating agents will comprise from about 0.1~ to about 3.0~ by weight of such composition.
Anti-Scalants Scale formation on dishes and machine parts is an important problem that needs to be resolved or at least mitigated in formulating a machine warewashing product, especially in the case of low-pho~phate (e. g. less than the equivalent of 20% by weight, particularly 10~ by weight of sodium triphosphate) and phosphate-free machine warewashing compositions, particularly zero-P machine warewashing compositions.
In order to reduce this problem, co-builders, such as polyacrylic acids or polyacrylates (PAA), acrylate/maleate CA 0221461~ 1997-09-03 C 6362 (V) copolymers, polyaspartates, ethylenediamine disuccinate and the various organic polyphosphonates, e.g. Dequest series, may be incorporated in one or more system components. For improved biodegradability, (as such co-builders), the block co-polymers of formula (I) as defined in published PCT
patent specification WO 94/17170 may also be used. In any component, the amount of anti-scalant may be in the range of from 0.5 to 10, preferably from 0.5 to 5, and more preferably from 1 to 5% by weight.
Surfactants Useful surfactants include anionic, nonionic, cationic, amphoteric, amphoteric types and mixtures of these surface active agents. It is understood that surfactants should be selected and used at such levels as conventionally known in the art so as not to deactivate enzymes in the formula.
Such surfactants are well known in the detergent art and are described at length in "Surface Active Agents and Detergents", Vol. II, by Schwartz, Perry & Birch, Interscience Publishers, Inc. 1959, herein incorporated by reference.
Surfactants, if present in the composition, may be selected from the following:
Anionic surfactants Anionic synthetic detergents can be broadly described as surface active compounds with one or more negatively charged functional groups. An important class of anionic compounds are the water-soluble salts, particularly the alkali metal salts, of organic sulfur reaction products having in their molecular structure an alkyl radical containing from about 6 to 24 carbon atoms and a radical selected from the group consisting of sulfonic and sulfuric acid ester radicals.
CA 022l46l~ l997-09-03 C 6362 (V) Primary Alkyl Sulfates Rl 70503M
where Rl7 is a primary alkyl group of 8 to 18 carbon atoms and M is a solubilizing cation. The alkyl group Rl7 may have a mixture of chain lengths. It is preferred that at least two thirds of the Rl7 alkyl groups have a chain length of 8 to 14 carbon atoms. This will be the case if R17 is coconut alkyl, for example. The solubilizing cation may be a range of cations which are in general monovalent and confer water solubility. Alkali metal, notably sodium, is especially envisaged. Other possibilities are ammonium and substituted ammonium ions, such as trialkanolammonium or trialkylammonium.
Alkyl Ether Sulfates Rl70 (CH2CH20) nSO3M
where Rl7 is a primary alkyl group of 8 to 18 carbon atoms, n has an average value in the range from 1 to 6 and M is a solubilizing cation. The alkyl group Rl7 may have a 20 mixture of chain lengths. It is preferred that at least two thirds of the Rl7 alkyl groups have a chain length of 8 to 14 carbon atoms. This will be the case if Rl7 is coconut alkyl, for example. Preferably n has an average value of 2 to 5.
Fatty Acid Ester Sulfonates Rl~CH (SO~M) COzRl9 where Rl8 is an alkyl group of 6 to 16 atoms, R19 is an alkyl group of 1 to 4 carbon atoms and M is a solubilizing cation. The group Rla may have a mixture of chain lengths.
Preferably at least two thirds of these groups have 6 to 12 carbon atoms.
This will be the case when the moiety Rl~CH(-)CO2(-) is derived from a coconut source, for instance. It is CA 0221461~ 1997-09-03 C 636~
~ .~
preferred that Rl9 is a straight chain alkyl, notably methyl or ethyl.
Alkyl Benzene Sulfonates R20ArSO~M
where RZ~ is an alkyl group of 8 to 18 carbon atoms, Ar is -a benzene ring (C6H4) and M is a solubilizing cation. The group R20 may be a mixture of chain lengths. Straight chains of 11 to 14 carbon atoms are preferred.
Organic phosphate based anionic surfactants include organic phosphate esters such as complex mono- or diester phosphates of hydroxyl- terminated alkoxide condensates, or salts thereof. Included in the organic phosphate esters are phosphate ester derivatives of polyoxyalkylated alkylaryl phosphate esters, of ethoxylated linear alcohols and ethoxylates of phenol.
Also included are nonionic alkoxylates having a sodium alkylenecarboxylate moiety linked to a terminal hydroxyl group of the nonionic through an ether bond. Counterions to the salts of all the foregoing may be those of alkali metal, alkaline earth metal, ammonium, alkanolammonium and alkylammonium types.
Particularly preferred anionic surfactants are the fatty acid ester sulfonates with formula:
R CH (503M) CO2R
where the moiety Rl8CH(-) CO2 (-) is derived from a coconut source and Rl9 is either methyl or ethyl.
Nonionic surfactants Nonionic surfactants can be broadly defined as surface active compounds with one or more uncharged hydrophilic substituents. A major class of nonionic surfactants are those compounds produced by the condensation of alkylene CA 0221461~ 1997-09-03 C 63 62 ' (V) oxide groups with an organic hydrophobic material which may be aliphatic or alkyl aromatic in nature. The length of the hydrophilic or polyoxyalkylene radical which is condensed with any particular hydrophobic group can be readily adjusted to yield a water-soluble compound having the desired degree of balance between hydrophilic and hydrophobic elements. Illustrative, but not limiting examples, of various suitable nonionic surfactant types are:
polyoxyethylene or polyoxypropylene condensates of aliphatic carboxylic acids, whether linear- or branched-chain and unsaturated or saturated, containing from about 8 to about 18 carbon atoms in the aliphatic chain and incorporating from about 2 to about 50 ethylene oxide and/or propylene oxide units. Suitable carboxylic acids include "coconut" fatty acids (derived from coconut oil) which contain an average of about 12 carbon atoms, "tallow" fatty acids (derived from tallow-class fats) which contain an average of about 18 carbon atoms, palmitic acid, myristic acid, stearic acid and lauric acid, polyoxyethylene or polyoxypropylene condensates of aliphatic alcohols, whether linear- or branched-chain and unsaturated or saturated, containing from about 6 to about 24 carbon atoms and incorporating from about 2 to about 50 ethylene oxide and/or propylene oxide units. Suitable alcohols include "coconut" fatty alcohol, "tallow" fatty alcohol, lauryl alcohol, myristyl alcohol and oleyl alcohol.
Ethoxylated fatty alcohols may be used alone or in admixture with anionic surfactants, especially the preferred surfactants above. The average chain lengths of the alkyl group R21 in the general formula: R2lO(CH2CH20)nH
CA 0221461~ 1997-09-03 C 63 62 (V) is from 6 to 24 carbon atoms. Preferably the group R21 may have chain lengths in a range from 9 to 18 carbon atoms.
The average value of n should be at least 2. The numbers of ethylene oxide residues may be a statistical distribution around the average value. However, as is known, the distribution can be affected by the manufacturing process or altered by fractionation after ethoxylation. Particularly preferred ethoxylated fatty alcohols have a group R2l which has 9 to 18 carbon atoms while n is from 2 to 8.
Also included within this category are nonionic surfactants having a formula:
R22 (CH~CHO~(CH2CH2O~(CH2CIHO~H
wherein R22 is a linear alkyl hydrocarbon radical having an average of 6 to 18 carbon atoms, R23 and R24 are each linear alkyl hydrocarbons of about 1 to about 4 carbon atoms, x is an integer of from 1 to 6, y is an integer of from 4 to 20 and z is an integer from 4 to 25.
One preferred nonionic surfactant of the above formula is Poly-Tergent SLF-18~ a registered trademark of the Olin Corporation, New Haven, Conn. having a composition of the above formula where R22 is a C6-C10 linear alkyl mixture, R23 and R24 are methyl, x averages 3, y averages 12 and z averages 16. Another preferred nonionic surfactant is CA 022l46l~ l997-09-03 C 6362 (V~
' ~
R25O(CH2lHO)j(CH2CH20~(CH2CH(O~R26)z 5 wherein R2s is a linear, aliphatic hydrocarbon radical having from about 4 to about 18 carbon atoms including - mixtures thereof; and R26 is a linear, aliphatic hydrocarbon radical having from about 2 to about 26 carbon atoms including mixtures thereof; j is an integer having a value of from 1 to about 3; k is an integer having a value from 5 to about 30; and z is an integer having a value of from 1 to about 3. Most preferred are compositions in which j is 1, k is from about 10 to about 20 and z is 1.
These surfactants are described in WO 94/22800. Other 15 preferred nonionic surfactants are linear fatty alcohol alkoxylates with a capped terminal group, as described in U. S . 4,340,766 to BASF.
Another nonionic surfactant included within this category 20 are compounds of formula:
R27~(CH2CH20)qH
wherein R27 is a C6-C24 linear or branched alkyl hydrocarbon radical and q is a number from 2 to 50; more preferably R27 25 iS a C8-C18 linear alkyl mixture and q is a number from 2 to 15.
polyoxyethylene or polyoxypropylene condensate~ of alkyl phenols, whether linear- or branched-chain and unsaturated 30 or saturated,containing from about 6 to 12 carbon atoms and incorporating from about 2 to about 25 moles of ethylene oxide and/or propylene oxide.
polyoxyethylene derivatives of sorbitan mono-, di-, and tri-fatty acid esters wherein the fatty acid component has between 12 and 24 carbon atoms. The preferred CA 0221461~ 1997-09-03 C 6362 (~1) ' .
sorbitan trilaurate, sorbitan monopalmitate, sorbitan tripalmitate, sorbitan monostearate, sorbitan monoisostearate, sorbitan tripalmitate, sorbitol tristearate, sorbitan monooleate, and sorbitan trioleate.
The polyoxyethylene chains may contain between about 4 and 30 ethylene oxide units, preferably about 10 to 20. The sorbitan ester derivatives contain 1, 2 or 3 polyoxyethylene chains dependent upon whether they are mono-, di- or tri-acid esters.
polyoxyethylene-polyoxypropylene block copolymers having formula:
HO (CH2cH20) a (CH (CH3) CH20) b (CH2CH20) CH
or HO (CH (CH3) CH2O) d (CH2CH20) e (CH (CH3) CH20) fH
wherein a, b, c, d, e and f are integers from 1 to 350 reflecting the respective polyethylene oxide and polypropylene oxide blocks of said polymer. The polyoxyethylene component of the block polymer constitutes at least about 10% of the block polymer. The material preferably has a molecular weight of between about 1,000 and 15,000, more preferably from about 1,500 to about 6,000. These materials are well-known in the art. They are available under the trademark "Pluronic" and "Pluronic R", a product of BASF Corporation.
Amine oxides having formula:
R28R29R30N=o wherein R29, R29 and R30 are saturated aliphatic radicals or substituted saturated aliphatic radicals. Preferable amine oxides are those wherein R29 is an alkyl chain of about 10 CA 0221461~ 1997-09-03 C 6362 (V) to about 20 carbon atoms and R29 and R30 are methyl or ethyl groups or both R28 and R29 are alkyl chains of about 6 to about 14 carbon atoms and R30 is a methyl or ethyl group.
Amphoteric synthetic detergents may also be broadly described as derivatives of aliphatic and tertiary amines, in which the aliphatic radical may be straight chain or branched and wherein one of the aliphatic substituents contain from about 8 to about 18 carbons and one contains an anionic water-solubilizing group, i.e., carboxy, sulpho, sulphato, phosphato or phosphono. Examples of compounds falling within this definition are sodium 3-dodecylamino propionate and sodium 2-dodecylamino propane sulfonate.
Amphoteric synthetic detergents can be broadly described as derivatives of aliphatic quaternary ammonium, phosphonium and sulphonium compounds in which the aliphatic radical may be straight chained or branched, and wherein one of the aliphatic substituents contains from about 8 to about 18 carbon atoms and one contains an anionic water-solubilizing group, e.g., carboxy, sulpho, sulphato, phosphato or phosphono. These compounds are frequently referred to as betaines. Besides alkyl betaines, alkyl amino and alkyl amido betaines are encompassed within this invention.
