AU2018245984B2 - Dispersant system for automatic dish washing formulations - Google Patents
Dispersant system for automatic dish washing formulations Download PDFInfo
- Publication number
- AU2018245984B2 AU2018245984B2 AU2018245984A AU2018245984A AU2018245984B2 AU 2018245984 B2 AU2018245984 B2 AU 2018245984B2 AU 2018245984 A AU2018245984 A AU 2018245984A AU 2018245984 A AU2018245984 A AU 2018245984A AU 2018245984 B2 AU2018245984 B2 AU 2018245984B2
- Authority
- AU
- Australia
- Prior art keywords
- automatic dishwashing
- dishwashing composition
- acrylic acid
- present
- surfactant
- 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.)
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- 239000000203 mixture Substances 0.000 title claims abstract description 155
- 238000004851 dishwashing Methods 0.000 title claims abstract description 121
- 239000002270 dispersing agent Substances 0.000 title claims abstract description 38
- 238000009472 formulation Methods 0.000 title description 8
- NIXOWILDQLNWCW-UHFFFAOYSA-N 2-Propenoic acid Natural products OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 claims abstract description 43
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 claims abstract description 37
- 239000004094 surface-active agent Substances 0.000 claims abstract description 32
- 229920001577 copolymer Polymers 0.000 claims abstract description 26
- 229920002959 polymer blend Polymers 0.000 claims abstract description 25
- 239000000178 monomer Substances 0.000 claims abstract description 21
- 229920001519 homopolymer Polymers 0.000 claims abstract description 20
- 239000000654 additive Substances 0.000 claims abstract description 10
- 230000000996 additive effect Effects 0.000 claims abstract description 10
- 125000000217 alkyl group Chemical group 0.000 claims description 20
- 229920006395 saturated elastomer Polymers 0.000 claims description 19
- 238000000034 method Methods 0.000 claims description 12
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 claims description 11
- 150000001298 alcohols Chemical class 0.000 claims description 11
- KXDHJXZQYSOELW-UHFFFAOYSA-N Carbamic acid Chemical compound NC(O)=O KXDHJXZQYSOELW-UHFFFAOYSA-N 0.000 claims description 9
- BPQQTUXANYXVAA-UHFFFAOYSA-N Orthosilicate Chemical compound [O-][Si]([O-])([O-])[O-] BPQQTUXANYXVAA-UHFFFAOYSA-N 0.000 claims description 9
- 239000007844 bleaching agent Substances 0.000 claims description 9
- KRKNYBCHXYNGOX-UHFFFAOYSA-K Citrate Chemical compound [O-]C(=O)CC(O)(CC([O-])=O)C([O-])=O KRKNYBCHXYNGOX-UHFFFAOYSA-K 0.000 claims description 8
- 239000013522 chelant Substances 0.000 claims description 8
- 229910019142 PO4 Inorganic materials 0.000 claims description 7
- 125000003055 glycidyl group Chemical group C(C1CO1)* 0.000 claims description 7
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 claims description 7
- 239000010452 phosphate Substances 0.000 claims description 7
- 238000004140 cleaning Methods 0.000 claims description 4
- 102000004190 Enzymes Human genes 0.000 claims description 3
- 108090000790 Enzymes Proteins 0.000 claims description 3
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 claims description 3
- 239000003054 catalyst Substances 0.000 claims description 3
- 239000011574 phosphorus Substances 0.000 claims description 3
- 229910052698 phosphorus Inorganic materials 0.000 claims description 3
- 239000012190 activator Substances 0.000 claims description 2
- ABLZXFCXXLZCGV-UHFFFAOYSA-N Phosphorous acid Chemical class OP(O)=O ABLZXFCXXLZCGV-UHFFFAOYSA-N 0.000 claims 1
- MWKFXSUHUHTGQN-UHFFFAOYSA-N decan-1-ol Chemical compound CCCCCCCCCCO MWKFXSUHUHTGQN-UHFFFAOYSA-N 0.000 description 24
- IJGRMHOSHXDMSA-UHFFFAOYSA-N nitrogen Substances N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 21
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 18
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 17
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 15
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 15
- WQDUMFSSJAZKTM-UHFFFAOYSA-N Sodium methoxide Chemical compound [Na+].[O-]C WQDUMFSSJAZKTM-UHFFFAOYSA-N 0.000 description 14
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical class 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 13
- 238000006243 chemical reaction Methods 0.000 description 13
- 229910052757 nitrogen Inorganic materials 0.000 description 13
- LQZZUXJYWNFBMV-UHFFFAOYSA-N dodecan-1-ol Chemical compound CCCCCCCCCCCCO LQZZUXJYWNFBMV-UHFFFAOYSA-N 0.000 description 12
- IAYPIBMASNFSPL-UHFFFAOYSA-N Ethylene oxide Chemical group C1CO1 IAYPIBMASNFSPL-UHFFFAOYSA-N 0.000 description 11
- 238000005227 gel permeation chromatography Methods 0.000 description 11
- 229920000642 polymer Polymers 0.000 description 11
- 239000011734 sodium Substances 0.000 description 11
- 238000012360 testing method Methods 0.000 description 11
- -1 disilicate Chemical class 0.000 description 10
- 150000003839 salts Chemical class 0.000 description 10
- 229910052708 sodium Inorganic materials 0.000 description 10
- 238000001644 13C nuclear magnetic resonance spectroscopy Methods 0.000 description 8
- BBBUAWSVILPJLL-UHFFFAOYSA-N 2-(2-ethylhexoxymethyl)oxirane Chemical compound CCCCC(CC)COCC1CO1 BBBUAWSVILPJLL-UHFFFAOYSA-N 0.000 description 8
- XMVBHZBLHNOQON-UHFFFAOYSA-N 2-butyl-1-octanol Chemical compound CCCCCCC(CO)CCCC XMVBHZBLHNOQON-UHFFFAOYSA-N 0.000 description 8
- 230000000052 comparative effect Effects 0.000 description 8
- 239000011521 glass Substances 0.000 description 8
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 7
- 239000002736 nonionic surfactant Substances 0.000 description 7
- 238000010926 purge Methods 0.000 description 7
- 238000003756 stirring Methods 0.000 description 7
- 239000000126 substance Substances 0.000 description 7
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical class [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 description 6
- 235000013305 food Nutrition 0.000 description 6
- 229910052700 potassium Inorganic materials 0.000 description 6
- 239000011591 potassium Chemical class 0.000 description 6
- 239000002689 soil Substances 0.000 description 6
- CIEZZGWIJBXOTE-UHFFFAOYSA-N 2-[bis(carboxymethyl)amino]propanoic acid Chemical compound OC(=O)C(C)N(CC(O)=O)CC(O)=O CIEZZGWIJBXOTE-UHFFFAOYSA-N 0.000 description 5
- 238000004458 analytical method Methods 0.000 description 5
- 239000007795 chemical reaction product Substances 0.000 description 5
- 150000001875 compounds Chemical class 0.000 description 5
- 238000010438 heat treatment Methods 0.000 description 5
- 150000002829 nitrogen Chemical class 0.000 description 5
- 239000000843 powder Substances 0.000 description 5
- 239000011541 reaction mixture Substances 0.000 description 5
- 239000002904 solvent Substances 0.000 description 5
- YIWUKEYIRIRTPP-UHFFFAOYSA-N 2-ethylhexan-1-ol Chemical compound CCCCC(CC)CO YIWUKEYIRIRTPP-UHFFFAOYSA-N 0.000 description 4
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 4
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 4
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 4
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical class [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 4
- CERQOIWHTDAKMF-UHFFFAOYSA-N Methacrylic acid Chemical compound CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 description 4
- WPYMKLBDIGXBTP-UHFFFAOYSA-N benzoic acid Chemical compound OC(=O)C1=CC=CC=C1 WPYMKLBDIGXBTP-UHFFFAOYSA-N 0.000 description 4
- 229910052799 carbon Inorganic materials 0.000 description 4
- 150000004649 carbonic acid derivatives Chemical class 0.000 description 4
- 239000011777 magnesium Substances 0.000 description 4
- 239000003264 margarine Substances 0.000 description 4
- 235000013310 margarine Nutrition 0.000 description 4
- 150000004760 silicates Chemical class 0.000 description 4
- 229910000029 sodium carbonate Inorganic materials 0.000 description 4
- HLZKNKRTKFSKGZ-UHFFFAOYSA-N tetradecan-1-ol Chemical compound CCCCCCCCCCCCCCO HLZKNKRTKFSKGZ-UHFFFAOYSA-N 0.000 description 4
- 239000005968 1-Decanol Substances 0.000 description 3
