CN102220186A - 用于自动洗盘系统的减少积垢的添加剂 - Google Patents
用于自动洗盘系统的减少积垢的添加剂 Download PDFInfo
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- CN102220186A CN102220186A CN201110063246XA CN201110063246A CN102220186A CN 102220186 A CN102220186 A CN 102220186A CN 201110063246X A CN201110063246X A CN 201110063246XA CN 201110063246 A CN201110063246 A CN 201110063246A CN 102220186 A CN102220186 A CN 102220186A
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- China
- Prior art keywords
- acid
- weight
- composition
- polymkeric substance
- oxalic acid
- 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.)
- Pending
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- 238000004851 dishwashing Methods 0.000 title claims abstract description 10
- 239000000654 additive Substances 0.000 title description 2
- 230000000996 additive effect Effects 0.000 title description 2
- 239000000203 mixture Substances 0.000 claims abstract description 47
- 239000000178 monomer Substances 0.000 claims abstract description 19
- 229920000642 polymer Polymers 0.000 claims abstract description 12
- 150000001732 carboxylic acid derivatives Chemical class 0.000 claims abstract description 7
- 150000003839 salts Chemical class 0.000 claims abstract description 6
- KCXVZYZYPLLWCC-UHFFFAOYSA-N EDTA Chemical compound OC(=O)CN(CC(O)=O)CCN(CC(O)=O)CC(O)=O KCXVZYZYPLLWCC-UHFFFAOYSA-N 0.000 claims abstract description 5
- QPCDCPDFJACHGM-UHFFFAOYSA-N N,N-bis{2-[bis(carboxymethyl)amino]ethyl}glycine Chemical compound OC(=O)CN(CC(O)=O)CCN(CC(=O)O)CCN(CC(O)=O)CC(O)=O QPCDCPDFJACHGM-UHFFFAOYSA-N 0.000 claims abstract description 5
- 239000003599 detergent Substances 0.000 claims abstract description 5
- JYXGIOKAKDAARW-UHFFFAOYSA-N N-(2-hydroxyethyl)iminodiacetic acid Chemical compound OCCN(CC(O)=O)CC(O)=O JYXGIOKAKDAARW-UHFFFAOYSA-N 0.000 claims abstract description 4
- 229920000805 Polyaspartic acid Polymers 0.000 claims abstract description 4
- MGFYIUFZLHCRTH-UHFFFAOYSA-N nitrilotriacetic acid Chemical compound OC(=O)CN(CC(O)=O)CC(O)=O MGFYIUFZLHCRTH-UHFFFAOYSA-N 0.000 claims abstract description 4
- 108010064470 polyaspartate Proteins 0.000 claims abstract description 4
- CKLJMWTZIZZHCS-REOHCLBHSA-N L-aspartic acid Chemical compound OC(=O)[C@@H](N)CC(O)=O CKLJMWTZIZZHCS-REOHCLBHSA-N 0.000 claims abstract description 3
- 235000003704 aspartic acid Nutrition 0.000 claims abstract description 3
- OQFSQFPPLPISGP-UHFFFAOYSA-N beta-carboxyaspartic acid Natural products OC(=O)C(N)C(C(O)=O)C(O)=O OQFSQFPPLPISGP-UHFFFAOYSA-N 0.000 claims abstract description 3
- 229960003330 pentetic acid Drugs 0.000 claims abstract description 3
- 239000000126 substance Substances 0.000 claims description 40
- 238000005406 washing Methods 0.000 claims description 20
- 229910052757 nitrogen Inorganic materials 0.000 claims description 16
- MUBZPKHOEPUJKR-UHFFFAOYSA-N oxalic acid Substances OC(=O)C(O)=O MUBZPKHOEPUJKR-UHFFFAOYSA-N 0.000 claims description 14
- VZCYOOQTPOCHFL-UPHRSURJSA-N maleic acid Chemical compound OC(=O)\C=C/C(O)=O VZCYOOQTPOCHFL-UPHRSURJSA-N 0.000 claims description 9
- LDHQCZJRKDOVOX-UHFFFAOYSA-N 2-butenoic acid Chemical group CC=CC(O)=O LDHQCZJRKDOVOX-UHFFFAOYSA-N 0.000 claims description 7
- 150000002148 esters Chemical class 0.000 claims description 6
- KDYFGRWQOYBRFD-UHFFFAOYSA-N Succinic acid Natural products OC(=O)CCC(O)=O KDYFGRWQOYBRFD-UHFFFAOYSA-N 0.000 claims description 5
- KDYFGRWQOYBRFD-NUQCWPJISA-N butanedioic acid Chemical compound O[14C](=O)CC[14C](O)=O KDYFGRWQOYBRFD-NUQCWPJISA-N 0.000 claims description 5
- 125000000457 gamma-lactone group Chemical group 0.000 claims description 5
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 claims description 5
- KDYFGRWQOYBRFD-UHFFFAOYSA-L succinate(2-) Chemical compound [O-]C(=O)CCC([O-])=O KDYFGRWQOYBRFD-UHFFFAOYSA-L 0.000 claims description 5