Alkyl Glycosides R31o (R320) (Zl) wherein R31 is a monovalent organic radical (e.g., a monovalent saturated aliphatic, unsaturated aliphatic or aromatic radlcal such as alkyl, hydroxyalkyl, alkenyl, hydroxyalkenyl, aryl, alkylaryl, hydroxyalkylaryl, arylalkyl, alkenylaryl, arylalkenyl, etc.) containing from about 6 to about 30 (preferably from about 8 to 18 and more preferably from about 9 to about 13) carbon atoms; R32 is a divalent hydrocarbon radical containing from 2 to about 4 carbon atoms such as ethylene, propylene or CA 0221461~ 1997-09-03 C 6362 (V) . ~
butylene (most preferably the unit (R320) n represents repeating units of ethylene oxide, propylene oxide and/or random or block combinations thereof); n is a number having an average value of from 0 to about 12; Zl represents a moiety derived from a reducing saccharide containing 5 or 6 carbon atoms (most preferably a glucose unit); and p is a number having an average value of from 0.5 to about 10 preferably from about 0.5 to about 5 .
Examples of commercially available materials from Henkel Kommanditgesellschaft Aktien of Dusseldorf, Germany include APG~ 300, 325 and 350 with R3l being C9-Cll, n is 0 and p is 1.3, 1. 6 and 1.8-2.2 respectively; APG~ 500 and 550 with R3 is Cl2-Cl3, n is 0 and p is 1.3 and 1.8-2.2, respectively;
and APG~ 600 with R3l being Cl2-Cl4, n is 0 and p is 1.3.
While esters of glucose are contemplated especially, it is envisaged that corresponding materials based on other reducing sugars, such as galactose and mannose are also suitable.
- The amount of surfactant present in the final formula should be from about 0.5 to about 30~ by weight of the composition. The preferred range of surfactant is from 0.5 to 20~ by weight, more preferably from 0.5 to 10~ by weight.
Filler An inert filler material which is water-soluble may also be present in cleaning compositions. This material should not precipitate calcium or magnesium ions at the filler use level. Suitable for this purpose are organic or inorganic compounds. Organic fillers include sucrose esters and urea. Representative inorganic fillers include sodium sulfate, sodium chloride and potassium chloride. A
preferred filler is sodium sulfate. Its concentration may CA 0221461~ 1997-09-03 C 6362 (~) range from 0~ to 20~, preferably from about 2~ to about 10 by weight of the cleaning composition.
Thickeners & Stabilizers Thickeners are often desirable for liquid cleaning compositions. Thixotropic thickeners such as smectite clays including montmorillonite (bentonite), hectorite, saponite, and the like may be used to impart viscosity to liquid cleaning compositions. Silica, silica gel, and aluminosilicate may also be used as thickeners. Salts of polyacrylic acid (of molecular weight of from about 300,000 up to 6 million and higher), including polymers which are cross-linked may also be used alone or in combination with other thickeners. Use of clay thickeners for machine dishwashing compositions is disclosed for example in US-A-4,431,559; US-A-4,511,487; US-A-4,740,327; US-A-4,752,409.
Commercially available synthetic smectite clays include Laponite supplied by Laporte Industries. Commercially available bentonite clays include Korthix H and VWH ex Combustion Engineering, Inc.; Polargel T ex American Colloid Co.; and Gelwhite clays (particularly Gelwhite GP
and H) ex English China Clay Co. Polargel T is preferred as imparting a more intense white appearance to the composition than other clays. The amount of clay thickener employed in the compositions is from 0.1 to about 10~, preferably 0.5 to 5~. Use of salts of polymeric carboxylic acids is disclosed for example in GB-A-2,164,350, US-A-4,859,358 and US-A-4,836,948.
For liquid formulations with a "gel" appearance and rheology, particularly if a clear gel is desired, a chlorine-resistant polymeric thickener is particularly useful. US-A-4,260,528 discloses natural gums and resins for use in clear machine dishwashing detergents, which are not chlorine stable. Acrylic acid polymers that are cross-linked manufactured by, for example, B.F. Goodrich CA 0221461~ 1997-09-03 C 6362 (~) and sold under the trade name "Carbopol" have been found to be effective for production of clear gels, and Carbopol 940, 617 and 627, having a molecular weight of about 4,000,000 are particularly preferred for maintaining high 5 viscosity with excellent chlorine stability over extended periods. Further suitable chlorine-resistant polymeric thickeners are described in US-A-4,867,896 incorporated by reference herein.
The amount of thickener employed in the compositions is from 0 to 5~, preferably 0. 5-3~ .
Stabilizers and/or co-structurants such as long-chain calcium and sodium soaps and C12 to C1~ sulfates are 15 detailed in US-A- 3,956,158 and US-A-4,271,030 and the use of other metal salts of long-chain soaps is detailed in US-A-4,752,409. Other co-structurants include Laponite and metal oxides and their salts as described in US-A-4,933,101, herein incorporated by reference. The amount of 20 stabilizer which may be used in the liquid cleaning compositions is from about 0.01 to about 5~ by weight of the composition, preferably 0. 01-2~. Such stabilizers are optional in gel formulations. Co-structurants which are found especially suitable for gels include trivalent metal 25 ions at 0. 01-4~ of the compositions, Laponite and/or water-soluble structuring chelants at 0. 01-5~ . These co-structurants are more fully described in the US-A-5,141,664, hereby incorporated by reference.
30 De f oamer The formulations of the cleaning composition comprising surfactant may further include a defoamer. Suitable defoamers include mono-and distearyl acid phosphate, silicone oil and mineral oil. Even if the cleaning 35 composition has only defoaming surfactant, the defoamer assists to minimize foam which food soils can generate.
CA 0221461~ 1997-09-03 C 63 62 (~1) The compositions may include 0. 02 to 2~ by weight of defoamer, or preferably 0.05-1.0~. Preferred antifoam systems are described in Angevaare et al.; US S/N
08/539,923, herein incorporated by reference.
The following examples will serve to distinguish this invention from the prior art and illustrate its embodiments more fully. Unless otherwise indicated, all parts, percentages and proportions referred to are by weights.
Example 1 The lime soap dispersant properties of amphoteric polymers within the scope of the invention was compared to that of lime soap dispersants known in the prior art as described 15 below.
The polymers were evaluated for their lime soap dispersing power value (LSDP), which is a conventional measurement of the effectiveness of a material for dispersing lime soap.
20 The lime soap dispersing power value (LSDP) is defined as the (weight ratio of dispersant to sodium oleate X 100) based on the amount of dispersant required to disperse lime soap curd formed by 0. 025g sodium oleate and 30mls of water of 333 ppm. CaC03 equivalent hardness. According to the 25 test, a low LSDP value is an indication of an effective lime soap dispersant. A detailed description of the test is found in an article by H.C. Borghetty and C.A. Bergman, J. Am. Oil Chem. Soc., 27, pages 88-90, (1950). The materials used in the comparison are described in Table I
below:
CA 0221461~ 1997-09-03 C 6362 (V) Table 1 MAT~T~TAT.S SOURCE LSDP
Amphoteric Polymer PC2 Supplied by Rohm & Haas 1.5 5 Amphoteric Polymer E-2072 Supplied By ALCO 1.5 Amphoteric Polymer E-2075 Supplied By ALCO 2.5 C13-C15 Alcohol Described in WO
Ethoxylate (12EO) 94/07985 6.0 C12-C18 Alcohol Described in WO
Ethoxy Sulfate (3EO) 94/07985 4.0 Polyacrylic Acid (200,000 MW) 22.0 Polyacrylic Acid Acusol 445 supplied (4,500 MW) by Rohm and Haas 15.0 15 Polyacrylic Acid/ Supplied by Aldrich Acrylamide (200,000 17.5 MW) As this example illustrates, amphoteric polymers within the scope of the invention are extremely effective lime soap dispersants in comparison to similar polymers outside the scope of the invention and in comparison to the preferred lime soap dispersants claimed in WO 94/07984 and WO
Example 2 The effect on glass and plasticware appearance of polymers and surfactants having an LSDP of less than 8 were compared by determining the effectiveness of each material in preventing the formation of mineral spots and films on clear glass tumblers and inhibition of lime soap filming on CA 0221461~ 1997-09-03 C 6362 (V) polyethylene plates when incorporated into the lipase containing base formulation.
A base machine dishwashing detergent composition was prepared as described in Table 2 below.
Table 2 INGREDIENTS % BY WT.
STPP 51 . O
Sodium silicate (PQ Britesil 30.0 H20) Sodium Percarbonate 9.0 TAED 3.6 (tetraacetylethylenediamine) Protease (Novo Savinase 6T) 3.0 Amylase (Novo Termamyl 60T) 1.8 Lipase (Novo Lipolase lOOT) 0.2 Nonionic (BASF Plurafac 1.4 LF403) Lime soap dispersants were incorporated into the described base at a level of 5~ by wt. in addition to the above composition.
A ten cycle test procedure was used as follows:
Five glass tumblers and two polyethylene plates were placed in a Bosch model 6082 dishwasher along with a ballast load of clean dishware consisting of 9 ceramic dinner plates, 2 ceramic tea cups, 2 stainless steel plates, and 2 melamine plates. Twenty grams of ASTM standard soil consisting of CA 0221461~ 1997-09-03 C 6362 ~V) 80~ margarine and 20~ powdered milk was added to the dishwasher by spreading it onto the inside of the machine door. The 50~ C. Economy wash setting was used, with water of 300/320 ppm. permanent/temporary hardness expressed as CaCO3 equivalent (4:1 Ca/Mg ratio). 18.0 g detergent was added at the start of the main wash, along with lipase (Lipolase lOOT ex. Novo) and selected polymer (5~ by wt. in addition to the detergent composition) as specified. At the end of each complete cycle, fresh soil and detergent were added and the process repeated for a total of ten washes.
At the end of this process the tumblers and polyethylene items were visually graded for spotting and filming.
Grading scales of from 0 to 5 were used to measure film deposition, where a grade of 0 indicates no visible film and a grade of 5 indicates coverage with a very heavy, opaque film. When lipase is present in the detergent composition, a film buildup can occur on the hydrophobic polyethylene articles, caused primarily by precipitated Ca soap. Thus, film scores for the polyethylene articles give an indication of lime soap dispersant efficacy.
For spotting, the number of spots on each item was counted, with the average number of spots per article reported. The number of spots on the glass tumblers gives an indication of the effectiveness of the lipase. When lipase is present in the detergent composition, the lowest number of spots corresponds to the most effective lipase action.
The following spotting and filming grades were obtained (as 30 noted, filming on polyethylene items in the presence of lipase is primarily caused by lime soap deposition):
CA 0221461~ 1997-09-03 C 6362 (V) Composition Glass TumblersPolYethylene Items mineral film lime soap film score # of spots film score # of SPots (1) Base formulation 1.0 225 3.0 138 (2) Base + lipase, no dispersant 1.0 1 5.0 0 (3) Base + lipase +
amphoteric 1. 5 0 2.5 0 polymer ( PC2) 15 (4) Base + Lipase +
C13-C15 EO12 0.5 51 2.0 33 alcohol ethoxylate (5) Base + Lipase +
alcohol 0. 5 120 0.0 127 ethoxysulfate As this example demonstrates, addition of lipase to the 25 base formulation results in a significant reduction in the number of spots on the glass tumblers (Composition 2) . This is indicative of lipase functioning in the system. However, filming on polyethylene items is very high, due to lime soap deposition. Addition of an amphoteric polymer within 30 the scope of the invention (Composition 3) significantly reduces the film score on polyethylene items, while the excellent glassware appearance produced by lipase is retained, as seen by the low spotting scores on the glass tumblers. In contrast, while the materials described in 35 W094/07984 and WO/07985 (incorporated in Compositions 4 and 5) reduce lime soap deposition, they also greatly reduce C 6362 (V) CA 0221461~ 1997-09-03 the antispotting benefit originally provided by the lipase in the detergent composition.