- BVKZGUZCCUSVTD-UHFFFAOYSA-M Bicarbonate Chemical class OC([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-M 0.000 description 3
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 3
- 230000015572 biosynthetic process Effects 0.000 description 3
- 239000011575 calcium Substances 0.000 description 3
- 239000011203 carbon fibre reinforced carbon Substances 0.000 description 3
- 150000001860 citric acid derivatives Chemical class 0.000 description 3
- 239000003599 detergent Substances 0.000 description 3
- VTIIJXUACCWYHX-UHFFFAOYSA-L disodium;carboxylatooxy carbonate Chemical compound [Na+].[Na+].[O-]C(=O)OOC([O-])=O VTIIJXUACCWYHX-UHFFFAOYSA-L 0.000 description 3
- 238000001035 drying Methods 0.000 description 3
- 239000000945 filler Substances 0.000 description 3
- 239000006260 foam Substances 0.000 description 3
- 239000007788 liquid Substances 0.000 description 3
- 229910052744 lithium Chemical class 0.000 description 3
- 239000000463 material Substances 0.000 description 3
- 229920001223 polyethylene glycol Polymers 0.000 description 3
- 239000000047 product Substances 0.000 description 3
- 229940045872 sodium percarbonate Drugs 0.000 description 3
- 238000003786 synthesis reaction Methods 0.000 description 3
- NJWSNNWLBMSXQR-UHFFFAOYSA-N 2-hexyloxirane Chemical compound CCCCCCC1CO1 NJWSNNWLBMSXQR-UHFFFAOYSA-N 0.000 description 2
- CIWBSHSKHKDKBQ-JLAZNSOCSA-N Ascorbic acid Chemical compound OC[C@H](O)[C@H]1OC(=O)C(O)=C1O CIWBSHSKHKDKBQ-JLAZNSOCSA-N 0.000 description 2
- 239000005711 Benzoic acid Substances 0.000 description 2
- KZMGYPLQYOPHEL-UHFFFAOYSA-N Boron trifluoride etherate Chemical compound FB(F)F.CCOCC KZMGYPLQYOPHEL-UHFFFAOYSA-N 0.000 description 2
- 241000219198 Brassica Species 0.000 description 2
- 235000003351 Brassica cretica Nutrition 0.000 description 2
- 235000003343 Brassica rupestris Nutrition 0.000 description 2
- 125000006539 C12 alkyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 2
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 description 2
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 description 2
- 239000002202 Polyethylene glycol Substances 0.000 description 2
- 229920002125 Sokalan® Polymers 0.000 description 2
- 238000001994 activation Methods 0.000 description 2
- 230000004913 activation Effects 0.000 description 2
- 239000003513 alkali Substances 0.000 description 2
- 229910052783 alkali metal Inorganic materials 0.000 description 2
- 239000003242 anti bacterial agent Substances 0.000 description 2
- 235000010233 benzoic acid Nutrition 0.000 description 2
- QKSKPIVNLNLAAV-UHFFFAOYSA-N bis(2-chloroethyl) sulfide Chemical compound ClCCSCCCl QKSKPIVNLNLAAV-UHFFFAOYSA-N 0.000 description 2
- 239000003153 chemical reaction reagent Substances 0.000 description 2
- 238000001816 cooling Methods 0.000 description 2
- 125000002704 decyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 2
- GYZLOYUZLJXAJU-UHFFFAOYSA-N diglycidyl ether Chemical class C1OC1COCC1CO1 GYZLOYUZLJXAJU-UHFFFAOYSA-N 0.000 description 2
- 235000013345 egg yolk Nutrition 0.000 description 2
- 210000002969 egg yolk Anatomy 0.000 description 2
- 229940088598 enzyme Drugs 0.000 description 2
- 239000003205 fragrance Substances 0.000 description 2
- 238000005286 illumination Methods 0.000 description 2
- 235000008960 ketchup Nutrition 0.000 description 2
- WMFOQBRAJBCJND-UHFFFAOYSA-M lithium hydroxide Inorganic materials [Li+].[OH-] WMFOQBRAJBCJND-UHFFFAOYSA-M 0.000 description 2
- 229910052749 magnesium Inorganic materials 0.000 description 2
- 235000013336 milk Nutrition 0.000 description 2
- 239000008267 milk Substances 0.000 description 2
- 210000004080 milk Anatomy 0.000 description 2
- 235000010460 mustard Nutrition 0.000 description 2
- 239000004584 polyacrylic acid Substances 0.000 description 2
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Chemical compound [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 description 2
- 229920001592 potato starch Polymers 0.000 description 2
- 239000002243 precursor Substances 0.000 description 2
- 238000002360 preparation method Methods 0.000 description 2
- 238000010526 radical polymerization reaction Methods 0.000 description 2
- 238000005070 sampling Methods 0.000 description 2
- 229940071207 sesquicarbonate Drugs 0.000 description 2
- HEMHJVSKTPXQMS-UHFFFAOYSA-M sodium hydroxide Inorganic materials [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 2
- FWFUWXVFYKCSQA-UHFFFAOYSA-M sodium;2-methyl-2-(prop-2-enoylamino)propane-1-sulfonate Chemical group [Na+].[O-]S(=O)(=O)CC(C)(C)NC(=O)C=C FWFUWXVFYKCSQA-UHFFFAOYSA-M 0.000 description 2
- 239000007787 solid Substances 0.000 description 2
- 229910001220 stainless steel Inorganic materials 0.000 description 2
- 239000010935 stainless steel Substances 0.000 description 2
- FRPJTGXMTIIFIT-UHFFFAOYSA-N tetraacetylethylenediamine Chemical compound CC(=O)C(N)(C(C)=O)C(N)(C(C)=O)C(C)=O FRPJTGXMTIIFIT-UHFFFAOYSA-N 0.000 description 2
- 238000005406 washing Methods 0.000 description 2
- VKZRWSNIWNFCIQ-WDSKDSINSA-N (2s)-2-[2-[[(1s)-1,2-dicarboxyethyl]amino]ethylamino]butanedioic acid Chemical compound OC(=O)C[C@@H](C(O)=O)NCCN[C@H](C(O)=O)CC(O)=O VKZRWSNIWNFCIQ-WDSKDSINSA-N 0.000 description 1
- DCCWEYXHEXDZQW-BYPYZUCNSA-N (2s)-2-[bis(carboxymethyl)amino]butanedioic acid Chemical compound OC(=O)C[C@@H](C(O)=O)N(CC(O)=O)CC(O)=O DCCWEYXHEXDZQW-BYPYZUCNSA-N 0.000 description 1
- DNIAPMSPPWPWGF-GSVOUGTGSA-N (R)-(-)-Propylene glycol Chemical compound C[C@@H](O)CO DNIAPMSPPWPWGF-GSVOUGTGSA-N 0.000 description 1
- ITWBWJFEJCHKSN-UHFFFAOYSA-N 1,4,7-triazonane Chemical compound C1CNCCNCCN1 ITWBWJFEJCHKSN-UHFFFAOYSA-N 0.000 description 1
- PQHYOGIRXOKOEJ-UHFFFAOYSA-N 2-(1,2-dicarboxyethylamino)butanedioic acid Chemical compound OC(=O)CC(C(O)=O)NC(C(O)=O)CC(O)=O PQHYOGIRXOKOEJ-UHFFFAOYSA-N 0.000 description 1
- XHZPRMZZQOIPDS-UHFFFAOYSA-N 2-Methyl-2-[(1-oxo-2-propenyl)amino]-1-propanesulfonic acid Chemical compound OS(=O)(=O)CC(C)(C)NC(=O)C=C XHZPRMZZQOIPDS-UHFFFAOYSA-N 0.000 description 1
- HSXUNHYXJWDLDK-UHFFFAOYSA-N 2-hydroxypropane-1-sulfonic acid Chemical compound CC(O)CS(O)(=O)=O HSXUNHYXJWDLDK-UHFFFAOYSA-N 0.000 description 1
- VSSGDAWBDKMCMI-UHFFFAOYSA-N 2-methyl-2-(2-methylprop-2-enoylamino)propane-1-sulfonic acid Chemical compound CC(=C)C(=O)NC(C)(C)CS(O)(=O)=O VSSGDAWBDKMCMI-UHFFFAOYSA-N 0.000 description 1
- RFDGKSUFGFLBOX-UHFFFAOYSA-N 2-methyloxirane;oxirane;oxolane Chemical compound C1CO1.CC1CO1.C1CCOC1 RFDGKSUFGFLBOX-UHFFFAOYSA-N 0.000 description 1
- 229910000619 316 stainless steel Inorganic materials 0.000 description 1
- MAGFQRLKWCCTQJ-UHFFFAOYSA-N 4-ethenylbenzenesulfonic acid Chemical compound OS(=O)(=O)C1=CC=C(C=C)C=C1 MAGFQRLKWCCTQJ-UHFFFAOYSA-N 0.000 description 1
- IKHGUXGNUITLKF-UHFFFAOYSA-N Acetaldehyde Chemical compound CC=O IKHGUXGNUITLKF-UHFFFAOYSA-N 0.000 description 1
- 239000004382 Amylase Substances 0.000 description 1
- 102000013142 Amylases Human genes 0.000 description 1
- 108010065511 Amylases Proteins 0.000 description 1
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 description 1
- 108010059892 Cellulase Proteins 0.000 description 1
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 1
- 229910021580 Cobalt(II) chloride Inorganic materials 0.000 description 1
- KCXVZYZYPLLWCC-UHFFFAOYSA-N EDTA Chemical compound OC(=O)CN(CC(O)=O)CCN(CC(O)=O)CC(O)=O KCXVZYZYPLLWCC-UHFFFAOYSA-N 0.000 description 1
- DBVJJBKOTRCVKF-UHFFFAOYSA-N Etidronic acid Chemical compound OP(=O)(O)C(O)(C)P(O)(O)=O DBVJJBKOTRCVKF-UHFFFAOYSA-N 0.000 description 1
- 102000004882 Lipase Human genes 0.000 description 1
- 239000004367 Lipase Substances 0.000 description 1
- 108090001060 Lipase Proteins 0.000 description 1
- 238000005481 NMR spectroscopy Methods 0.000 description 1
- 108091005804 Peptidases Proteins 0.000 description 1
- 239000004721 Polyphenylene oxide Substances 0.000 description 1
- GOOHAUXETOMSMM-UHFFFAOYSA-N Propylene oxide Chemical compound CC1CO1 GOOHAUXETOMSMM-UHFFFAOYSA-N 0.000 description 1
- 239000004365 Protease Substances 0.000 description 1
- 102100037486 Reverse transcriptase/ribonuclease H Human genes 0.000 description 1
- UIIMBOGNXHQVGW-DEQYMQKBSA-M Sodium bicarbonate-14C Chemical compound [Na+].O[14C]([O-])=O UIIMBOGNXHQVGW-DEQYMQKBSA-M 0.000 description 1