- 239000002253 acid Substances 0.000 claims description 4
- UINXJMGJGZQEFI-DKWTVANSSA-N (2s)-2-aminobutanedioic acid;oxalic acid Chemical compound OC(=O)C(O)=O.OC(=O)[C@@H](N)CC(O)=O UINXJMGJGZQEFI-DKWTVANSSA-N 0.000 claims description 2
- KVPMCFRZLDLEJW-UHFFFAOYSA-N C(C(=O)O)(=O)O.NCCC(=O)O Chemical compound C(C(=O)O)(=O)O.NCCC(=O)O KVPMCFRZLDLEJW-UHFFFAOYSA-N 0.000 claims description 2
- 239000004348 Glyceryl diacetate Substances 0.000 claims description 2
- 229910052717 sulfur Inorganic materials 0.000 claims description 2
- 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 abstract 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 abstract 1
- XYBHHDIIOKAINY-UHFFFAOYSA-N 2-(1,2-dicarboxyethylamino)-3-hydroxybutanedioic acid Chemical compound OC(=O)C(O)C(C(O)=O)NC(C(O)=O)CC(O)=O XYBHHDIIOKAINY-UHFFFAOYSA-N 0.000 abstract 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 abstract 1
- UWRBFYBQPCJRRL-UHFFFAOYSA-N 3-[bis(carboxymethyl)amino]propanoic acid Chemical compound OC(=O)CCN(CC(O)=O)CC(O)=O UWRBFYBQPCJRRL-UHFFFAOYSA-N 0.000 abstract 1
- 229940071087 ethylenediamine disuccinate Drugs 0.000 abstract 1
- 125000000686 lactone group Chemical group 0.000 abstract 1
- NIXOWILDQLNWCW-UHFFFAOYSA-N Acrylic acid Chemical compound OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 10
- 239000013543 active substance Substances 0.000 description 8
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 7
- -1 phosphonate compounds Chemical class 0.000 description 7
- VZCYOOQTPOCHFL-OWOJBTEDSA-N Fumaric acid Chemical compound OC(=O)\C=C\C(O)=O VZCYOOQTPOCHFL-OWOJBTEDSA-N 0.000 description 6
- 230000000052 comparative effect Effects 0.000 description 6
- LVHBHZANLOWSRM-UHFFFAOYSA-N itaconic acid Chemical compound OC(=O)CC(=C)C(O)=O LVHBHZANLOWSRM-UHFFFAOYSA-N 0.000 description 6
- 238000002360 preparation method Methods 0.000 description 6
- 239000007787 solid Substances 0.000 description 6
- 239000012986 chain transfer agent Substances 0.000 description 5
- 229910052698 phosphorus Inorganic materials 0.000 description 5
- 239000011574 phosphorus Substances 0.000 description 5
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 5
- JHPBZFOKBAGZBL-UHFFFAOYSA-N (3-hydroxy-2,2,4-trimethylpentyl) 2-methylprop-2-enoate Chemical compound CC(C)C(O)C(C)(C)COC(=O)C(C)=C JHPBZFOKBAGZBL-UHFFFAOYSA-N 0.000 description 4
- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 description 4
- WCUXLLCKKVVCTQ-UHFFFAOYSA-M Potassium chloride Chemical compound [Cl-].[K+] WCUXLLCKKVVCTQ-UHFFFAOYSA-M 0.000 description 4
- 239000000945 filler Substances 0.000 description 4
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 4
- 238000006116 polymerization reaction Methods 0.000 description 4
- 159000000000 sodium salts Chemical class 0.000 description 4
- DZSVIVLGBJKQAP-UHFFFAOYSA-N 1-(2-methyl-5-propan-2-ylcyclohex-2-en-1-yl)propan-1-one Chemical compound CCC(=O)C1CC(C(C)C)CC=C1C DZSVIVLGBJKQAP-UHFFFAOYSA-N 0.000 description 3
- 102000004190 Enzymes Human genes 0.000 description 3
- 108090000790 Enzymes Proteins 0.000 description 3
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 3
- 229920002125 Sokalan® Polymers 0.000 description 3
- 229910052783 alkali metal Inorganic materials 0.000 description 3
- CERQOIWHTDAKMF-UHFFFAOYSA-N alpha-methacrylic acid Natural products CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 description 3
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 description 3
- 238000009472 formulation Methods 0.000 description 3
- 239000001530 fumaric acid Substances 0.000 description 3
- 238000005227 gel permeation chromatography Methods 0.000 description 3
- 239000004584 polyacrylic acid Substances 0.000 description 3
- 239000001103 potassium chloride Substances 0.000 description 3