Exam~le 3 The ability of amphoteric polymers to reduce lime soap deposition without inhibiting the antispotting benefit provided by lipase was further demonstrated as follows:
The ten wash cycle test procedure described in example 2 was followed. The base dishwashing detergent composition as described in Table 2 was used for this example, but was dosed at 26.0 g instead of the 18.0 g used in example 2.
Amphoteric polymers were added to this composition at a level of 4%, as opposed to the 5% used in the previous example. All other test parameters were identical to those for example 1.
The following spotting and filming grades were obtained (as noted, filming on polyethylene items is primarily caused by lime soap deposition):
CA 022l46l~ l997-09-03 C 6362 ~V) Composition Glass TumblersPolyethylene Items mineral film lime soap 5 film score # of spots film score # of spots (1) Base + lipase, no dispersant 2.1 0 1.5 225 (2) Base + lipase +
amphoteric polymer (PC2) 2.2 2 0 23 15 (3) Base + lipase +
amphoteric polymer (Alco E-2072) 2.3 2 0.3 30 (4) Base + lipase +
amphoteric polymer (Alco E-2075) 1.9 2 0.3 16 This example further illustrates the effectiveness of amphoteric polymers within the scope of the invention in 25 improving glass and plasticware appearance by inhibiting the deposition of lime soap while maintaining the antispotting benefit provided by lipase.
Machine Dishwashinq Compo~ition ContAi n; n~ Am~hoteric PolYmers Field of Invention The invention relates to detergent compositions containing amphoteric polymers to control the deposition of lime soap, particularly machine dishwashing compositions containing lipolytic enzymes.
Backqround of the Invention A critical criteria for an effective machine dishwashing composition is the appearance of both the washed glassware and plastic articles to the consumer. Spotting and filming of such tableware, when washed with commercial products, generally results from mineral deposition during the evaporation of undrained wash solution in the drying step.
The deposited minerals are from many sources, including salts of ingredients in the product formulations, calcium carbonate from temporary water hardness, and suspended 20 soil.
The deposition on the surfaces of the washed articles make them look dull due to the presence of spots, streaks or surface covering film. The most intense spotting problems are related to the deposition of hydrophobic soil fragments. In the final rinse stage, this hydrophobic soil is thought to break-up the water film, leaving droplets ~ehind on the tableware which result in mineral deposits observed as white spots upon evaporation of the water component.
A prior art solution to the removal of these white mineral spots has been the addition of a rinse aid composition to the rinsing water of the machine cycle. Although the visual appearance of the washed tableware is improved, some CA 0221461~ 1997-09-03 C 6-~62 ~v) spotting, but especially mineral film formation has still been observed even with the use of this additional product.
Moreover, use of a rinse aid is inconvenient to the consumer.
The major fraction of the hydrophobic soil fragments that are present on washed tableware is believed to be triglyceride and fatty ester soil. Consequently, machine dishwashing and rinse aid compositions incorporating lipolytic enzymes which assist in breaking down these soiIs have been described in EP-A-346,136 and EP-A-271,155. Although lipolytic enzymes can reduce the formation of mineral spots due to hydrophobic soil fragments, the enzymes can also cause a different type of white deposits to build up on hydrophobic surfaces such as plastics. These fatty deposits are due to precipitation of lime soaps which are formed from the mixture of calcium and magnesium ions in the wash water with fatty acids, which are liberated from the triglyceride and fatty ester soils by the action of the lipolytic enzymes. The higher the level of fatty soil present in the dishwasher, the worse the problem of lime soap deposition.
Prior art solutions to these problems include formulations of machine dishwashing compositions incorporating certain lime soap dispersants with lipolytic enzymes as described in W0-94/07984 and W0-94/07985 (Proctor & Gamble). Tableware washed with compositions containing lipases and these lime soap dispersants have been observed to have low lime soap film scores (i.e. little to no filming is observed).
However, a large number of white mineral spots on the washed articles have been observed. It is thus believed that the lime soap dispersants described in these publications actually inhibit the action of the lipase.
CA 0221461~ 1997-09-03 C 6-~62 (.V) Hydrophobically modified copolymers, of especially acrylic acid, have been described in copending Gordon et al.; U.S.
Serial No. 08/457,690 for incorporation in machine dishwashing compositions. Calcium soap deposition is reduced by the presence of these polymers.
US-A-4,891,149 describes polymeric lime soap dispersants which consist of copolymers and water soluble salts of copolymers of acrylic acid, methacrylic acid and mixtures thereof and acrylamide, alkyl or alkylol substituted acrylamide, or mixture of said acrylamides. Optionally, enzymes may also be added to the formulations.
US-A-5,308,532 (Rohm & Haas) describes aminoacryloyl -containing terpolymers which are useful for reducing mineral spotting and filming of tableware. Thus, the detergent formulation acts by preventing hydrophobic deposits on glassware and does not address the issue of preventing lime soap deposition. The use of lipolytic enzymes in combination with such terpolymers to control the deposition of lime soaps is neither taught nor suggested.
It is therefore an object of the present invention to provide machine dishwashing compositions and methods of using them to prevent lime soap deposition on washed tableware.
Another object of the invention is to selectively combine lipolytic enzymes with particular amphoteric polymers in a detergent composition to control lime soap deposition and virtually prevent spotting and lime soap filming on cleaned tableware.
Summary of the Invention CA 0221461~ 1997-09-03 C 6.362 (V) Accordingly, the present invention provides a machine washing composition comprising:
(a) an effective amount of a amphoteric polymer wherein in a 1~ aqueous wash liquor having a pH of about 7 or greater, positive charges on the polymer comprise between 1~ and 50~, preferably between 2~ and 20~, most preferably between 5 and 15~ of the total charges on the polymer having a formula selected from:
i) AXByCz where in a 1~ aqueous wash liquor pH
A is an anionic moiety, B is a cationic moiety and C is an anionic, cationic, amphoteric or uncharged moiety and mixtures thereof, x, y, and z refer to mole percentages, x is 50-99~, preferably 80-98~, most preferably 85-95~, and y is 1-50~, preferably 2-20~, most preferably 5-15~ and z is 0 to 25~, preferably 0 to 18~;
or ii) DdEf where at the wash pH D is an amphoteric moiety, E is an anionic, cationic, or uncharged moiety and mixture thereof, d and f refer to mole percentages, and d is 1-100~ and f is 0-99~ provided the above stated charge distribution is satisfied;
(b) 0.01~ to about 4 wt. ~ of a lipolytic enzyme; and (c) about 1 to about 75~ by wt. of a builder material.
A bleaching agent is optionally included.
Detailed DescriPtion of Preferred Embodiments The amphoteric polymers incorporated in the compositions of the invention are present in an effective amount, preferably about 0.1 to about 25~, more preferably from CA 022l46l~ l997-09-03 C 6362 (V) about 1 to about 15~, most preferably from about 2 to about 10~ by wt.
Wash pH is defined as the measured pH of a 1~ aqueous solution of dishwasher water in the main wash cycle after addition and dissolution of the detergent composition. At a wash pH preferably between about 7 and about 12, most preferably between about 8 and about 11, positive charges on the polymer comprise between 1~ and 50~, preferably between 2~ and 20~, most preferably between 5 and 15~ of the total charges on the polymer.
The amphoteric polymers are addition polymers which may be prepared by (1) copolymerizing selected monomers which are anionic at the wash pH with selected monomers which are cationic at the wash pH, or (2) by polymerizing selected amphoteric monomers.
A first means of preparing the amphoteric polymers which are useful in the invention consists of copolymerizing from about 50 to about 99~ , preferably from about 80 to about 98~, most preferably from about 85 to about 98% by wt. of the anionic monomer (A) with about 1 to about 50~, preferably from about 2 to about 20~, most preferably from about 2 to about 15~ by wt. of the cationic monomer.
Optionally, a charged or uncharged moiety (C) is also copolymerized.
The monomers (A) used to prepare the amphoteric polymers are substituted vinyl compounds which have anionic character at wash pH. Preferred monomers are substituted vinyl compounds of formula l CA 0221461~ 1997-09-03 C 6 ~62 (V) (I) Rl R2 wherein R1, R2, and R3 are independently a hydrogen, C1 to C3 alkyl, a carboxylate group or a carboxylate group substituted with a C1 to C30 straight or branched alkyl, aromatic heterocycle or a polyalkylamine oxide with the requirement that at least one of R1, R2, or R3 must be a carboxylate or substituted carboxylate;
Preferred monomers include acrylic acid, methacrylic acid, maleic acid, ~-ethacrylic acid, ~,~,-dimethacrylic acid, methylenemalonic acid, vinylacetic acid, allylacetic acid, ethylidineacetic acid, propylidineacitic acid, crotonic acid, fumaric acid, itaconic acid, citraconic acid, mesaconic acid and the like. Most preferred monomers include acrylic acid, methacrylic acid, and maleic acid.
The monomers (B) used to form the amphoteric polymers of the invention which have cationic character at wash pH are substituted vinyl compounds of formula ll I I ~) wherein R4 is a hydrogen, aromatic, heterocycle or a polyalkylamine oxide; Rs is a hydrogen or a Cl to C30 straight or branched alkyl; and Q i8 a nitrogen-containing organic radical, said radical having a pKa value of ~ 7.
CA 0221461~ 1997-09-03 C 6~62 (~) methacrylate, dialkylaminoalkyl acrylate, dialkylaminoalkyl methacrylamide and dialkylaminoalkyl acrylamide.
The monomers of formula II are preferably quaternized wherein Q is preferably selected from the group consisting of formula 111 --CH2N (CH3)~,CH2CH=CH2 X (III) wherein X~ is any suitable counterion such as halogen, hydroxide, sulfate, hydrosulfate, phosphate, formate and lS acetate or, a compound of formula lV
-Z-CH2-CR6R7(CH2)mN ' R8R9R'0 (IV) wherein Z is selected from the group consisting of O, COO
and CONR11 in which R11 is a hydrogen or a C1 to C3 alkyl group; R6 and R7 are each independently selected from the group consisting of hydrogen, C1 to C4 alkyl or R6 and R7 taken together form a C3 to C7 aliphatic heterocycle; m is 0 to 2 provided that when m is 0 a C-N bond is present in lieu of the (CH2)m group and R8, R9, and R10are each independently selected from a group consisting of hydrogen or a Cl to C~ alkyl; or R8 and R9 are taken together with the nitrogen to which they are attached to form a 3 to 7 membered non-aromatic nitrogen heterocycle; and X is any suitable counterion such as a halogen, hydroxide, sulfate, hydrosulfate, phosphate, formate and acetate.
CA 0221461~ 1997-09-03 C 6362 (V.) Preferred examples of the quaternized monomers are (3-acrylamidopropyl) trimethylammonium chloride (APTAC), (3-methacrylamidopropyl) trimethylammonium chloride (MAPTAC), and dimethyldiallylammonium chloride (DMDAC). Other suitable examples include such materials as vinylbenzyltrialkylammonium salts and the like.
Monomers (C) which are anionic or cationic are selected from compounds of formula I or II, respectively.
Amphoteric monomers (C) may be selected from compounds of formula V described below.
/ IRl3 \ IRl~ 1~l t R ~ Rl6 Y
wherein, Rl2 is a C3 to C6 monoethylenically unsaturated carboxylate; Rl3 and Rl~ each independently represent hydrogen or a Cl to C3 alkyl; Rls and Rl6 each independently represent a hydrogen or a Cl to C3 alkyl; x is 1 to 3; and y is 1 to 3.
Suitable carboxylates represented by Rl2 include, but are not limited to, acrylic acid, methacrylic acid, ~-ethacrylic acid, ~,~,-dimethacrylic acid, methylenemalonic acid, vinylacetic acid, allylacetic acid, ethylidineacetic acid, propylidineacitic acid, crotonic acid, maleic acid, fumaric acid, itaconic acid, citraconic acid, mesaconic acid, and alkali metal and ammonium salts thereof.