- 239000013543 active substance Substances 0.000 description 1
- 230000001476 alcoholic effect Effects 0.000 description 1
- 229910000288 alkali metal carbonate Inorganic materials 0.000 description 1
- 150000008041 alkali metal carbonates Chemical class 0.000 description 1
- 150000008044 alkali metal hydroxides Chemical class 0.000 description 1
- 229910052910 alkali metal silicate Inorganic materials 0.000 description 1
- 150000001340 alkali metals Chemical class 0.000 description 1
- 150000001412 amines Chemical class 0.000 description 1
- 150000003863 ammonium salts Chemical class 0.000 description 1
- 235000019418 amylase Nutrition 0.000 description 1
- 235000010323 ascorbic acid Nutrition 0.000 description 1
- 229960005070 ascorbic acid Drugs 0.000 description 1
- 239000011668 ascorbic acid Substances 0.000 description 1
- ZETCGWYACBNPIH-UHFFFAOYSA-N azane;sulfurous acid Chemical class N.OS(O)=O ZETCGWYACBNPIH-UHFFFAOYSA-N 0.000 description 1
- 239000002585 base Substances 0.000 description 1
- 229920001400 block copolymer Polymers 0.000 description 1
- 230000005587 bubbling Effects 0.000 description 1
- YIKPWSKEXRZQIY-UHFFFAOYSA-N butanedioic acid;ethane-1,2-diamine Chemical compound NCCN.OC(=O)CCC(O)=O.OC(=O)CCC(O)=O YIKPWSKEXRZQIY-UHFFFAOYSA-N 0.000 description 1
- 229910052791 calcium Inorganic materials 0.000 description 1
- 229910000019 calcium carbonate Inorganic materials 0.000 description 1
- 238000011088 calibration curve Methods 0.000 description 1
- 125000004432 carbon atom Chemical group C* 0.000 description 1
- 150000005323 carbonate salts Chemical class 0.000 description 1
- 229940106157 cellulase Drugs 0.000 description 1
- 239000012986 chain transfer agent Substances 0.000 description 1
- 238000012512 characterization method Methods 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- GVPFVAHMJGGAJG-UHFFFAOYSA-L cobalt dichloride Chemical compound [Cl-].[Cl-].[Co+2] GVPFVAHMJGGAJG-UHFFFAOYSA-L 0.000 description 1
- 239000003086 colorant Substances 0.000 description 1
- 238000010411 cooking Methods 0.000 description 1
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- 238000000354 decomposition reaction Methods 0.000 description 1
- 239000000975 dye Substances 0.000 description 1
- 239000000839 emulsion Substances 0.000 description 1
- 238000007046 ethoxylation reaction Methods 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
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- 150000002191 fatty alcohols Chemical class 0.000 description 1
- 238000010528 free radical solution polymerization reaction Methods 0.000 description 1
- 235000011187 glycerol Nutrition 0.000 description 1
- 239000008187 granular material Substances 0.000 description 1
- 239000008233 hard water Substances 0.000 description 1
- PMYUVOOOQDGQNW-UHFFFAOYSA-N hexasodium;trioxido(trioxidosilyloxy)silane Chemical compound [Na+].[Na+].[Na+].[Na+].[Na+].[Na+].[O-][Si]([O-])([O-])O[Si]([O-])([O-])[O-] PMYUVOOOQDGQNW-UHFFFAOYSA-N 0.000 description 1
- BAUYGSIQEAFULO-UHFFFAOYSA-L iron(2+) sulfate (anhydrous) Chemical compound [Fe+2].[O-]S([O-])(=O)=O BAUYGSIQEAFULO-UHFFFAOYSA-L 0.000 description 1
- 229910000359 iron(II) sulfate Inorganic materials 0.000 description 1
- 239000011968 lewis acid catalyst Substances 0.000 description 1
- 235000019421 lipase Nutrition 0.000 description 1
- UOGMEBQRZBEZQT-UHFFFAOYSA-L manganese(2+);diacetate Chemical compound [Mn+2].CC([O-])=O.CC([O-])=O UOGMEBQRZBEZQT-UHFFFAOYSA-L 0.000 description 1
- 229910021645 metal ion Inorganic materials 0.000 description 1
- 125000005395 methacrylic acid group Chemical group 0.000 description 1
- DNIAPMSPPWPWGF-UHFFFAOYSA-N monopropylene glycol Natural products CC(O)CO DNIAPMSPPWPWGF-UHFFFAOYSA-N 0.000 description 1
- 238000005580 one pot reaction Methods 0.000 description 1
- 150000004967 organic peroxy acids Chemical class 0.000 description 1
- 150000002976 peresters Chemical class 0.000 description 1
- 238000011056 performance test Methods 0.000 description 1
- JRKICGRDRMAZLK-UHFFFAOYSA-L persulfate group Chemical group S(=O)(=O)([O-])OOS(=O)(=O)[O-] JRKICGRDRMAZLK-UHFFFAOYSA-L 0.000 description 1
- UEZVMMHDMIWARA-UHFFFAOYSA-M phosphonate Chemical compound [O-]P(=O)=O UEZVMMHDMIWARA-UHFFFAOYSA-M 0.000 description 1
- 229920000570 polyether Polymers 0.000 description 1
- 238000006116 polymerization reaction Methods 0.000 description 1
- 229910000027 potassium carbonate Inorganic materials 0.000 description 1
- 159000000001 potassium salts Chemical class 0.000 description 1
- OTYBMLCTZGSZBG-UHFFFAOYSA-L potassium sulfate Chemical compound [K+].[K+].[O-]S([O-])(=O)=O OTYBMLCTZGSZBG-UHFFFAOYSA-L 0.000 description 1
- 229910052939 potassium sulfate Inorganic materials 0.000 description 1
- 235000011151 potassium sulphates Nutrition 0.000 description 1
- 238000004886 process control Methods 0.000 description 1
- 235000013772 propylene glycol Nutrition 0.000 description 1
- 235000019419 proteases Nutrition 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
- 239000000376 reactant Substances 0.000 description 1
- 238000001448 refractive index detection Methods 0.000 description 1
- 238000007789 sealing Methods 0.000 description 1
- 238000001542 size-exclusion chromatography Methods 0.000 description 1
- 239000002002 slurry Substances 0.000 description 1
- 239000001509 sodium citrate Substances 0.000 description 1
- NLJMYIDDQXHKNR-UHFFFAOYSA-K sodium citrate Chemical compound O.O.[Na+].[Na+].[Na+].[O-]C(=O)CC(O)(CC([O-])=O)C([O-])=O NLJMYIDDQXHKNR-UHFFFAOYSA-K 0.000 description 1
- HRZFUMHJMZEROT-UHFFFAOYSA-L sodium disulfite Chemical compound [Na+].[Na+].[O-]S(=O)S([O-])(=O)=O HRZFUMHJMZEROT-UHFFFAOYSA-L 0.000 description 1
- 229940001584 sodium metabisulfite Drugs 0.000 description 1
- 235000010262 sodium metabisulphite Nutrition 0.000 description 1
- 229960001922 sodium perborate Drugs 0.000 description 1
- 229910052938 sodium sulfate Inorganic materials 0.000 description 1
- 235000011152 sodium sulphate Nutrition 0.000 description 1
- MWNQXXOSWHCCOZ-UHFFFAOYSA-L sodium;oxido carbonate Chemical class [Na+].[O-]OC([O-])=O MWNQXXOSWHCCOZ-UHFFFAOYSA-L 0.000 description 1
- YKLJGMBLPUQQOI-UHFFFAOYSA-M sodium;oxidooxy(oxo)borane Chemical compound [Na+].[O-]OB=O YKLJGMBLPUQQOI-UHFFFAOYSA-M 0.000 description 1
- 238000001228 spectrum Methods 0.000 description 1
- 238000007725 thermal activation Methods 0.000 description 1
- 238000004448 titration Methods 0.000 description 1
- 238000012546 transfer Methods 0.000 description 1
- NLVXSWCKKBEXTG-UHFFFAOYSA-N vinylsulfonic acid Chemical compound OS(=O)(=O)C=C NLVXSWCKKBEXTG-UHFFFAOYSA-N 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
- C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
- C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
- C11D3/16—Organic compounds
- C11D3/37—Polymers
- C11D3/3746—Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds
- C11D3/378—(Co)polymerised monomers containing sulfur, e.g. sulfonate
-
- C—CHEMISTRY; METALLURGY
- C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
- C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
- C11D1/00—Detergent compositions based essentially on surface-active compounds; Use of these compounds as a detergent
- C11D1/66—Non-ionic compounds
- C11D1/72—Ethers of polyoxyalkylene glycols
- C11D1/721—End blocked ethers
-
- C—CHEMISTRY; METALLURGY
- C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
- C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
- C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
- C11D3/16—Organic compounds
- C11D3/37—Polymers
- C11D3/3746—Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds
- C11D3/3757—(Co)polymerised carboxylic acids, -anhydrides, -esters in solid and liquid compositions
Abstract
An automatic dishwashing composition is provided, comprising: a dispersant polymer blend, comprising an acrylic acid homopolymer; and a copolymer of acrylic acid and a sulfonated monomer; wherein the dispersant polymer blend has a blend ratio of the acrylic acid homopolymer to the copolymer of 3:1 to 1:3; a surfactant; a builder; and optionally, an additive.