CA 0221461~ 1997-09-03 C 6362 (V) Preferably, the unsaturated carboxylic acid is acrylic or methacrylic acid.
Uncharged monomers (C) are selected from C1-Cs alkyl esters of acrylic acid, methacrylic acid, and itaconic acid; C1C4 hydroxyalkyl esters of acrylic acid, methacrylic acid, and itaconic acid, alkylene oxide esters of acrylic acid, methacrylic acid, and itaconic acid having 1-20 alkylene oxide repeat units; and Cl-C20 EO1-EO20 ethoxyalkyl esters of acrylic acid, methacrylic acid, and itaconic acid;
styrene; vinyl alcohol; vinyl acetate; methyl vinyl ether;
and allyl alcohols. Preferably the uncharged monomer is C1-C4 alkyl ester of acrylic acid, methacrylic acid, or itaconic acid, C1-C4 hydroxyalkyl ester of acrylic acid, methacrylic acid, or itaconic acid, or C1-C20 EO1-EO20 ethoxyalkyl ester of acrylilc acid, methacrylic acid, or itaconic acid.
If these optional monomers (C) are present they should be present only in an amount of less than 25~ of the total monomer distribution.
Preferably the amphoteric polymers (AXByCz wherein z is 0) produced from the monomers of formulas l and ll are formed of monomers of acrylic acid polymerized with quaternized basic monomers.
A second means of obtaining amphoteric polymers useful in the invention is the polymerization of an amphoteric monomer (D) having a formula (V) as described above.
The amphoteric monomers of formula (V) may be homopolymerized or copolymerized with non-amphoteric polymerizable monomers (E) in an amount from about 0 to about 99~ by wt., preferably from 0 to about 75~ by wt., 3 5 with the requirement that the previously defined polymer charge distribution be satisfied.
CA 0221461~ 1997-09-03 C 6362 (~) Suitable anionic, and cationic monomers from which the moiety E is selected are represented by formulas I and II.
Uncharged monomers are selected from C1-C4 alkyl esters of acrylic acid, methacrylic acid, and itaconic acid; C1-C4 hydroxyalkyl esters of acrylic acid, methacrylic acid, and itaconic acid, alkylene oxide esters of acrylic acid, methacrylic acid, and itaconic acid having 1-20 alkylene oxide repeat units; and Cl-C20 EO1-EO20 ethoxyalkyl esters of acrylic acid, methacrylic acid, and itaconic acid;
styrene; vinyl alcohol; vinyl acetate; methyl vinyl ether;
and allyl alcohols. Preferably the uncharged monomer is C1-C4 alkyl ester of acrylic acid, methacrylic acid, or itaconic acid, C1-C4 hydroxyalkyl ester of acrylic acid, methacrylic acid, or itaconic acid, or C1-C20 EO1-EO20 ethoxyalkyl ester of acrylilc acid, methacrylic acid, or itaconic acid.
Suitable examples of amphoteric polymers include, but are not limited to, a copolymer of acrylic acid and 3-acrylamidopropyl trimethylammonium chloride as described inEP-A- 560, 519 Rohm and Haas, and EXP-2072 and EXP-2075 (terpolymers of acrylic acid, dimethyldiallylammonium chloride and C14-20 EO 20 itaconate ester available from Alco). Preferably, the polymers are the copolymers of acrylic acid and 3-acrylamido-propyl trimethylammonium chloride.
LiPolYtic EnzYmes Li~olytic enzymes are an essential component of the machine washing compositions of the invention. They are present at levels of active enzyme of from 0.01 to 4% by wt., preferably 0.01~ to 3% by wt., most preferably from 0.05%
to 1.5% by wt. of the composition, based on lipolytic activity of 100 LU/mg. Lipolytic activity is commonly defined by the amount of titratable fatty acid liberated from triglyceride under specified conditions. One lipase CA 0221461~ 1997-09-03 C 6362 (v) unit (LU) of activity is equivalent to liberation of one micromole of butyric acid per minute from an emulsion of tributyrin and gum arabic in the presence of Ca++ and NaCl at 30 Deg. C and pH 7.
Lipases facilitate the degradation or alteration of soils and stains comprising triglycerides or fatty esters.
Lipases suitable for use herein include those of animal, plant and microbiological origin. Suitable lipases are also found in many strains of bacteria and fungi. For example, lipases suitable for use herein can be obtained from Pseudomonas, Aspergillus, Staphylococcus, Toxins, Mycobacterium Tuberculosis, Mycotorula Lipolytica and Sclerotinia microorganisms. Lipases from chemically or genetically modified mutants are also included herein.
Mixtures of lipase from various strains are also included herein.
Suitable animal lipases are found in the body fluids and organs of many species. A preferred class of animal lipase herein are the pancreatic lipases.
A preferred lipase herein is obtained by cloning the gene from Humicola lanuginosa and expressing the gene in Aspergillus oryza, as host, as described in EP-A-0258068, which is commercially available from Novo Industri A/S, Denmark, under the tradename Lipolase.
Tradenames of other suitable lipases are Lipomax, ex. Gist Brocades (now Genencor), the Netherlands and Lipase G-1000, ex. Solvay Enzymes, USA.
Hypohalite Bleachinq Aqent Hypohalite may be used as long as the bleach is added to avoid deactivation of the enzymes of the formulation. A
preferred method of preventing enzyme deactivation is CA 0221461~ 1997-09-03 C 6362 (V) ~ .
encapsulation of the bleach is described in-US-A-5,200,236, herein incorporated by reference. In the patented method, the bleaching agent is encapsulated as a core in a paraffin wax material having a melting point from about 40~C to 50~C. The wax coating has a thickness of from 100 to 1500 mlcrons .
Suitable reactive chlorine or bromine oxidizing materials are chloro and bromo amides such as trichloroisocyanuric, tribromoisocyanuric, dibromoisocyanuric and dichloroisocyanuric acids, and salts thereof with water solubilizing cations such as potassium and sodium.
Hydantoin compounds such as 1,3-dichloro-5,5-dimethylhydantoin are also quite suitable.
PeroxY Bleachinq Aqents The oxygen bleaching agents of the compositions include organic peroxy acids and diacylperoxides. Typical monoperoxy acids useful herein include alkyl peroxy acids and aryl peroxy acids such as:
i) peroxybenzoic acid and ring-substituted peroxybenzoic acids, e.g., peroxy-alpha-naphthoic acid, and magnesium monoperoxyphthalate ii) aliphatic and substituted aliphatic monoperoxy acids, e.g., peroxylauric acid, epsilon-phthalimido-peroxyhexanoic acid and o-carboxybenzamido peroxyhexanoic acid, N-nonylamidoperadipic acid and N-nonylamidopersuccinic acid.
iii) Cationic peroxyacids such as those described in US-A-5,422,028, US-A-5,294,362; and US-A-5,292,447, Atty. Docket No. 95-0394-UNI; Case 7392, Oakes et al.; and U.S. S/N
08/210, 973, Oakes et al., herein incorporated by reference.
CA 0221461~ 1997-09-03 C 6362 (V) iv) Sulfonyl peroxyacids such as compounds described in US-A-5,039,447 (Monsanto Co.), herein incorporated by reference.
Typical diperoxy acids useful herein include alkyl diperoxy acids and aryl diperoxy acids, such as:
v) 1,12-diperoxydodecanedioic acid vi) 1,9-diperoxyazelaic acid vii) diperoxybrassylic acid; diperoxysecacic acid and diperoxy-isophthalic acid viii) 2-decyldiperoxybutan-1,4-dioic acid ix) N,N1-terephthaloyl-di(6-aminopercaproic acid).
A typical diacylperoxide useful herein includes dibenzoylperoxide.
Inorganic peroxygen compounds are also suitable for the present invention. Examples of these materials useful in the invention are salts of monopersulfate, perborate monohydrate, perborate tetrahydrate, and percarbonate.
Preferred oxygen bleaching agents include epsilon-phthalimido-peroxyhexanoic acid, o-carboxybenzaminoperoxyhexanoic acid, and mixtures thereof.
Most preferred bleaching agents include perborate monohydrate and percarbonate.
The oxygen bleaching agent is present in the composition in an amount from about of 1 to 20 weight percent, preferably 1 to 15 weight percent.
The oxygen bleaching agent may be incorporated directly into the formulation or may be encapsulated by any number of encapsulation techniques known in the art to produce stable capsules in alkaline liquid formulations.
CA 0221461~ 1997-09-03 C 6362 (V) Bleach Precursors Suitable peroxygen peracid precursors for peroxy bleach compounds have been amply described in the literature, including GB Nos. 836,988; 855,735; 907,356; 907;358;
907,950; 1,003,310 and 1,246,339; US-A-3,332,882 and US-A-4,128,494.
Typical examples of precursors are polyacylated alkylene diamines, such as N,N,N1,N1-tetraacetylethylene diamine (TAED) and N,N,N1,N1-tetraacetylmethylene diamine (TAMD);
acylated glycolurils, such as tetraacetylglycoluril (TAGU);
triacetylcyanurate, sodium sulfophenyl ethyl carbonic acid ester, sodium acetyloxybenene sulfonate (SABS), sodium nonanoyloxy benzene sulfonate (SNOBS) and choline sulfophenyl carbonate. Peroxybenzoic acid precursors are known in the art, e.g., as described in GB-A-836,988.
Examples of suitable precursors are phenylbenzoate; phenyl p-nitrobenzoate; o-nitrophenyl benzoate; o-carboxyphenyl benzoate; p-bromophenylbenzoate; sodium or potassium benzoyloxy benzene-sulfonate; and benzoic anhydride.
Preferred peroxygen bleach precursors are sodium p-benzoyloxybenzene sulfonate, N,N,N1,N1-tetraacetylethylene diamine, sodium nonanoyloxybenzene sulfonate and choline sulfophenyl carbonate.
Bleach catalysts which may also be used in the detergent compositions include maganese catalysts such as those described in US-A-5,246,621.
Deter~ent Builder Materials The compositions of this invention contains either organic builders, particularly carboxylates, or inorganic builders, particularly phosphorous containing compounds.
Phosphorus Cont~; n; n~ Builders CA 0221461~ 1997-09-03 C 6362 (V) Examples of phosphorus-containing inorganic builders include the water-soluble salts, especially alkali metal pyrophosphates, orthophosphates and polyphosphates, particularly ammonium and alkanol ammonium salts, and phosphonates. Particularly preferred phosphate builders include sodium and potassium tripolyphosphates, pyrophosphates, hexametaphosphates and trimetaphosphates.
When phosphate builders are incorporated into the formula, they are present in an amount of about 10 to about 75~ by wt., most preferably 15 to about 60 wt. ~.
NonPhosPhorus Inor~anic BuilderR
Non-phosphorus-containing inorganic builders may be additionally used such as water-soluble alkali metal carbonates, bicarbonates, sesquicarbonates, borates, silicates, layered silicates such as SKS-6 ex Hoechst, metasilicates, phytic acid, borate and crystalline and amorphous aluminosilicates. Specific examples include sodium carbonate (with or without calcite seeds), potassium carbonate, sodium and potassium bicarbonates, silicates, including layered silicates and zeolites.
Orqanic Builders Organic detergent builders useful in the present invention include a variety of polycarboxylate compounds. As used herein "polycarboxylate" refers to compounds having a plurality of carboxylate groups, preferably at least three (3) carboxylates. Monomeric or polymeric carboxylates are preferred. Examples of organic builders include alkali metal citrates, succinates, malonates, fatty acid sulfonates, fatty acid carboxylates, nitrilotriacetates, phytates, phosphonates, alkanehydroxyphosphonates, oxydisuccinates, alkyl and alkenyl disuccinates, oxydiacetates, carboxymethyloxy succinates, ethylenediamine tetraacetates, tartrate monosuccinates, tartrate disuccinates, tartrate monoacetates, tartrate diacetates, CA 0221461~ 1997-09-03 C 6362 (V) oxidized starches, oxidized heteropolymeric polysaccharides, and polyhydroxysulfonates.
Polycarboxylates include polyacrylates, polymaleates, polyacetates, polyhydroxyacrylates, polyacrylate/polymaleate and polyacrylate/ polymethacrylate copolymers, acrylate/maleate/vinyl alcohol terpolymers, aminopolycarboxylates and polyacetal carboxylates, and polyaspartates and mixtures thereof. Such carboxylates are described in US-A-4,144,226, US-A-4,146,495 and US-A-4,686,062, herein incorporated by reference.
Alkali metal citrates, nitrilotriacetates, oxydisuccinates, polyphosphonates and acrylate/maleate copolymers and acrylate/maleate/vinyl alcohol terpolymers are especially preferred organic builders.
When the builder is comprised primarily of either monomeric or polymeric carboxylates or mixtures thereof the builder should be present in an amount of 10 to 60 wt. ~, most preferably 15 to 50 wt. ~.
The foregoing detergent builders are meant to illustrate but not limit the types of builders that can be employed in the present invention.
EnzYmes Additional enzymes capable of facilitating the removal of soils from a substrate may also be present in an amount of up to about 10% by wt., preferably 1 to about 5 wt. ~.
Such enzymes include proteases (e.g., Alcalase~, Savinase~
and Esperase~ from Novo Industries A/S and Purafect OxP~, ex. Genencor) and amylases (e.g., Termamyl~ and Duramyl~
from Novo Industries and Purafect OxAm~, ex. Genencor).
CA 022l46l~ l997-09-03 C 6362 (V) ODtional Inqredients Minor amounts of various other components may optionally be present in the cleaning composition. These include filler, non-carboxylic thickening agents, defoamer, bleach 5 scavengers including but not limited to sodium bisulfite, reducing sugars, and short chain alcohols; solvents and hydrotropes such as ethanol, isopropanol and xylene sulfonates; enzyme stabilizing agents; soil suspending agents; antiredeposition agents; anti-corrosion agents, such as benzotriazole and isocyanuric acid described in US-A-5,374,369; ingredients to enhance decor care such as certain aluminum salts described in U.S. Serial No.
08/444,502 and 08/444,503, herein incorporated by reference; colorants; perfumes; opacifiers such as titanium 15 dioxide; and other functional additives.
Sequestrants The detergent compositions herein may also optionally contain one or more transition metal tsuch as Fe, Mn, or 20 Cu) chelating agents. Such chelating agents can be selected from the group consisting of amino carboxylates, amino phosphonates, polyfunctionally-substituted aromatic chelating agents and mixtures therein. Without intending to be bound by theory, it is believed that the benefit of 25 these materials is due in part to their exceptional ability to remove transition metal ions such as Fe, Mn, and Cu from washing ~olutions by formation of soluble chelates.
Amino carboxylates useful as optional chelating agents 30 include ethylenediaminetetraacetates; N-hydroxyethylethylenediaminetriacetates; nitrilotriacetates;
ethylenediamine tetraproprionates; triethylenetetraamine-hexaacetates; diethylenetriaminepentaacetates;
ethylenediamine disuccinate; ethanoldiglycines; alkali 35 metal, ammonium, and substituted ammonium salts therein and mixtures therein.
CA 0221461~ 1997-09-03 C 6362 (V) .
Phosphonates and amino phosphonates are also suitable for use as chelating agents in the compositions of the invention when at least low levels of total phosphorus are permitted in detergent compositions, and include ethylenediaminetetrakis (methylenephosphonates), nitrilotris (methylenephosphonates) and diethylenetriaminepentakis (methylenephosphonates).
Preferably, these phosphonates and aminophosphonates do not contain alkyl or alkenyl groups with more than about 6 carbon atoms.
Polyfunctionally-substituted aromatic chelating agents are also useful in the compositions herein. See US-A-3,812,044, Preferred compounds of this type in acid formare dihydroxydisulfobenzenes such as 1,2-dihydroxy-3,5-disulfobenzene.
If utilized, these chelating agents will generally comprise from about 0.1~ to about 10~ by weight of the detergent compositions herein. More preferably, if utilized, the chelating agents will comprise from about 0.1~ to about 3.0~ by weight of such composition.
Anti-Scalants Scale formation on dishes and machine parts is an important problem that needs to be resolved or at least mitigated in formulating a machine warewashing product, especially in the case of low-pho~phate (e. g. less than the equivalent of 20% by weight, particularly 10~ by weight of sodium triphosphate) and phosphate-free machine warewashing compositions, particularly zero-P machine warewashing compositions.
In order to reduce this problem, co-builders, such as polyacrylic acids or polyacrylates (PAA), acrylate/maleate CA 0221461~ 1997-09-03 C 6362 (V) copolymers, polyaspartates, ethylenediamine disuccinate and the various organic polyphosphonates, e.g. Dequest series, may be incorporated in one or more system components. For improved biodegradability, (as such co-builders), the block co-polymers of formula (I) as defined in published PCT
patent specification WO 94/17170 may also be used. In any component, the amount of anti-scalant may be in the range of from 0.5 to 10, preferably from 0.5 to 5, and more preferably from 1 to 5% by weight.
Surfactants Useful surfactants include anionic, nonionic, cationic, amphoteric, amphoteric types and mixtures of these surface active agents. It is understood that surfactants should be selected and used at such levels as conventionally known in the art so as not to deactivate enzymes in the formula.
Such surfactants are well known in the detergent art and are described at length in "Surface Active Agents and Detergents", Vol. II, by Schwartz, Perry & Birch, Interscience Publishers, Inc. 1959, herein incorporated by reference.
Surfactants, if present in the composition, may be selected from the following:
Anionic surfactants Anionic synthetic detergents can be broadly described as surface active compounds with one or more negatively charged functional groups. An important class of anionic compounds are the water-soluble salts, particularly the alkali metal salts, of organic sulfur reaction products having in their molecular structure an alkyl radical containing from about 6 to 24 carbon atoms and a radical selected from the group consisting of sulfonic and sulfuric acid ester radicals.
CA 022l46l~ l997-09-03 C 6362 (V) Primary Alkyl Sulfates Rl 70503M
where Rl7 is a primary alkyl group of 8 to 18 carbon atoms and M is a solubilizing cation. The alkyl group Rl7 may have a mixture of chain lengths. It is preferred that at least two thirds of the Rl7 alkyl groups have a chain length of 8 to 14 carbon atoms. This will be the case if R17 is coconut alkyl, for example. The solubilizing cation may be a range of cations which are in general monovalent and confer water solubility. Alkali metal, notably sodium, is especially envisaged. Other possibilities are ammonium and substituted ammonium ions, such as trialkanolammonium or trialkylammonium.
Alkyl Ether Sulfates Rl70 (CH2CH20) nSO3M
where Rl7 is a primary alkyl group of 8 to 18 carbon atoms, n has an average value in the range from 1 to 6 and M is a solubilizing cation. The alkyl group Rl7 may have a 20 mixture of chain lengths. It is preferred that at least two thirds of the Rl7 alkyl groups have a chain length of 8 to 14 carbon atoms. This will be the case if Rl7 is coconut alkyl, for example. Preferably n has an average value of 2 to 5.
Fatty Acid Ester Sulfonates Rl~CH (SO~M) COzRl9 where Rl8 is an alkyl group of 6 to 16 atoms, R19 is an alkyl group of 1 to 4 carbon atoms and M is a solubilizing cation. The group Rla may have a mixture of chain lengths.
Preferably at least two thirds of these groups have 6 to 12 carbon atoms.
This will be the case when the moiety Rl~CH(-)CO2(-) is derived from a coconut source, for instance. It is CA 0221461~ 1997-09-03 C 636~
~ .~
preferred that Rl9 is a straight chain alkyl, notably methyl or ethyl.
Alkyl Benzene Sulfonates R20ArSO~M
where RZ~ is an alkyl group of 8 to 18 carbon atoms, Ar is -a benzene ring (C6H4) and M is a solubilizing cation. The group R20 may be a mixture of chain lengths. Straight chains of 11 to 14 carbon atoms are preferred.
Organic phosphate based anionic surfactants include organic phosphate esters such as complex mono- or diester phosphates of hydroxyl- terminated alkoxide condensates, or salts thereof. Included in the organic phosphate esters are phosphate ester derivatives of polyoxyalkylated alkylaryl phosphate esters, of ethoxylated linear alcohols and ethoxylates of phenol.
Also included are nonionic alkoxylates having a sodium alkylenecarboxylate moiety linked to a terminal hydroxyl group of the nonionic through an ether bond. Counterions to the salts of all the foregoing may be those of alkali metal, alkaline earth metal, ammonium, alkanolammonium and alkylammonium types.
Particularly preferred anionic surfactants are the fatty acid ester sulfonates with formula:
R CH (503M) CO2R
where the moiety Rl8CH(-) CO2 (-) is derived from a coconut source and Rl9 is either methyl or ethyl.
Nonionic surfactants Nonionic surfactants can be broadly defined as surface active compounds with one or more uncharged hydrophilic substituents. A major class of nonionic surfactants are those compounds produced by the condensation of alkylene CA 0221461~ 1997-09-03 C 63 62 ' (V) oxide groups with an organic hydrophobic material which may be aliphatic or alkyl aromatic in nature. The length of the hydrophilic or polyoxyalkylene radical which is condensed with any particular hydrophobic group can be readily adjusted to yield a water-soluble compound having the desired degree of balance between hydrophilic and hydrophobic elements. Illustrative, but not limiting examples, of various suitable nonionic surfactant types are:
polyoxyethylene or polyoxypropylene condensates of aliphatic carboxylic acids, whether linear- or branched-chain and unsaturated or saturated, containing from about 8 to about 18 carbon atoms in the aliphatic chain and incorporating from about 2 to about 50 ethylene oxide and/or propylene oxide units. Suitable carboxylic acids include "coconut" fatty acids (derived from coconut oil) which contain an average of about 12 carbon atoms, "tallow" fatty acids (derived from tallow-class fats) which contain an average of about 18 carbon atoms, palmitic acid, myristic acid, stearic acid and lauric acid, polyoxyethylene or polyoxypropylene condensates of aliphatic alcohols, whether linear- or branched-chain and unsaturated or saturated, containing from about 6 to about 24 carbon atoms and incorporating from about 2 to about 50 ethylene oxide and/or propylene oxide units. Suitable alcohols include "coconut" fatty alcohol, "tallow" fatty alcohol, lauryl alcohol, myristyl alcohol and oleyl alcohol.
Ethoxylated fatty alcohols may be used alone or in admixture with anionic surfactants, especially the preferred surfactants above. The average chain lengths of the alkyl group R21 in the general formula: R2lO(CH2CH20)nH
CA 0221461~ 1997-09-03 C 63 62 (V) is from 6 to 24 carbon atoms. Preferably the group R21 may have chain lengths in a range from 9 to 18 carbon atoms.
The average value of n should be at least 2. The numbers of ethylene oxide residues may be a statistical distribution around the average value. However, as is known, the distribution can be affected by the manufacturing process or altered by fractionation after ethoxylation. Particularly preferred ethoxylated fatty alcohols have a group R2l which has 9 to 18 carbon atoms while n is from 2 to 8.
Also included within this category are nonionic surfactants having a formula:
R22 (CH~CHO~(CH2CH2O~(CH2CIHO~H
wherein R22 is a linear alkyl hydrocarbon radical having an average of 6 to 18 carbon atoms, R23 and R24 are each linear alkyl hydrocarbons of about 1 to about 4 carbon atoms, x is an integer of from 1 to 6, y is an integer of from 4 to 20 and z is an integer from 4 to 25.
One preferred nonionic surfactant of the above formula is Poly-Tergent SLF-18~ a registered trademark of the Olin Corporation, New Haven, Conn. having a composition of the above formula where R22 is a C6-C10 linear alkyl mixture, R23 and R24 are methyl, x averages 3, y averages 12 and z averages 16. Another preferred nonionic surfactant is CA 022l46l~ l997-09-03 C 6362 (V~
' ~
R25O(CH2lHO)j(CH2CH20~(CH2CH(O~R26)z 5 wherein R2s is a linear, aliphatic hydrocarbon radical having from about 4 to about 18 carbon atoms including - mixtures thereof; and R26 is a linear, aliphatic hydrocarbon radical having from about 2 to about 26 carbon atoms including mixtures thereof; j is an integer having a value of from 1 to about 3; k is an integer having a value from 5 to about 30; and z is an integer having a value of from 1 to about 3. Most preferred are compositions in which j is 1, k is from about 10 to about 20 and z is 1.