Description
DISPERSANT SYSTEM FOR AUTOMATIC DISH WASHING FORMULATIONS
[0001] The present invention relates to dispersant systems for use in automatic dish washing formulations. In particular, the present invention relates to automatic dishwashing compositions incorporating such dispersant systems having reduced spotting and/or filming on dishware.
[0002] Automatic dishwashing compositions are generally recognized as a class of detergent compositions distinct from those used for fabric washing or water treatment. Automatic dishwashing compositions are expected by users to produce a spotless and film- free appearance on washed articles after a complete cleaning cycle.
[0003] A family of hydroxypolyethers as low foam surfactants are disclosed by Welch et al. in U.S. Patent No. 5,294,365 for use as rinse aids in phosphate containing machine dishwashing detergent formulations. Welch et al. disclose a compound of the formula
CH3 OH
R1 [0(CH2CH20)„ (CH2CHO) JCH2CHCH2OR2 wherein R1 and R2 are the same or different and are a linear or branched Ci-i8 alkyl radical; n is a number from 15 to 45; and m is a number of from 0 to 3.
[0004] Notwithstanding phosphate-free compositions are increasingly desirable.
Phosphate-free compositions rely on non-phosphate builders, such as salts of citrate, carbonate, silicate, disilicate, bicarbonate, amino carboxylates and others to sequester calcium and magnesium from hard water and block them from leaving an insoluble visible deposit on the dishware following drying. Phosphate-free compositions, however, have a greater tendency to leave spots on glassware and other surfaces.
[0005] Compositions that exhibit improved properties in automatic dishwashing and that are phosphate-free would be an advance in the industry. Accordingly, there remains a need for new surfactants having anti-spotting properties. In particular, there remains a need for new surfactants having anti-spotting properties that facilitate automatic dishwashing formulations that are both phosphate-free and anti-spotting.
[0006] The present invention provides an automatic dishwashing composition, comprising: 0.5 to 15 wt% of a dispersant polymer blend, comprising: an acrylic acid homopolymer; and a copolymer of acrylic acid and a sulfonated monomer; wherein the dispersant polymer blend has a blend ratio of the acrylic acid homopolymer to the copolymer of 3: 1 to 1:3, based on weight; 0.5 to 15 wt% of a surfactant; 1 to 75 wt% of a builder; 0 to 75 wt% of an additive.
[0007] The present invention provides an automatic dishwashing composition, comprising: 0.5 to 15 wt% of a dispersant polymer blend, comprising: an acrylic acid homopolymer; and a copolymer of acrylic acid and a sulfonated monomer; wherein the dispersant polymer blend has a blend ratio of the acrylic acid homopolymer to the copolymer of 3:1 to 1:3, based on weight; 0.5 to 15 wt% of a surfactant; 1 to 75 wt% of a builder; 0 to 75 wt% of an additive; wherein the automatic dishwashing composition contains less than 0.1 wt% phosphate; wherein the automatic dishwashing composition contains less than 0.1 wt% amino carboxylate chelant; and wherein the surfactant is a glycidyl ether-capped ethoxylated alcohol of formula I:
wherein Ri is a linear, saturated Cs-24 alkyl group, R2 is a linear or branched saturated C6-20 alkyl group, m has an average value of 10 to 50, and n has an average value of > 1 to 2.
[0008] The present invention also provides a method of cleaning an article in an automatic dishwashing machine, the method comprising: applying to the article the automatic dishwashing composition of the present invention.
DETAILED DESCRIPTION
[0009] When incorporated in automatic dishwashing compositions (particularly phosphate- free automatic dishwashing compositions), the dispersant formulations of the present invention comprise a blend of an acrylic acid homopolymer and a copolymer of acrylic acid and a sulfonated monomer (preferably, wherein the automatic dishwashing compositions further comprise a surfactant of the present invention based on the reaction of certain glycidyl ethers with a group of ethoxylated alcohols), which automatic dishwashing compositions dramatically improve the antispotting and/or scale (filming) performance of the automatic dishwashing composition.
[0010] Unless otherwise indicated, ratios, percentages, parts, and the like are by weight. Weight percentages (or wt%) in the composition are percentages of dry weight, i.e., excluding any water that may be present in the composition. Percentages of monomer units in the polymer are percentages of solids weight, i.e., excluding any water present in a polymer emulsion.
[0011] As used herein, unless otherwise indicated, the terms "molecular weight" and "Mw" are used interchangeably to refer to the weight average molecular weight as measured in a conventional manner with gel permeation chromatography (GPC) and conventional standards, such as polyethylene glycol standards. GPC techniques are discussed in detail in Modem Size Exclusion Chromatography, W. W. Yau, J. J. Kirkland, D. D. Bly; Wiley- lnterscience, 1979, and in A Guide to Materials Characterization and Chemical Analysis, J. P. Sibilia; VCH, 1988, p.81-84. Molecular weights are reported herein in units of Daltons.
[0012] The term "ethylenically unsaturated" is used to describe a molecule or moiety having one or more carbon-carbon double bonds, which renders it polymerizable. The term "ethylenically unsaturated" includes monoethylenically unsaturated (having one carbon- carbon double bond) and multi-ethylenically unsaturated (having two or more carbon- carbon double bonds). As used herein the term "(meth)acrylic" refers to acrylic or methacrylic.
[0013] The terms "ethyleneoxy" and "EO" as used herein and in the appended claims refer
[0014] The term "phosphate-free" as used herein and in the appended claims means compositions containing < 1 wt% (preferably, < 0.5 wt%; more preferably, < 0.2 wt%; still more preferably, < 0.1 wt%; yet still more preferably, < 0.01 wt%; most preferably, less than the detectable limit) of phosphate (measured as elemental phosphorus).
[0015] The term "structural units" as used herein and in the appended claims refers to the remnant of the indicated monomer; thus a structural unit of acrylic acid is illustrated:
where the dotted lines represent the points of attachment to the polymer backbone.
[0016] Preferably, the automatic dishwashing composition of the present invention, comprises: 0.5 to 15 wt% (preferably, 0.5 to 10 wt%; more preferably, 1 to 8 wt%; most preferably, 2.5 to 7.5 wt%) of a dispersant polymer blend, comprising: an acrylic acid homopolymer; and a copolymer of acrylic acid and a sulfonated monomer; wherein the dispersant polymer blend has a blend ratio of the acrylic acid homopolymer to the copolymer of 3: 1 to 1:3 (preferably, 2.5: 1 to 1:2.5; more preferably, 2: 1 to 1:2; most preferably, 1.5: 1 to 1 : 1.5), based on weight; 0.5 to 15 wt% (preferably, 0.5 to 10 wt%; more preferably, 1 to 8 wt%; most preferably, 2.5 to 7.5 wt%) of a surfactant (preferably, wherein
the surfactant is a non- ionic surfactant); 1 to 75 wt% of a builder; and 0 to 75 wt% of an additive.
[0017] Preferably, the automatic dishwashing composition of the present invention, comprises: 0.5 to 15 wt% (preferably, 0.5 to 10 wt%; more preferably, 1 to 8 wt%; most preferably, 2.5 to 7.5 wt%) of a dispersant polymer blend, comprising: an acrylic acid homopolymer; and a copolymer of acrylic acid and a sulfonated monomer; wherein the dispersant polymer blend has a blend ratio of the acrylic acid homopolymer to the copolymer of 3: 1 to 1:3 (preferably, 2.5: 1 to 1:2.5; more preferably, 2: 1 to 1:2; most preferably, 1.5: 1 to 1 : 1.5), based on weight; 0.5 to 15 wt% (preferably, 0.5 to 10 wt%; more preferably, 1 to 8 wt%; most preferably, 2.5 to 7.5 wt%) of a surfactant (preferably, wherein the surfactant is a non- ionic surfactant); 1 to 75 wt% of a builder; and 0 to 75 wt% of an additive; wherein the builder is selected from the group consisting of a carbonate, a citrate, a silicate and mixtures thereof.