These surfactants are described in WO 94/22800. Other 15 preferred nonionic surfactants are linear fatty alcohol alkoxylates with a capped terminal group, as described in U. S . 4,340,766 to BASF.
Another nonionic surfactant included within this category 20 are compounds of formula:
R27~(CH2CH20)qH
wherein R27 is a C6-C24 linear or branched alkyl hydrocarbon radical and q is a number from 2 to 50; more preferably R27 25 iS a C8-C18 linear alkyl mixture and q is a number from 2 to 15.
polyoxyethylene or polyoxypropylene condensate~ of alkyl phenols, whether linear- or branched-chain and unsaturated 30 or saturated,containing from about 6 to 12 carbon atoms and incorporating from about 2 to about 25 moles of ethylene oxide and/or propylene oxide.
polyoxyethylene derivatives of sorbitan mono-, di-, and tri-fatty acid esters wherein the fatty acid component has between 12 and 24 carbon atoms. The preferred CA 0221461~ 1997-09-03 C 6362 (~1) ' .
sorbitan trilaurate, sorbitan monopalmitate, sorbitan tripalmitate, sorbitan monostearate, sorbitan monoisostearate, sorbitan tripalmitate, sorbitol tristearate, sorbitan monooleate, and sorbitan trioleate.
The polyoxyethylene chains may contain between about 4 and 30 ethylene oxide units, preferably about 10 to 20. The sorbitan ester derivatives contain 1, 2 or 3 polyoxyethylene chains dependent upon whether they are mono-, di- or tri-acid esters.
polyoxyethylene-polyoxypropylene block copolymers having formula:
HO (CH2cH20) a (CH (CH3) CH20) b (CH2CH20) CH
or HO (CH (CH3) CH2O) d (CH2CH20) e (CH (CH3) CH20) fH
wherein a, b, c, d, e and f are integers from 1 to 350 reflecting the respective polyethylene oxide and polypropylene oxide blocks of said polymer. The polyoxyethylene component of the block polymer constitutes at least about 10% of the block polymer. The material preferably has a molecular weight of between about 1,000 and 15,000, more preferably from about 1,500 to about 6,000. These materials are well-known in the art. They are available under the trademark "Pluronic" and "Pluronic R", a product of BASF Corporation.
Amine oxides having formula:
R28R29R30N=o wherein R29, R29 and R30 are saturated aliphatic radicals or substituted saturated aliphatic radicals. Preferable amine oxides are those wherein R29 is an alkyl chain of about 10 CA 0221461~ 1997-09-03 C 6362 (V) to about 20 carbon atoms and R29 and R30 are methyl or ethyl groups or both R28 and R29 are alkyl chains of about 6 to about 14 carbon atoms and R30 is a methyl or ethyl group.
Amphoteric synthetic detergents may also be broadly described as derivatives of aliphatic and tertiary amines, in which the aliphatic radical may be straight chain or branched and wherein one of the aliphatic substituents contain from about 8 to about 18 carbons and one contains an anionic water-solubilizing group, i.e., carboxy, sulpho, sulphato, phosphato or phosphono. Examples of compounds falling within this definition are sodium 3-dodecylamino propionate and sodium 2-dodecylamino propane sulfonate.
Amphoteric synthetic detergents can be broadly described as derivatives of aliphatic quaternary ammonium, phosphonium and sulphonium compounds in which the aliphatic radical may be straight chained or branched, and wherein one of the aliphatic substituents contains from about 8 to about 18 carbon atoms and one contains an anionic water-solubilizing group, e.g., carboxy, sulpho, sulphato, phosphato or phosphono. These compounds are frequently referred to as betaines. Besides alkyl betaines, alkyl amino and alkyl amido betaines are encompassed within this invention.
Alkyl Glycosides R31o (R320) (Zl) wherein R31 is a monovalent organic radical (e.g., a monovalent saturated aliphatic, unsaturated aliphatic or aromatic radlcal such as alkyl, hydroxyalkyl, alkenyl, hydroxyalkenyl, aryl, alkylaryl, hydroxyalkylaryl, arylalkyl, alkenylaryl, arylalkenyl, etc.) containing from about 6 to about 30 (preferably from about 8 to 18 and more preferably from about 9 to about 13) carbon atoms; R32 is a divalent hydrocarbon radical containing from 2 to about 4 carbon atoms such as ethylene, propylene or CA 0221461~ 1997-09-03 C 6362 (V) . ~
butylene (most preferably the unit (R320) n represents repeating units of ethylene oxide, propylene oxide and/or random or block combinations thereof); n is a number having an average value of from 0 to about 12; Zl represents a moiety derived from a reducing saccharide containing 5 or 6 carbon atoms (most preferably a glucose unit); and p is a number having an average value of from 0.5 to about 10 preferably from about 0.5 to about 5 .
Examples of commercially available materials from Henkel Kommanditgesellschaft Aktien of Dusseldorf, Germany include APG~ 300, 325 and 350 with R3l being C9-Cll, n is 0 and p is 1.3, 1. 6 and 1.8-2.2 respectively; APG~ 500 and 550 with R3 is Cl2-Cl3, n is 0 and p is 1.3 and 1.8-2.2, respectively;
and APG~ 600 with R3l being Cl2-Cl4, n is 0 and p is 1.3.
While esters of glucose are contemplated especially, it is envisaged that corresponding materials based on other reducing sugars, such as galactose and mannose are also suitable.
- The amount of surfactant present in the final formula should be from about 0.5 to about 30~ by weight of the composition. The preferred range of surfactant is from 0.5 to 20~ by weight, more preferably from 0.5 to 10~ by weight.
Filler An inert filler material which is water-soluble may also be present in cleaning compositions. This material should not precipitate calcium or magnesium ions at the filler use level. Suitable for this purpose are organic or inorganic compounds. Organic fillers include sucrose esters and urea. Representative inorganic fillers include sodium sulfate, sodium chloride and potassium chloride. A
preferred filler is sodium sulfate. Its concentration may CA 0221461~ 1997-09-03 C 6362 (~) range from 0~ to 20~, preferably from about 2~ to about 10 by weight of the cleaning composition.
Thickeners & Stabilizers Thickeners are often desirable for liquid cleaning compositions. Thixotropic thickeners such as smectite clays including montmorillonite (bentonite), hectorite, saponite, and the like may be used to impart viscosity to liquid cleaning compositions. Silica, silica gel, and aluminosilicate may also be used as thickeners. Salts of polyacrylic acid (of molecular weight of from about 300,000 up to 6 million and higher), including polymers which are cross-linked may also be used alone or in combination with other thickeners. Use of clay thickeners for machine dishwashing compositions is disclosed for example in US-A-4,431,559; US-A-4,511,487; US-A-4,740,327; US-A-4,752,409.
Commercially available synthetic smectite clays include Laponite supplied by Laporte Industries. Commercially available bentonite clays include Korthix H and VWH ex Combustion Engineering, Inc.; Polargel T ex American Colloid Co.; and Gelwhite clays (particularly Gelwhite GP
and H) ex English China Clay Co. Polargel T is preferred as imparting a more intense white appearance to the composition than other clays. The amount of clay thickener employed in the compositions is from 0.1 to about 10~, preferably 0.5 to 5~. Use of salts of polymeric carboxylic acids is disclosed for example in GB-A-2,164,350, US-A-4,859,358 and US-A-4,836,948.
For liquid formulations with a "gel" appearance and rheology, particularly if a clear gel is desired, a chlorine-resistant polymeric thickener is particularly useful. US-A-4,260,528 discloses natural gums and resins for use in clear machine dishwashing detergents, which are not chlorine stable. Acrylic acid polymers that are cross-linked manufactured by, for example, B.F. Goodrich CA 0221461~ 1997-09-03 C 6362 (~) and sold under the trade name "Carbopol" have been found to be effective for production of clear gels, and Carbopol 940, 617 and 627, having a molecular weight of about 4,000,000 are particularly preferred for maintaining high 5 viscosity with excellent chlorine stability over extended periods. Further suitable chlorine-resistant polymeric thickeners are described in US-A-4,867,896 incorporated by reference herein.
The amount of thickener employed in the compositions is from 0 to 5~, preferably 0. 5-3~ .
Stabilizers and/or co-structurants such as long-chain calcium and sodium soaps and C12 to C1~ sulfates are 15 detailed in US-A- 3,956,158 and US-A-4,271,030 and the use of other metal salts of long-chain soaps is detailed in US-A-4,752,409. Other co-structurants include Laponite and metal oxides and their salts as described in US-A-4,933,101, herein incorporated by reference. The amount of 20 stabilizer which may be used in the liquid cleaning compositions is from about 0.01 to about 5~ by weight of the composition, preferably 0. 01-2~. Such stabilizers are optional in gel formulations. Co-structurants which are found especially suitable for gels include trivalent metal 25 ions at 0. 01-4~ of the compositions, Laponite and/or water-soluble structuring chelants at 0. 01-5~ . These co-structurants are more fully described in the US-A-5,141,664, hereby incorporated by reference.
30 De f oamer The formulations of the cleaning composition comprising surfactant may further include a defoamer. Suitable defoamers include mono-and distearyl acid phosphate, silicone oil and mineral oil. Even if the cleaning 35 composition has only defoaming surfactant, the defoamer assists to minimize foam which food soils can generate.
CA 0221461~ 1997-09-03 C 63 62 (~1) The compositions may include 0. 02 to 2~ by weight of defoamer, or preferably 0.05-1.0~. Preferred antifoam systems are described in Angevaare et al.; US S/N
08/539,923, herein incorporated by reference.
The following examples will serve to distinguish this invention from the prior art and illustrate its embodiments more fully. Unless otherwise indicated, all parts, percentages and proportions referred to are by weights.
Example 1 The lime soap dispersant properties of amphoteric polymers within the scope of the invention was compared to that of lime soap dispersants known in the prior art as described 15 below.
The polymers were evaluated for their lime soap dispersing power value (LSDP), which is a conventional measurement of the effectiveness of a material for dispersing lime soap.
20 The lime soap dispersing power value (LSDP) is defined as the (weight ratio of dispersant to sodium oleate X 100) based on the amount of dispersant required to disperse lime soap curd formed by 0. 025g sodium oleate and 30mls of water of 333 ppm. CaC03 equivalent hardness. According to the 25 test, a low LSDP value is an indication of an effective lime soap dispersant. A detailed description of the test is found in an article by H.C. Borghetty and C.A. Bergman, J. Am. Oil Chem. Soc., 27, pages 88-90, (1950). The materials used in the comparison are described in Table I
below:
CA 0221461~ 1997-09-03 C 6362 (V) Table 1 MAT~T~TAT.S SOURCE LSDP
Amphoteric Polymer PC2 Supplied by Rohm & Haas 1.5 5 Amphoteric Polymer E-2072 Supplied By ALCO 1.5 Amphoteric Polymer E-2075 Supplied By ALCO 2.5 C13-C15 Alcohol Described in WO
Ethoxylate (12EO) 94/07985 6.0 C12-C18 Alcohol Described in WO
Ethoxy Sulfate (3EO) 94/07985 4.0 Polyacrylic Acid (200,000 MW) 22.0 Polyacrylic Acid Acusol 445 supplied (4,500 MW) by Rohm and Haas 15.0 15 Polyacrylic Acid/ Supplied by Aldrich Acrylamide (200,000 17.5 MW) As this example illustrates, amphoteric polymers within the scope of the invention are extremely effective lime soap dispersants in comparison to similar polymers outside the scope of the invention and in comparison to the preferred lime soap dispersants claimed in WO 94/07984 and WO
Example 2 The effect on glass and plasticware appearance of polymers and surfactants having an LSDP of less than 8 were compared by determining the effectiveness of each material in preventing the formation of mineral spots and films on clear glass tumblers and inhibition of lime soap filming on CA 0221461~ 1997-09-03 C 6362 (V) polyethylene plates when incorporated into the lipase containing base formulation.
A base machine dishwashing detergent composition was prepared as described in Table 2 below.
Table 2 INGREDIENTS % BY WT.
STPP 51 . O
Sodium silicate (PQ Britesil 30.0 H20) Sodium Percarbonate 9.0 TAED 3.6 (tetraacetylethylenediamine) Protease (Novo Savinase 6T) 3.0 Amylase (Novo Termamyl 60T) 1.8 Lipase (Novo Lipolase lOOT) 0.2 Nonionic (BASF Plurafac 1.4 LF403) Lime soap dispersants were incorporated into the described base at a level of 5~ by wt. in addition to the above composition.
A ten cycle test procedure was used as follows:
Five glass tumblers and two polyethylene plates were placed in a Bosch model 6082 dishwasher along with a ballast load of clean dishware consisting of 9 ceramic dinner plates, 2 ceramic tea cups, 2 stainless steel plates, and 2 melamine plates. Twenty grams of ASTM standard soil consisting of CA 0221461~ 1997-09-03 C 6362 ~V) 80~ margarine and 20~ powdered milk was added to the dishwasher by spreading it onto the inside of the machine door. The 50~ C. Economy wash setting was used, with water of 300/320 ppm. permanent/temporary hardness expressed as CaCO3 equivalent (4:1 Ca/Mg ratio). 18.0 g detergent was added at the start of the main wash, along with lipase (Lipolase lOOT ex. Novo) and selected polymer (5~ by wt. in addition to the detergent composition) as specified. At the end of each complete cycle, fresh soil and detergent were added and the process repeated for a total of ten washes.
At the end of this process the tumblers and polyethylene items were visually graded for spotting and filming.
Grading scales of from 0 to 5 were used to measure film deposition, where a grade of 0 indicates no visible film and a grade of 5 indicates coverage with a very heavy, opaque film. When lipase is present in the detergent composition, a film buildup can occur on the hydrophobic polyethylene articles, caused primarily by precipitated Ca soap. Thus, film scores for the polyethylene articles give an indication of lime soap dispersant efficacy.
For spotting, the number of spots on each item was counted, with the average number of spots per article reported. The number of spots on the glass tumblers gives an indication of the effectiveness of the lipase. When lipase is present in the detergent composition, the lowest number of spots corresponds to the most effective lipase action.
The following spotting and filming grades were obtained (as 30 noted, filming on polyethylene items in the presence of lipase is primarily caused by lime soap deposition):
CA 0221461~ 1997-09-03 C 6362 (V) Composition Glass TumblersPolYethylene Items mineral film lime soap film score # of spots film score # of SPots (1) Base formulation 1.0 225 3.0 138 (2) Base + lipase, no dispersant 1.0 1 5.0 0 (3) Base + lipase +
amphoteric 1. 5 0 2.5 0 polymer ( PC2) 15 (4) Base + Lipase +
C13-C15 EO12 0.5 51 2.0 33 alcohol ethoxylate (5) Base + Lipase +
alcohol 0. 5 120 0.0 127 ethoxysulfate As this example demonstrates, addition of lipase to the 25 base formulation results in a significant reduction in the number of spots on the glass tumblers (Composition 2) . This is indicative of lipase functioning in the system. However, filming on polyethylene items is very high, due to lime soap deposition. Addition of an amphoteric polymer within 30 the scope of the invention (Composition 3) significantly reduces the film score on polyethylene items, while the excellent glassware appearance produced by lipase is retained, as seen by the low spotting scores on the glass tumblers. In contrast, while the materials described in 35 W094/07984 and WO/07985 (incorporated in Compositions 4 and 5) reduce lime soap deposition, they also greatly reduce C 6362 (V) CA 0221461~ 1997-09-03 the antispotting benefit originally provided by the lipase in the detergent composition.
Exam~le 3 The ability of amphoteric polymers to reduce lime soap deposition without inhibiting the antispotting benefit provided by lipase was further demonstrated as follows:
The ten wash cycle test procedure described in example 2 was followed. The base dishwashing detergent composition as described in Table 2 was used for this example, but was dosed at 26.0 g instead of the 18.0 g used in example 2.
Amphoteric polymers were added to this composition at a level of 4%, as opposed to the 5% used in the previous example. All other test parameters were identical to those for example 1.
The following spotting and filming grades were obtained (as noted, filming on polyethylene items is primarily caused by lime soap deposition):
CA 022l46l~ l997-09-03 C 6362 ~V) Composition Glass TumblersPolyethylene Items mineral film lime soap 5 film score # of spots film score # of spots (1) Base + lipase, no dispersant 2.1 0 1.5 225 (2) Base + lipase +
amphoteric polymer (PC2) 2.2 2 0 23 15 (3) Base + lipase +
amphoteric polymer (Alco E-2072) 2.3 2 0.3 30 (4) Base + lipase +
amphoteric polymer (Alco E-2075) 1.9 2 0.3 16 This example further illustrates the effectiveness of amphoteric polymers within the scope of the invention in 25 improving glass and plasticware appearance by inhibiting the deposition of lime soap while maintaining the antispotting benefit provided by lipase.
Claims (21)
1. A method of preventing the deposition of lime soap on tableware in a machine dishwasher comprising the steps of:
a) selecting a detergent composition comprising:
i) an effective amount of an amphoteric polymer wherein in a 1% aqueous solution having a pH of about 7 or greater, positively charged monomers are present on the polymer comprising between 1% and 50% by mole of the polymer, the polymer having a formula selected from the group consisting of:
AxByCz wherein in a 1% aqueous wash liquor pH A is an anionic moiety, B is a cationic moiety and C is selected from the group consisting of anionic moiety, cationic moiety, amphoteric moiety, uncharged moiety and mixtures thereof, and x is 50-99 mole % and y is 1-50 mole %, and z is 0-25 mole %, or or DdEf wherein in a 1% aqueous wash liquor pH, D is an amphoteric moiety, E is selected from the group consisting of anionic moiety, cationic moiety, uncharged moiety and mixtures thereof, d is 1 to 100 mole %, f is 0-99 mole %;
ii) 0.01% to about 4 wt % of a lipolytic enzyme, and iii) about 1 to about 75% by wt. of a builder material;
and b) applying the detergent composition to soiled tableware to substantially prevent deposition of lime soap on cleaned tableware.
a) selecting a detergent composition comprising:
i) an effective amount of an amphoteric polymer wherein in a 1% aqueous solution having a pH of about 7 or greater, positively charged monomers are present on the polymer comprising between 1% and 50% by mole of the polymer, the polymer having a formula selected from the group consisting of:
AxByCz wherein in a 1% aqueous wash liquor pH A is an anionic moiety, B is a cationic moiety and C is selected from the group consisting of anionic moiety, cationic moiety, amphoteric moiety, uncharged moiety and mixtures thereof, and x is 50-99 mole % and y is 1-50 mole %, and z is 0-25 mole %, or or DdEf wherein in a 1% aqueous wash liquor pH, D is an amphoteric moiety, E is selected from the group consisting of anionic moiety, cationic moiety, uncharged moiety and mixtures thereof, d is 1 to 100 mole %, f is 0-99 mole %;
ii) 0.01% to about 4 wt % of a lipolytic enzyme, and iii) about 1 to about 75% by wt. of a builder material;
and b) applying the detergent composition to soiled tableware to substantially prevent deposition of lime soap on cleaned tableware.
2. A method according to claim 1, wherein x is 80 to about 98 mole %, y is 2-20 mole % and z is 0 to 18 mole %.
3. A method according to claim 1, wherein the anionic moiety A is a substituted vinyl compound.
4. A method according to claim 3, wherein the substituted vinyl compound is a compound of formula l (I) wherein R1, R2, and R3 each are independently a hydrogen, C1 to C3 alkyl, a carboxylate group or a carboxylate group substituted with a C1 to C30 straight or branched alkyl, aromatic heterocycle or a polyalkylamine oxide provided that at least one of R1, R2, or R3 is a carboxylate or a substituted carboxylate.
5. A method according to claim 4 wherein the compounds are selected from the group consisting of acrylic acid, methacrylic acid, maleic acid, .alpha.-ethacrylic acid, .beta.,.beta.,-dimethacrylic acid, methylenemalonic acid, vinylacetic acid, allylacetic acid, ethylidineacetic acid, propylidineacitic acid, crotonic acid, fumaric acid, itaconic acid, citraconic acid, mesaconic acid and mixtures thereof.
6. A method according to claim 5 wherein the compounds are selected from the group consisting of acrylic acid, methacrylic acid and maleic acid.
7. A method according to claim 1 wherein the cationic moiety (B) is a substituted vinyl compound of formula 11 (II) wherein R4 is a hydrogen, aromatic, heterocycle or a polyalkylamine oxide; R5 is a hydrogen or a C1 to C30 straight or branched alkyl; and Q is a nitrogen-containing organic radical, said radical having a pKa value of > 7.
8. A method according to claim 7 wherein the compounds of formula II are selected from the group consisting of vinylamine, dialkylaminoalkyl methacrylate, dialkylaminoalkyl acrylate, dialkylaminoalkyl methacrylamide and dialkylaminoalkyl acrylamide.
9. A method according to claim 7 wherein Q is a compound selected from the group consisting of formula 111 CH2N+(CH3)2CH2CH=CH2X (III) wherein X is any suitable counterion such as halogen, hydroxide, sulfate, hydrosulfate, phosphate, formate and acetate;
or formula 1V
-Z-CH2-CR6R7(CH2)mN+R8R9R10 (IV) wherein Z is selected from the group consisting of O, COO
and CONR11 in which R11 is a hydrogen or a C1 to C3 alkyl group; R6 and R7 are each independently selected from the group consisting of hydrogen, C1 to C4 alkyl or R6 and R7 taken together form a C3 to C7 aliphatic heterocycle; m is 0 to 2 provided that when m is 0 a C-N bond is present in lieu of the (CH2)m group and R8, R9, and R10 are each independently selected from a group consisting of hydrogen or a C1 to C4 alkyl; or R8 and R9 are taken together with the nitrogen to which they are attached to form a 3 to 7 membered non-aromatic nitrogen heterocycle; and X is any suitable counterion such as a halogen, hydroxide, sulfate, hydrosulfate, phosphate, formate and acetate.
or formula 1V
-Z-CH2-CR6R7(CH2)mN+R8R9R10 (IV) wherein Z is selected from the group consisting of O, COO
and CONR11 in which R11 is a hydrogen or a C1 to C3 alkyl group; R6 and R7 are each independently selected from the group consisting of hydrogen, C1 to C4 alkyl or R6 and R7 taken together form a C3 to C7 aliphatic heterocycle; m is 0 to 2 provided that when m is 0 a C-N bond is present in lieu of the (CH2)m group and R8, R9, and R10 are each independently selected from a group consisting of hydrogen or a C1 to C4 alkyl; or R8 and R9 are taken together with the nitrogen to which they are attached to form a 3 to 7 membered non-aromatic nitrogen heterocycle; and X is any suitable counterion such as a halogen, hydroxide, sulfate, hydrosulfate, phosphate, formate and acetate.
10. A method according to claim 1 wherein the amphoteric moiety (D) has formula (V) wherein R12 is a C3-C6 monoethylenically unsaturated carboxylate;
R13 and R14 each independently represent hydrogen or a C1-3 alkyl; R15 and R16 each represent a hydrogen or a C1-3 alkyl, x is 1-3 and y is 1-3.
R13 and R14 each independently represent hydrogen or a C1-3 alkyl; R15 and R16 each represent a hydrogen or a C1-3 alkyl, x is 1-3 and y is 1-3.