[0018] Preferably, the automatic dishwashing composition of the present invention, comprises: 0.5 to 15 wt% (preferably, 0.5 to 10 wt%; more preferably, 1 to 8 wt%; most preferably, 2.5 to 7.5 wt%) of a dispersant polymer blend, comprising: an acrylic acid homopolymer; and a copolymer of acrylic acid and a sulfonated monomer; wherein the dispersant polymer blend has a blend ratio of the acrylic acid homopolymer to the copolymer of 3: 1 to 1:3 (preferably, 2.5: 1 to 1:2.5; more preferably, 2: 1 to 1:2; most preferably, 1.5: 1 to 1 : 1.5), based on weight; 0.5 to 15 wt% (preferably, 0.5 to 10 wt%; more preferably, 1 to 8 wt%; most preferably, 2.5 to 7.5 wt%) of a surfactant (preferably, wherein the surfactant is a non- ionic surfactant); 1 to 75 wt% of a builder; and 0 to 75 wt% of an additive; wherein the surfactant is a glycidyl ether-capped ethoxylated alcohol of formula I:
wherein Ri is a linear saturated Cs-24 alkyl group (preferably, a linear saturated Cio-14 alkyl group; more preferably, a linear saturated Cio-12 alkyl group; more preferably, a linear saturated C10 alkyl group or a linear saturated C12 alkyl group); R2 is a linear saturated or branched saturated C6-20 alkyl group (preferably, a branched saturated Ce-ιο alkyl group; more preferably, a 2-ethylhexyl group); m has an average value of 10 to 50 (preferably, 10
to 30; more preferably, 15 to 30; still more preferably, 18 to 22; yet still more preferably, 19 to 21; most preferably, 20); and n has an average value of > 1 to 2 (preferably, 1.1 to 2; more preferably, 1.2 to 1.6); and wherein the automatic dishwashing composition contains less than 0.1 wt% (preferably, < 0.05 wt%; more preferably, < 0.01 wt%; still more preferably, < the detectable limit; most preferably free) of amino carboxylate chelant (e.g., MGDA). The glycidyl ether-capped ethoxylated alcohol surfactant of formula I may include a mixture of compounds containing a range of alkyl groups at Ri and R2 differing in carbon number, but having average carbon numbers that conform to the ranges described above.
[0019] Preferably, the automatic dishwashing composition of the present invention, includes 0.5 to 15 wt%, based on the dry weight of the automatic dishwashing composition, of a dispersant polymer blend. More preferably, the automatic dishwashing composition of the present invention, includes 0.5 to 10 wt%, based on the dry weight of the automatic dishwashing composition, of a dispersant polymer blend. Still more preferably, the automatic dishwashing composition of the present invention, includes 1 to 8 wt%, based on the dry weight of the automatic dishwashing composition, of a dispersant polymer blend. Most preferably, the automatic dishwashing composition of the present invention, includes 2.5 to 7.5 wt%, based on the dry weight of the automatic dishwashing composition, of a dispersant polymer blend.
[0020] Preferably, the automatic dishwashing composition of the present invention, includes > 1 wt% (more preferably, > 2 wt%; more preferably, > 3 wt%; more preferably, > 5 wt%) of the dispersant polymer blend, based on the dry weight of the automatic dishwashing composition. Preferably, the automatic dishwashing composition of the present invention, includes < 10 wt% (more preferably, < 8 wt%; more preferably, < 6 wt%; more preferably, < 4 wt%) of the dispersant polymer blend, based on the dry weight of the automatic dishwashing composition.
[0021] Preferably, the dispersant polymer blend included in the automatic dishwashing composition of the present invention comprises a blend of an acrylic acid homopolymer and a copolymer of acrylic acid and a sulfonated monomer, wherein the dispersant polymer blend has a blend ratio of the acrylic acid homopolymer to the copolymer of 3: 1 to 1:3 (preferably, 2.5: 1 to 1 :2.5; more preferably, 2: 1 to 1:2; most preferably, 1.5: 1 to 1: 1.5), based on weight.
[0022] Preferably, the acrylic acid homopolymer used in the automatic dishwashing composition of the present invention, has a weight average molecular weight, Μψ, of 1,000
to 40,000 (preferably, 1,000 to 20,000; more preferably, 1,000 to 10,000; still more preferably, 1,000 to 5,000; most preferably, 2,000 to 4,000) Daltons.
[0023] Preferably, the copolymer of acrylic acid and a sulfonated monomer used in the automatic dishwashing composition of the present invention, has a weight average molecular weight, Mw, of 2,000 to 100,000 (preferably, 5,000 to 60,000; more preferably,
8,000 to 25,000; still more preferably, 10,000 to 20,000; most preferably, 12,500 to 17,500)
Daltons.
[0024] Preferably, the copolymer of acrylic acid and a sulfonated monomer used in the automatic dishwashing composition of the present invention, comprises structural units of at least one sulfonated monomer. More preferably, the copolymer of acrylic acid and a sulfonated monomer used in the automatic dishwashing composition of the present invention comprises structural units of at least one sulfonated monomer selected from the group consisting of 2-acrylamido-2-methylpropane sulfonic acid (AMPS),
2-methacrylamido-2-methylpropane sulfonic acid, 4-styrenesulfonic acid, vinylsulfonic acid, 3-allyloxy sulfonic acid, 2-hydroxy-l -propane sulfonic acid (HAPS),
2-sulfoethyl(meth)acrylic acid, 2- sulfopropyl(meth) acrylic acid, 3 -sulfopropyl(meth) acrylic acid, 4-sulfobutyl(meth)acrylic acid and salts thereof.
[0025] Preferably, the copolymer of acrylic acid and a sulfonated monomer used in the automatic dishwashing composition of the present invention, comprises: 5 to 65 wt% (more preferably, 15 to 40 wt%; most preferably, 20 to 35 wt%) of acrylic acid structural units.
[0026] Preferably, the copolymer of acrylic acid and a sulfonated monomer used in the automatic dishwashing composition of the present invention, comprises: 50 to 95 wt% (preferably, 70 to 93 wt%) of structural units of acrylic acid and 5 to 50 wt% (preferably, 7 to 30 wt%) of structural units of 2-acrylamido-2-methylpropane sulfonic acid sodium salt. More preferably, the copolymer of acrylic acid and a sulfonated monomer used in the automatic dishwashing composition of the present invention, comprises: 50 to 95 wt% (preferably, 70 to 93 wt%) of structural units of acrylic acid and 5 to 50 wt% (preferably, 7 to 30 wt%) of structural units of 2-acrylamido-2-methylpropane sulfonic acid sodium salt; wherein the copolymer has a weight average molecular weight, Mw, of 2,000 to 100,000 (more preferably, 10,000 to 20,000; most preferably, 12,500 to 17,500) Daltons.
[0027] Polymers included in the dispersant polymer blend used in the automatic dishwashing composition of the present invention are commercially available from various sources, and/or they may be prepared using literature techniques. For instance, low- molecular weight polymers included in the dispersant polymer blend may be prepared by
free-radical polymerization. A preferred method for preparing these polymers is by homogeneous polymerization in a solvent. The solvent may be water or an alcoholic solvent such as 2-propanol or 1,2-propanediol. The free-radical polymerization is initiated by the decomposition of precursor compounds such as alkali persulfates or organic peracids and peresters. The activation of the precursors may be by the action of elevated reaction temperature alone (thermal activation) or by the admixture of redox- active agents such as a combination of iron(II) sulfate and ascorbic acid (redox activation). In these cases, a chain- transfer agent is typically used to modulate polymer molecular weight. One class of preferred chain-transfer agents employed in solution polymerizations is the alkali or ammonium bisulfites. Specifically mentioned is sodium meta-bisulfite.
[0028] The polymers included in the dispersant polymer blend used in the automatic dishwashing composition of the present invention may be in the form of a water-soluble solution polymer, slurry, dried powder, or granules or other solid forms.
[0029] Preferably, the automatic dishwashing composition of the present invention comprises 0.5 to 15 wt% (preferably, 0.5 to 10 wt%; more preferably, 1 to 8 wt%; most preferably, 2.5 to 7.5 wt%) of a surfactant. Preferably, the surfactant used in the automatic dishwashing composition of the present invention is a non-ionic surfactant. More preferably, the surfactant used in the automatic dishwashing composition of the present invention is a non-ionic surfactant selected from the group consisting of ethylene oxide-propylene oxide-butylene oxide di- or tri-block copolymers, alkoxylated fatty alcohols, amine oxides, alkyl ether sulfates, or alkylpolyglycosides. Preferably, the surfactant used in the automatic dishwashing composition of the present invention is a non-ionic surfactant having a cloud point of less than 45 °C. Preferably, the surfactant used in the automatic dishwashing composition of the present invention is a non-ionic surfactant based on a polyoxyalkylene polyether derivative.
[0030] Preferably, the surfactant used in the automatic dishwashing composition of the present invention is a glycidyl ether-capped ethoxylated alcohol of formula I:
wherein Ri is a linear saturated Cs-24 alkyl group (preferably, a linear saturated Cio-14 alkyl group; more preferably, a linear saturated Cio-12 alkyl group; more preferably, a linear saturated C10 alkyl group or a linear saturated C12 alkyl group); R2 is a linear saturated or branched saturated C6-2o alkyl group (preferably, a branched saturated Ce-ιο alkyl group; more preferably, a 2-ethylhexyl group); m has an average value of 10 to 50 (preferably, 10 to 30; more preferably, 15 to 30; still more preferably, 18 to 22; yet still more preferably, 19 to 21; most preferably, 20); and n has an average value of > 1 to 2 (preferably, 1.1 to 2; more preferably, 1.2 to 1.6). The glycidyl ether-capped ethoxylated alcohol surfactant of formula I may include a mixture of compounds containing a range of alkyl groups at Ri and R2 differing in carbon number, but having average carbon numbers that conform to the ranges described above.
[0031] The glycidyl ether-capped ethoxylated alcohol surfactants of formula I can be readily prepared using known synthetic procedures. For instance, a typical procedure for preparing the compounds is as follows. An alcohol conforming to the formula RiOH (wherein Ri is a linear, saturated Cs-24 alkyl group) is added to a reactor, and heated in the presence of a base (for example, sodium methoxide or potassium hydroxide). The mixture should be relatively free of water. To this mixture is then added the desired amount of ethylene oxide (EO) under pressure. After the EO has been consumed (as indicated by a substantial fall in reactor pressure), the resulting ethoxylated alcohol may be isolated and subjected to reaction with an alkyl glycidyl ether (wherein the alkyl group contains from 6 to 20 carbon atoms) at a molar ratio of alcohol: glycidyl ether ranging from 1 : 1.1 to 1 :2 under basic conditions. Alternatively, the ethoxylated alcohol may remain in the original reactor and be subjected to further reaction by addition of alkyl glycidyl ether. The molar ratio of catalyst to alcohol can be between 0.01 : 1 and 1 : 1, but preferably is 0.02: 1 to 0.5: 1. Alternatively, a Lewis acid catalyst (for example, boron trifluoride etherate) may be employed at a molar ratio to alcohol of 0.01: 1 to 0.25: 1. The reactions with EO and with alkyl glycidyl ether are generally conducted in the absence of solvent and at temperatures between 25 and 200 °C, and preferably between 80 and 160 °C.
[0032] Preferably, the builder used in the automatic dishwashing composition of the present invention, comprises one or more carbonates, citrates and silicates.
[0033] Preferably, the automatic dishwashing composition of the present invention, comprises: 1 to 75 wt% of a builder. Preferably, the automatic dishwashing composition of the present invention, comprises: > 1 wt% (more preferably, > 10 wt%; more preferably, > 20 wt%; more preferably, > 25 wt%) of the builder, based on the dry weight of the
automatic dishwashing composition. Preferably, the automatic dishwashing composition of the present invention, comprises: < 75 wt% (preferably, < 60 wt%; more preferably, < 50 wt%; most preferably, < 40 wt%) of the builder, based on the dry weight of the automatic dishwashing composition. Weight percentages of carbonates, citrates and silicates are based on the actual weights of the salts, including metal ions.
[0034] The term "carbonate(s)" as used herein and in the appended claims refers to alkali metal or ammonium salts of carbonate, bicarbonate, percarbonate, and/or sesquicarbonate. Preferably, the carbonate used in the automatic dishwashing composition (if any) is selected from the group consisting of carbonate salts of sodium, potassium and lithium (more preferably, salts of sodium or potassium; most preferably, salts of sodium). More preferably, the carbonate used in the automatic dishwashing composition (if any) is selected from the group consisting of sodium carbonate, sodium bicarbonate, sodium percarbonate and mixtures thereof.
[0035] Preferably, the builder used in the automatic dishwashing composition of the present invention includes a carbonate. More preferably, the builder used in the automatic dishwashing composition of the present invention includes a mixture of carbonates.
Preferably, when the builder used in the automatic dishwashing composition of the present invention includes a carbonate, the automatic dishwashing composition preferably, comprises 10 to 75 wt% (preferably, 15 to 70 wt%; more preferably, 25 to 60 wt%; most preferably 30 to 50 wt%) of the carbonate(s).
[0036] The term "citrate(s)" as used herein and in the appended claims refers to alkali metal citrates. Preferably, the citrate used in the automatic dishwashing composition (if any) is selected from the group consisting of citrate salts of sodium, potassium and lithium (more preferably, salts of sodium or potassium; most preferably, salts of sodium). More preferably, the citrate used in the automatic dishwashing composition (if any) is sodium citrate.
[0037] Preferably, the builder used in the automatic dishwashing composition of the present invention includes a citrate. More preferably, the builder used in the automatic dishwashing composition of the present invention includes a mixture of carbonates. Preferably, when the builder used in the automatic dishwashing composition of the present invention includes a carbonate, the automatic dishwashing composition preferably, comprises 0 to 40 wt% (preferably, 21 to 40 wt%; more preferably, 25 to 35 wt%; most preferably 27.5 to 32.5 wt%) of the citrate(s).
[0038] The term "silicate(s)" as used herein and in the appended claims refers to alkali metal silicates. Preferably, the silicate used in the automatic dishwashing composition (if any) is selected from the group consisting of silicate salts of sodium, potassium and lithium (more preferably, salts of sodium or potassium; most preferably, salts of sodium). More preferably, the silicate used in the automatic dishwashing composition (if any) is sodium disilicate. Preferably, the builder used in the automatic dishwashing composition of the present invention includes a silicate. Preferably, when the builder used in the automatic dishwashing composition of the present invention includes a silicate, the automatic dishwashing composition preferably, comprises 0 to 10 wt% (preferably, 0.1 to 5 wt%; more preferably, 0.5 to 3 wt%; most preferably 1.5 to 2.5 wt%) of the silicate(s).
[0039] The automatic dishwashing composition of the present invention, optionally further comprises: an additive. Preferably, the automatic dishwashing composition of the present invention, optionally further comprises: an additive selected from the group consisting of an alkaline source, a bleaching agent (e.g., sodium percarbonate, sodium perborate) and optionally a bleach activator (e.g., tetraacetylethylenediamine (TAED)) and/or a bleach catalyst (e.g., manganese(II) acetate, cobalt(II) chloride, bis(TACN)magnesium trioxide diacetate); an enzyme (e.g., protease, amylase, lipase, or cellulase); an amino carboxylate chelant (e.g., methylglycinediacetic acid (MGDA), glutamic acid-N,N-diacetic acid (GLDA), iminodisuccinic acid (IDS A), 1,2-ethylenediamine disuccinic acid (EDDS), aspartic acid diacetic acid (ASDA), or mixtures or salts thereof); a phosphonate such as 1-hydroxy ethylidene-l, l-diphosphonic acid (HEDP); foam suppressants; colors;
fragrances; silicates; poly (ethylene glycol); additional builders; antibacterial agents and/or fillers. Fillers in tablets or powders are inert, water-soluble substances, typically sodium or potassium salts, e.g., sodium or potassium sulfate and/or chloride, and typically are present in amounts ranging from 0 wt% to 75 wt%. Fillers in gel formulations may include those mentioned above and also water and other solvents (e.g., glycerin). Fragrances, dyes, foam suppressants, enzymes and antibacterial agents usually total no more than 10 wt%, alternatively no more than 5 wt%, of the composition.
[0040] The automatic dishwashing composition of the present invention, optionally further comprises: an alkaline source. Suitable alkaline sources include, without limitation, alkali metal carbonates and alkali metal hydroxides, such as sodium or potassium carbonate, bicarbonate, sesquicarbonate, sodium, lithium, or potassium hydroxide, or mixtures of the foregoing. Sodium carbonate is preferred. The amount of alkaline source in the automatic dishwashing composition of the present invention, when present, may range, for instance,
from at least 1 weight percent (preferably, at least 20 weight percent) and up to 80 weight percent (preferably, up to 60 weight percent), based on the dry weight of the automatic dishwashing composition.
[0041] The automatic dishwashing composition of the present invention, optionally further comprises: a bleaching agent. A preferred bleaching agent is sodium percarbonate. The amount of the bleaching agent in the automatic dishwashing composition of the present invention, when present, is preferably at a concentration of 1 to 25 wt% (more preferably, 1 to 10 wt%, based on the dry weight of the automatic dishwashing composition.
[0042] Preferably, the automatic dishwashing composition of the present invention has a pH (at 1 wt% in water) of at least 9 (preferably, > 10). Preferably, the automatic dishwashing composition of the present invention has a pH (at 1 wt% in water) of no greater than 13.
[0043] Preferably, the automatic dishwashing composition of the present invention can be formulated in any typical form, e.g., as a tablet, powder, block, monodose, sachet, paste, liquid or gel. The automatic dishwashing compositions of the present invention are useful for cleaning ware, such as eating and cooking utensils, dishes, in an automatic dishwashing machine.
[0044] Preferably, the automatic dishwashing composition of the present invention can be used under typical operating conditions. For instance, when used in an automatic dishwashing machine, typical water temperatures during the washing process preferably are from 20 °C to 85 °C, preferably 30 °C to 70 °C. Typical concentrations for the automatic dishwashing composition as a percentage of total liquid in the dishwasher preferably are from 0.1 to 1 wt%, preferably from 0.2 to 0.7 wt%. With selection of an appropriate product form and addition time, the automatic dishwashing compositions of the present invention may be present in the prewash, main wash, penultimate rinse, final rinse, or any combination of these cycles.
[0045] Preferably, the automatic dishwashing composition of the present invention comprises < 1 wt% (preferably, < 0.5 wt%; more preferably, < 0.2 wt%; still more preferably, < 0.1 wt%; yet still more preferably, < 0.01 wt%; most preferably, < the detectable limit) of phosphate (measured as elemental phosphorus). Preferably, the automatic dishwashing composition of the present invention is phosphate free.
[0046] Preferably, the automatic dishwashing composition of the present invention comprises < 0.1 wt% (preferably, < 0.05 wt%; more preferably, < 0.01 wt%; most preferably, < the detectable limit) of amino carboxylate chelant (e.g., MGDA). Preferably,
the automatic dishwashing composition of the present invention is amino carboxylate chelant (e.g., MGDA) free.
[0047] Some embodiments of the present invention will now be described in detail in the following Examples.