11. The method according to claim 10 wherein R12 is a carboxylate selected from the group consisting of acrylic acid, methacrylic acid, .alpha.-ethacrylic acid, .beta.,.beta.,-dimethacrylic acid, methylenemalonic acid, vinylacetic acid, allylacetic acid, ethylidineacetic acid, propylidineacitic acid, crotonic acid, maleic acid, fumaric acid, itaconic acid, citraconic acid, mesaconic acid, and alkali metal and ammonium salts thereof.
12. The method according to claim 1 wherein the amphoteric polymer is a copolymer of acrylic acid and 3-acrylamidopropyl trimethylammonium chloride.
13. The method according to claim 1 wherein the amphoteric polymer is a terpolymer of acrylic acid, dimethyldiallylammonium chloride, and C14-20 EO 20 itaconate ester.
14. The method according to claim 1 wherein the amphoteric polymer is present in an amount of from 0.1 to about 25 wt. %.
15. The method according to claim 1 wherein the detergent composition further comprises a protease, an amylase and mixtures thereof.
16. A detergent composition useful for preventing deposition of lime soap on tableware in a machine dishwasher comprising:
i) an effective amount of an amphoteric polymer wherein in a 1% aqueous solution having a pH of about 7 or greater, positively charged monomers are present on the polymer comprising between 1% and 50% by mole of the polymer, the polymer having a formula selected from the group consisting of:
AxByCz wherein in a 1% aqueous wash liquor pH A is an anionic moiety, B is a cationic moiety and C is selected from the group consisting of anionic moiety, cationic moiety, amphoteric moiety, uncharged moiety and mixtures thereof, and x is 50-99 mole % and y is 1-50 mole %, and z is 0-25 mole %, or DdEf wherein in a 1% aqueous wash liquor pH, D is an amphoteric moiety, E is selected from the group consisting of anionic moiety, cationic moiety, uncharged moiety and mixtures thereof, d is 1 to 100 mole %, f is 0-99 mole %;
ii) 0.01% to about 4 wt % of a lipolytic enzyme; and iii) about 1 to about 75% by wt. of a builder material.
i) an effective amount of an amphoteric polymer wherein in a 1% aqueous solution having a pH of about 7 or greater, positively charged monomers are present on the polymer comprising between 1% and 50% by mole of the polymer, the polymer having a formula selected from the group consisting of:
AxByCz wherein in a 1% aqueous wash liquor pH A is an anionic moiety, B is a cationic moiety and C is selected from the group consisting of anionic moiety, cationic moiety, amphoteric moiety, uncharged moiety and mixtures thereof, and x is 50-99 mole % and y is 1-50 mole %, and z is 0-25 mole %, or DdEf wherein in a 1% aqueous wash liquor pH, D is an amphoteric moiety, E is selected from the group consisting of anionic moiety, cationic moiety, uncharged moiety and mixtures thereof, d is 1 to 100 mole %, f is 0-99 mole %;
ii) 0.01% to about 4 wt % of a lipolytic enzyme; and iii) about 1 to about 75% by wt. of a builder material.
17. A composition according to claim 16 wherein x is 80 to about 98 mole %, y is 2-20 mole % and z is 0 to 18 mole %.
18. A composition according to claim 16 wherein the anionic moiety A is a substituted vinyl compound.
19. A composition according to claim 18 wherein the substituted vinyl compound is a compound of formula 1 (I) wherein R1, R2, and R3 each are independently a hydrogen, C1 to C3 alkyl, a carboxylate group or a carboxylate group substituted with a C1 to C30 straight or branched alkyl, aromatic heterocycle or a polyalkylamine oxide provided that at least one of R1, R2, or R3 is a carboxylate or a substituted carboxylate;
20. A composition according to claim 19 wherein the compounds are selected from the group consisting of acrylic acid, methacrylic acid, maleic acid, .alpha.-ethacrylic acid, .beta.,.beta.,- dimethacrylic acid, methylenemalonic acid, vinylacetic acid, allylacetic acid, ethylidineacetic acid, propylidineacitic acid, crotonic acid, fumaric acid, itaconic acid, citraconic acid, mesaconic acid and mixtures thereof.
21. A method of preventing the deposition of lime soap on tableware in a machine dishwasher as claimed in claim 1 and substantially as described herein.
Applications Claiming Priority (2)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
US70784396A | 1996-09-09 | 1996-09-09 | |
US08/707843 | 1996-09-09 |
Publications (1)
Publication Number | Publication Date |
---|---|
CA2214615A1 true CA2214615A1 (en) | 1998-03-09 |
Family
ID=24843382
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
CA002214615A Abandoned CA2214615A1 (en) | 1996-09-09 | 1997-09-03 | Machine dishwashing composition containing amphoteric polymers |
Country Status (5)
Country | Link |
---|---|
EP (1) | EP0835925A3 (en) |
BR (1) | BR9704666A (en) |
CA (1) | CA2214615A1 (en) |
TR (1) | TR199700924A2 (en) |
ZA (1) | ZA977875B (en) |
Cited By (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US20210324304A1 (en) * | 2018-10-22 | 2021-10-21 | Dow Global Technologies Llc | Automatic dishwashing composition with dispersant polymer |
Families Citing this family (17)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
EP0998548B1 (en) * | 1997-07-23 | 2004-09-29 | Unilever N.V. | Automatic dishwashing compositions containing water soluble cationic or amphoteric polymers |
WO1999058633A1 (en) * | 1998-05-11 | 1999-11-18 | Unilever Plc | Machine dishwashing compositions and rinse aid compositions |
DE19824356A1 (en) * | 1998-05-30 | 1999-12-02 | Henkel Ecolab Gmbh & Co Ohg | Cleaning solution for crockery, especially glassware, which does not leave a smell associated with the washing process |
FR2796391B1 (en) * | 1999-07-15 | 2003-09-19 | Rhodia Chimie Sa | CLEANING COMPOSITION FOR HARD SURFACES |
FR2796390B1 (en) | 1999-07-15 | 2001-10-26 | Rhodia Chimie Sa | USING AN AMPHOTERIC POLYMER TO TREAT A HARD SURFACE |
US6924260B2 (en) | 1999-07-15 | 2005-08-02 | Rhodia Chimie | Method of reducing and preventing soil redeposition in an automatic dishwashing machine |
US6326343B1 (en) * | 2000-09-08 | 2001-12-04 | Unilever Home & Personal Care Usa, Division Of Conopco, Inc. | Three-in-one composition for dishwashing machines |
DE10342631B4 (en) | 2003-09-15 | 2006-04-13 | Henkel Kgaa | Machine dishwashing detergent with special polymer mixture |
DE10342632A1 (en) | 2003-09-15 | 2005-04-07 | Henkel Kgaa | Machine dishwashing detergents with special polymers |
DE102004005344A1 (en) * | 2004-02-04 | 2005-09-01 | Henkel Kgaa | Machine dishwashing detergent #### |
GT200600375A (en) | 2005-08-17 | 2007-03-14 | ACID CLEANING COMPOSITION CONTAINING A HYDROPHILIZATION POLYMER | |
BRPI1009893A2 (en) | 2009-03-20 | 2016-03-15 | Ciba Geigy Corp | hard surface cleaner or hard surface treatment, and method for reducing the drying time, preferably on vertical surfaces, of a liquid cleaning composition. |
DE102009029636A1 (en) * | 2009-09-21 | 2011-03-24 | Henkel Ag & Co. Kgaa | Machine dishwashing detergent |
JP5837362B2 (en) * | 2011-08-24 | 2015-12-24 | 花王株式会社 | Solid composition for automatic dishwasher |
US8740993B2 (en) | 2012-03-23 | 2014-06-03 | Ecolab Usa Inc. | Method for reduced encrustation of textiles using a polymer comprising maleic acid, vinyl acetate, and alkyl acrylate |
US8623151B2 (en) | 2012-03-23 | 2014-01-07 | Ecolab Usa Inc. | Terpolymer containing maleic acid, vinyl acetate, and alkyl acrylate monomers for aluminum protection |
EP3167037A1 (en) * | 2014-07-08 | 2017-05-17 | Novozymes A/S | Organic film removal from plastic objects |
Family Cites Families (5)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JPS5813700A (en) * | 1981-07-17 | 1983-01-26 | 花王株式会社 | Detergent composition |
DE3614336A1 (en) * | 1986-04-28 | 1987-10-29 | Henkel Kgaa | LIQUID, AQUEOUS CLEANER FOR HARD SURFACES |
DE69330230T2 (en) * | 1992-09-25 | 2002-02-28 | Procter & Gamble | USE OF A LIME SOAP DISPERSER AND LIPASE-BASED DETERGENT COMPOSITION |
AU7402194A (en) * | 1993-08-10 | 1995-02-28 | Procter & Gamble Company, The | Manual dishwashing composition comprising lipase enzymes and lime soap dispersant |
EP0698659A1 (en) * | 1994-08-23 | 1996-02-28 | The Procter & Gamble Company | Detergent compositions comprising lipolytic enzymes |
-
1997
- 1997-08-26 EP EP97202617A patent/EP0835925A3/en not_active Withdrawn
- 1997-09-02 ZA ZA977875A patent/ZA977875B/en unknown
- 1997-09-03 CA CA002214615A patent/CA2214615A1/en not_active Abandoned
- 1997-09-09 BR BR9704666A patent/BR9704666A/en not_active Application Discontinuation
- 1997-09-09 TR TR97/00924A patent/TR199700924A2/en unknown
Cited By (2)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US20210324304A1 (en) * | 2018-10-22 | 2021-10-21 | Dow Global Technologies Llc | Automatic dishwashing composition with dispersant polymer |
US11920110B2 (en) * | 2018-10-22 | 2024-03-05 | Dow Global Technologies Llc | Automatic dishwashing composition with dispersant polymer |
Also Published As
Publication number | Publication date |
---|---|
EP0835925A3 (en) | 1999-01-27 |
EP0835925A2 (en) | 1998-04-15 |
ZA977875B (en) | 1999-03-02 |
TR199700924A2 (en) | 1998-03-21 |
BR9704666A (en) | 1999-07-20 |
Similar Documents
Publication | Publication Date | Title |
---|---|---|
DE69826671T2 (en) | MACHINE DISHWASHER CONTAINING WATER-SOLUBLE CATIONIC OR AMPHOTERE POLYMERS | |
US6281180B1 (en) | Automatic dishwashing compositions containing water soluble cationic or amphoteric polymers | |
CA2214615A1 (en) | Machine dishwashing composition containing amphoteric polymers | |
EP0139329B1 (en) | Dishwashing compositions | |
EP0874894B1 (en) | A peracid based dishwashing detergent composition | |
US6703358B1 (en) | Cleaning composition for hard surfaces | |
JP4014632B2 (en) | Detergent composition | |
EP0636170A1 (en) | Thixotropic liquid automatic dishwashing composition with enzyme. | |
JPH09511004A (en) | Detergent composition comprising a lipoxidase enzyme | |
US5624892A (en) | Process for incorporating aluminum salts into an automatic dishwashing composition | |
AU727942B2 (en) | Anti-foam system for automatic dishwashing compositions | |
US5698506A (en) | Automatic dishwashing compositions containing aluminum salts | |
MXPA97003153A (en) | Cleaning compositions that understand xilana | |
GB2285051A (en) | Rinse aid composition | |
US5783539A (en) | Process for incorporating aluminum salts into an automatic dishwashing composition | |
JP2002508026A (en) | Dishwashing composition comprising phospholipase and amylase | |
JPH09510742A (en) | Detergent composition | |
AU729402B2 (en) | An anti-foam system based on hydrocarbon polymers and hydrophobic particulate solids | |
US5731277A (en) | Automatic dishwashing compositions containing aluminum tetrahydroxide | |
AU9258498A (en) | Machine dishwashing compositions and rinse aid compositions | |
EP0883670B1 (en) | Machine dishwashing gel compositions | |
CA2236881C (en) | A peracid based dishwashing detergent composition | |
JPH09510743A (en) | Detergent composition |
Legal Events
Date | Code | Title | Description |
---|---|---|---|
EEER | Examination request | ||
FZDE | Discontinued |