Preparation of Surfactants
[0048] Materials: 1 ,2-epoxyoctane, 2-ethylhexyl glycidyl ether, 1-decanol, 1-dodecanol, 2- butyl-l-octanol, sodium methoxide solution were obtained from Sigma- Aldrich and used without further purification. 2-Ethylhexanol which had been reacted first with 5 equivalents of propylene oxide followed by 15 equivalents of ethylene oxide was obtained as a 90 % solution in water from Dow Chemical and is referred to below as "2EH-P05-E015."
Analytical Methods
[0049] NMR: Quantitative 13C spectra were obtained on a Bruker 500 MHz instrument, running generally 6144 scans, experiment zgig30, pulse length 13.25 μ8, recycle delay 5.000 s, 2 Hz line broadening.
[0050] Polymer Molecular Weight. Weight average molecular weight may be measured by gel permeation chromatography (GPC) using known methodology. GPC analysis was conducted on an Agilent 1100 Series GPC by dissolving 0.010 g of sample in 10 mL of THF and injecting a 50 aliquot of this solution onto a series of two Polymer Labs PLgel 5 μιη MIXED-E columns (300 x 7.5 mm) and eluting with THF (either pure or containing 5 % water) at a flow rate of 1.0 niL/min at 35 °C using differential refractive index detection (35 °C). A conventional calibration curve was generated using narrow polyethylene glycol standards.
[0051] Alkoxylation reactions were carried out in a 2-L 316 stainless steel conical bottom (minimum stirring volume 20 mL) Parr reactor, model 4530, equipped with a 1/4 hp magnetic drive agitator, 1500 watt (115V) Calrod electric heater, 1/4 inch water filled cooling coil, 1/16 inch dip tube for sampling, internal thermowell, 1/4 inch rupture disc set at 1024 psig, 1/4 inch relief valve set at 900 psig, an oxide addition line submerged below the liquid level, and a 2 inch diameter pitch-blade agitator. The bottom of the agitator shaft had a custom-made stainless steel paddle shaped to the contour of the reactor to allow stirring at very low initial volumes. The oxide addition system consisted of a 1 liter stainless steel addition cylinder, which was charged, weighed, and attached to the oxide load line. The reactor system was controlled by a Siemens SIMATIC PCS7 process control system. Reaction temperatures were measured with Type K thermocouples, pressures were measured with Ashcroft pressure transducers, ball valves were operated with Swagelok
pneumatic valve actuators, cooling water flow was controlled with ASCO electric valves, and oxide addition rates were controlled by a mass flow control system consisting of a Brooks Quantim® Coriolis mass flow controller (model
QMBC3L1B2A1A1 A1DH1C7A1DA) and a TESCOM back pressure regulator (model 44-1163-24-109A) which maintained a 100 psig pressure differential across the mass flow controller to afford steady flow rates.
[0052] Reagent ratios are occasionally abbreviated "X eq.": wherein the added reagent is considered to have a molar ratio of X: 1 relative to the original reactant.
Example 1: Synthesis of Decanol Ethoxylate
[0053] The 2-L Parr reactor was charged with 121.3 g of 1-decanol and 0.50 g of powdered 85% potassium hydroxide, and after a pressure check and series of nitrogen purges, the mixture warmed to 130 °C for the addition of 670.2 g of ethylene oxide (approximately 20 eq.) at an addition rate of 1 to 2 g/min. After the addition was complete and the pressure stabilized, the reaction product was cooled and unloaded to afford 785.6 g. GPC results: Mw = 1220, MN = 1140. 13C NMR in DMSO-rfe (δ, ppm): 72.4, 70.3, 69.7, 69.8, 69.6, 60.2, 31.4, 29.3, 29.1, 29.1, 29.0, 28.8, 25.7, 22.1, 13.8.
Example 2: Synthesis of Dodecanol Ethoxylate
[0054] The 2-L Parr reactor was charged with 100.2 g of 1-decanol and 0.56 g of powdered 85% potassium hydroxide, and after a pressure check and series of nitrogen purges, the mixture warmed to 130 °C for the addition of 473.0 g of ethylene oxide (approximately 20 eq.) at an addition rate of 2 g/min. After the addition was complete and the pressure stabilized, the reaction product was cooled and unloaded to afford 564.77 g. GPC results: Mw = 1110, MN = 1045. 13C NMR in DMSO-rfe (δ, ppm): 72.4, 70.4, 59.9, 69.6, 60.1, 31.4, 29.3, 29.1, 29.1, 29.0, 28.8, 25.7, 22.1, 13.8.
Example 3: Decanol Ethoxylate/2-Ethylhexyl Glycidyl Ether
[0055] To a round-bottom glass flask equipped with overhead stirrer, thermocouple, nitrogen sweep, and heating mantle were added 50 g of decanol ethoxylate from Example 1. Heat was applied until the decanol ethoxylate melted, then stirring was begun and 2.6 g sodium methoxide solution (25 % in methanol, 25 mol % based on ethoxylate) was slowly added. The reactor was heated to 140 °C, and upon reaching this temperature, addition of 13.5 g 2-ethylhexyl glycidyl ether (approximately 1.7 eq.) was begun and continued for 1 h. After addition, the reaction was stirred for an additional 6 h at 140 °C, then was allowed to cool overnight. The next day, the reaction mixture was heated to 50 °C, quenched with 0.43 g acetic acid, and then poured into a vial. 13C NMR in DMSO-ifc (δ, ppm): 73.3, 72.8,
72.4, 70.3, 70.2, 69.9, 69.6, 68.5, 60.2, 31.4, 30.1, 29.3, 29.1, 29.0, 28.6, 25.7, 23.4, 22.6, 22.2, 13.8, 10.7.
Example 4: Dodecanol Ethoxylate/2-Ethylhexyl Glycidyl Ether
[0056] To a round-bottom glass flask equipped with overhead stirrer, thermocouple, nitrogen sweep, and heating mantle were added 51.5 g of dodecanol ethoxylate from
Example 2. Heat was applied until the decanol ethoxylate melted, then stirring was begun and 2.6 g sodium methoxide solution (25 % in methanol, 25 mol % based on ethoxylate) was slowly added. The reactor was heated to 140 °C, and upon reaching this temperature, addition of 13.5 g 2-ethylhexyl glycidyl ether (approximately 1.3 eq.) was begun and continued for 1 h. After addition, the reaction was stirred for an additional 6 h at 140 °C, then was allowed to cool overnight. The next day, the reaction mixture was heated to 50 °C, quenched with 0.43 g acetic acid, and then poured into a vial. 13C NMR in DMSO-cfc (δ, ppm): 73.3, 72.9, 72.5, 70.4, 70.1, 69.9, 69.6, 68.4, 60.1, 31.4, 30.1, 29.2, 28.8, 28.6, 25.7, 23.4, 22.6, 22.1, 13.8, 10.7.
Example 5: Synthesis of 2-Butyloctanol Ethoxylate
[0057] The 2-L Parr reactor was charged with 85.90 g of 2-butyl-l-octanol and 0.48 g of powdered 85% potassium hydroxide, and after a pressure check and series of nitrogen purges, the mixture warmed to 130 °C for the addition of 406.4 g of ethylene oxide (approximately 20 eq.) at an addition rate of 2 g/min. After the addition was complete and the pressure stabilized, the reaction product was cooled and unloaded to afford 493.2 g. GPC results: Mw = 1390, MN = 1190. 13C NMR in DMSO-ifc (δ, ppm): 73.4, 72.4, 70.2, 69.9, 60.2, 58.0, 31.3, 30.9, 39.6, 29.2, 28.5, 26.2, 22.6, 22.1, 13.8.
Comparative Example CI: Decanol Ethoxylate/l,2-Epoxyoctane
[0058] To a round-bottom glass flask equipped with overhead stirrer, thermocouple, nitrogen sweep, and heating mantle were added 50 g of decanol ethoxylate from Example 1. Heat was applied until the decanol ethoxylate melted, then stirring was begun and 2.6 g sodium methoxide solution (25 % in methanol, 25 mol % based on ethoxylate) was slowly added. The reactor was heated to 90 °C, and upon reaching this temperature, addition of 9.3 g 1 ,2-epoxy octane (approximately 1.7 eq.) was begun and continued for 1 h. After addition, the reaction was stirred for an additional 6 h at 140 °C, then was allowed to cool overnight. The next day, the reaction mixture was heated to 90 °C and heated an additional 6 h, then was allowed to cool to 50 °C, quenched with 0.43 g acetic acid, and then poured into a vial. 13C NMR in DMSO-ifc (δ, ppm): 75.6, 72.4, 70.4, 70.0, 69.9, 69.6, 68.8, 68.6, 60.2, 33.7, 31.4, 29.3, 29.1, 29.1, 29.0, 28.9, 25.7, 25.0, 22.1, 13.8, 13.8.
Comparative Example C2: 2-Butyloctanol Ethoxylate/2- Ethylhexyl Glvcidyl Ether
[0059] To a round-bottom glass flask equipped with overhead stirrer, thermocouple, nitrogen sweep, and heating mantle were added 51.5 g of 2-butyloctanol ethoxylate from Example 5. Heat was applied until the decanol ethoxylate melted, then stirring was begun and 2.6 g sodium methoxide solution (25 % in methanol, 25 mol % based on ethoxylate) was slowly added. The reactor was heated to 140 °C, and upon reaching this temperature, addition of 13.5 g 2-ethylhexyl glycidyl ether (approximately 1.3 eq.) was begun and continued for 1 h. After addition, the reaction was stirred for an additional 6 h at 140 °C, then was allowed to cool overnight. The next day, the reaction mixture was heated to 50 °C, quenched with 0.43 g acetic acid, and then poured into a vial. 13C NMR in DMSO-cfc (δ, ppm): 73.5, 73.3, 72.7, 72.4, 70.5, 70.1, 69.9, 68.5, 60.2, 58.3, 37.6, 31.3, 30.9, 30.6, 30.1, 29.2, 28.5, 26.2, 23.4, 22.6, 22.1, 13.8, 10.8.
Comparative Example C3: 2-Ethylhexanol Alkoxylate/2- Ethylhexyl Glvcidyl Ether
[0060] To a round-bottom glass flask equipped with overhead stirrer, thermocouple, nitrogen sweep, and heating mantle were added 57.8 g of 2EH-P05-E015 (90 %). The kettle was heated to 140 °C with stirring and active nitrogen bubbling for 3 h to remove water. After cooling overnight, the temperature was raised to 70 °C and then 2.6 g sodium methoxide solution (25 % in methanol, 25 mol % based on ethoxylate) was slowly added. The reactor was heated to 140 °C, and upon reaching this temperature, addition of 13.5 g 2- ethylhexyl glycidyl ether (approximately 1.3 eq.) was begun and continued for 1 h. After addition, the reaction was stirred for an additional 6 h at 140 °C, then was allowed to cool overnight. The next day, the reaction mixture was heated to 50 °C, quenched with 0.43 g acetic acid, and then poured into a vial. 13C NMR in DMSO-ifc (δ, ppm): 74.6, 74.6, 74.4, 74.3, 74.2, 73.3, 73.2, 72.9, 72.5, 72.4, 72.2, 70.6, 70.1, 69.8, 68.4, 67.9, 30.1, 28.5, 23.4, 22.5, 17.2, 13.9, 10.9.
Automatic Dishwashing Tests
[0061] The surfactants described in Examples 3-4 and Comparative Examples C1-C3 above are tested for their anti-spotting performance during automatic dishwashing. The dishwashing formulation used is shown in TABLE 1.
TABLE 1
[0062] The food soil used in the automatic dishwashing tests is shown in TABLE 2.
TABLE 2
Procedure for preparing food soil
[0063] Heat water to 70°C and add the potato starch, quark powder, benzoic acid and margarine. Agitate until the margarine is well dissolved. Then add the milk and agitate well. Let the mix cool down. When the temperature is lower than 45 °C, add the egg yolks, ketchup and mustard. Mix well.
Dishwashing Test Conditions
[0064] Machine: Miele SS-ADW, Model G1222SC Labor. Program: V4, 50 °C wash cycle with heated wash, fuzzy logic disengaged, heated dry. Water: 375 ppm hardness (as CaC03, confirmed by EDTA titration), Ca:Mg = 3:1, 250 ppm sodium carbonate. Food soil: 50 g (introduced at t = 0, frozen in cup).
Spotting test
[0065] After drying in open air spotting ratings were determined by trained evaluators by observations of glass tumblers in a light box with controlled illumination from below and ranging from 1 (no spots) to 5 (heavily spotted). Results are shown in TABLE 3 AND 4.
TABLE 3. S ottin Test A
Example 6: Preparation and Testing of Surfactant Mixture
[0066] Surfactant is prepared via one-pot ethoxylation and capping of
dodecanol/tetradecanol. A 2-L Parr reactor was charged with 79.03 g of a mixture containing 68-78 % dodecanol and 20 to 30 % tetradecanol (available from Procter & Gamble as CO- 1270) and 2.85 g of powdered 85% potassium hydroxide, and after a pressure check and a series of nitrogen purges, the mixture warmed to 125 °C. A slow nitrogen purge through the dip pipe and out the reactor vent removed 8.5 g of condensate. The pressure was released and the vent valve closed for the addition of 394.0 g of ethylene oxide (approximately 22 eq.) at an addition rate of 1 to 3 g/min. The total addition time was 3 hours. The pressure stabilized about 10 minutes after the addition was complete. The mixture was held at temperature for an additional 50 minutes, then cooled to 100 °C and held overnight. The reactor was vented and the reaction product was cooled to 50 °C while purging slowly with nitrogen through the dip tube. The system was opened and a 2.6 g sample of the product was removed for analysis. To the remaining material held at 50 °C in the Parr reactor were charged 106 g of 2-ethylhexyl glycidyl ether (approximately 1.4 molar equivalents), and after sealing, a pressure check, and a series of nitrogen purges, the mixture was warmed to 140 °C at a rate of 1 °C/min and held at temperature for 6 hours, then cooled to 60 °C at a rate of 1 °C/min. After opening and sampling for analysis to confirm reaction completion, the reaction product was unloaded to afford 548.3 g. GPC results: Μψ = 1300, MN = 1230.
Testing in Automatic Dishwashing
[0067] Rinse performance tests were performed using the conditions described above.
After 5 cycles, the glasses for a condition including 1 g (5 % of detergent) of surfactant of this Example 6 were compared in their spotting and filming ratings. The spotting and filming ratings for Example 6 were 1.5 and 2.1, respectively, compared with 2.9 and 1.9, respectively, for a 1,2-epoxydecane-capped ethoxylated alcohol surfactant DEHYPON E-
127, a product of BASF Corp.
Comparative Examples C4-C5 and Example 7
Automatic Dishwashing Scale Tests
[0068] Automatic dishwashing compositions were prepared in each of Comparative
Examples C4-C5 and Example 7 having the formulation shown in TABLE 5.
TABLE 5
[0069] In Comparative Example C4, the dispersant used was a polyacrylic acid homopolymer having a weight average molecular weight of -3,600 Daltons (Acusol™ 420N dispersant, available from The Dow Chemical Company). In Comparative Example C5, the dispersant used was a copolymer of acrylic acid and a sulfonated monomer having a weigh average molecular weight of ~ 15,000 Daltons (Acusol™ 588 dispersant, available from The Dow Chemical Company). In Example 7, the dispersant used was a dispersant blend with a 1 : 1 weight blend of a polyacrylic acid homopolymer having a weight average molecular weight of -3,600 Daltons (Acusol™ 420N dispersant, available from The Dow Chemical Company) and a copolymer of acrylic acid and a sulfonated monomer having a weigh average molecular weight of - 15,000 Daltons (Acusol™ 588 dispersant, available from The Dow Chemical Company).
[0070] The food soil used in the automatic dishwashing tests is shown in TABLE 6.
TABLE 6
Procedure for preparing food soil
[0071] Heat water to 80°C and add the potato starch, quark powder, benzoic acid and margarine. Agitate until the margarine is well dissolved. Then add the milk and agitate well. Let the mix cool down. When the temperature is lower than 45 °C, add the egg yolks, ketchup and mustard. Mix well.
Dishwashing Test Conditions
[0072] Machine: Miele SS-ADW, Model G1222SC Labor. Program: Wash at 65 °C for 30 minutes. Water: 37 °fH total hardness, Ca:Mg = 3:1, temporary hardness 25 °fH. Food soil: 50 g (introduced at t = 0, frozen in cup). Number of cycles: 30.
Scale test
[0073] After drying in open air scale ratings were determined by trained evaluators by observations of glass tumblers in a light box with controlled illumination from below and ranging from 1 (no film) to 5 (high level of filming). Results are shown in TABLE 7.
TABLE 7
Claims (10)
1. An automatic dishwashing composition, comprising:
0.5 to 15 wt% of a dispersant polymer blend, comprising:
an acrylic acid homopolymer; and
a copolymer of acrylic acid and a sulfonated monomer;
wherein the dispersant polymer blend has a blend ratio of the acrylic acid homopolymer to the copolymer of 3:1 to 1:3;
0.5 to 15 wt% of a surfactant;
1 to 75 wt% of a builder; and
0 to 75 wt% of an additive.
2. The automatic dishwashing composition of claim 1, wherein the builder is selected from the group consisting of a carbonate, a citrate, a silicate and mixtures thereof.
3. The automatic dishwashing composition of claim 1, further comprising an additive selected from the group consisting of a bleaching agent, a bleach activator, a bleach catalyst, an enzyme, a phosphonate salt and an aminocarboxylate chelant.
4. The automatic dishwashing composition of claim 1, wherein the automatic dishwashing composition is amino carboxylate chelant free.
5. The automatic dishwashing composition of claim 1, wherein the automatic dishwashing composition contains less than 0.5 wt% phosphate (measured as elemental phosphorus).
6. The automatic dishwashing composition of claim 5, wherein the automatic dishwashing composition contains less than 0.1 wt% amino carboxylate chelant.
7. The automatic dishwashing composition of claim 6, wherein the surfactant is a glycidyl ether-capped ethoxylated alcohol of formula I:
wherein Ri is a linear, saturated Cs-24 alkyl group, R2 is a linear or branched saturated C6-20 alkyl group, m has an average value of 10 to 50, and n has an average value of > 1 to 2.
8. The automatic dishwashing composition of claim 7, wherein Ri is a linear, saturated Cio-14 alkyl group.
9. The automatic dishwashing composition of claim 7, wherein R2 is a branched saturated Ce-ιο alkyl group.
10. A method of cleaning an article in an automatic dishwashing machine, the method comprising:
applying to the article the automatic dishwashing composition of claim 1.
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