- 235000011164 potassium chloride Nutrition 0.000 description 3
- 239000000843 powder Substances 0.000 description 3
- VZCYOOQTPOCHFL-UHFFFAOYSA-N trans-butenedioic acid Natural products OC(=O)C=CC(O)=O VZCYOOQTPOCHFL-UHFFFAOYSA-N 0.000 description 3
- HRPVXLWXLXDGHG-UHFFFAOYSA-N Acrylamide Chemical compound NC(=O)C=C HRPVXLWXLXDGHG-UHFFFAOYSA-N 0.000 description 2
- LSNNMFCWUKXFEE-UHFFFAOYSA-M Bisulfite Chemical compound OS([O-])=O LSNNMFCWUKXFEE-UHFFFAOYSA-M 0.000 description 2
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 description 2
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 2
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 description 2
- 238000004458 analytical method Methods 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 239000011575 calcium Substances 0.000 description 2
- 125000004432 carbon atom Chemical group C* 0.000 description 2
- 239000003795 chemical substances by application Substances 0.000 description 2
- 238000004140 cleaning Methods 0.000 description 2
- 229920001577 copolymer Polymers 0.000 description 2
- 239000013530 defoamer Substances 0.000 description 2
- 238000010528 free radical solution polymerization reaction Methods 0.000 description 2
- 239000000499 gel Substances 0.000 description 2
- 239000011521 glass Substances 0.000 description 2
- BHEPBYXIRTUNPN-UHFFFAOYSA-N hydridophosphorus(.) (triplet) Chemical group [PH] BHEPBYXIRTUNPN-UHFFFAOYSA-N 0.000 description 2
- TVZISJTYELEYPI-UHFFFAOYSA-N hypodiphosphoric acid Chemical compound OP(O)(=O)P(O)(O)=O TVZISJTYELEYPI-UHFFFAOYSA-N 0.000 description 2
- 239000007788 liquid Substances 0.000 description 2
- 239000011777 magnesium Substances 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 238000000034 method Methods 0.000 description 2
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- 0 *C(CC(*)(*)O1)C1=O Chemical compound *C(CC(*)(*)O1)C1=O 0.000 description 1
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 description 1
- JJJOZVFVARQUJV-UHFFFAOYSA-N 2-ethylhexylphosphonic acid Chemical compound CCCCC(CC)CP(O)(O)=O JJJOZVFVARQUJV-UHFFFAOYSA-N 0.000 description 1
- RFVNOJDQRGSOEL-UHFFFAOYSA-N 2-hydroxyethyl octadecanoate Chemical compound CCCCCCCCCCCCCCCCCC(=O)OCCO RFVNOJDQRGSOEL-UHFFFAOYSA-N 0.000 description 1
- XEEYSDHEOQHCDA-UHFFFAOYSA-N 2-methylprop-2-ene-1-sulfonic acid Chemical compound CC(=C)CS(O)(=O)=O XEEYSDHEOQHCDA-UHFFFAOYSA-N 0.000 description 1
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 description 1
- KXDHJXZQYSOELW-UHFFFAOYSA-N Carbamic acid Chemical compound NC(O)=O KXDHJXZQYSOELW-UHFFFAOYSA-N 0.000 description 1
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 1
- KRKNYBCHXYNGOX-UHFFFAOYSA-K Citrate Chemical compound [O-]C(=O)CC(O)(CC([O-])=O)C([O-])=O KRKNYBCHXYNGOX-UHFFFAOYSA-K 0.000 description 1
- 208000006558 Dental Calculus Diseases 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
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 description 1
- BAPJBEWLBFYGME-UHFFFAOYSA-N Methyl acrylate Chemical compound COC(=O)C=C BAPJBEWLBFYGME-UHFFFAOYSA-N 0.000 description 1
- WHNWPMSKXPGLAX-UHFFFAOYSA-N N-Vinyl-2-pyrrolidone Chemical compound C=CN1CCCC1=O WHNWPMSKXPGLAX-UHFFFAOYSA-N 0.000 description 1
- BPQQTUXANYXVAA-UHFFFAOYSA-N Orthosilicate Chemical compound [O-][Si]([O-])([O-])[O-] BPQQTUXANYXVAA-UHFFFAOYSA-N 0.000 description 1
- 108010077895 Sarcosine Proteins 0.000 description 1
- PMZURENOXWZQFD-UHFFFAOYSA-L Sodium Sulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=O PMZURENOXWZQFD-UHFFFAOYSA-L 0.000 description 1
- 241000270666 Testudines Species 0.000 description 1
- DPDMMXDBJGCCQC-UHFFFAOYSA-N [Na].[Cl] Chemical compound [Na].[Cl] DPDMMXDBJGCCQC-UHFFFAOYSA-N 0.000 description 1
- 150000001340 alkali metals Chemical class 0.000 description 1
- XYLMUPLGERFSHI-UHFFFAOYSA-N alpha-Methylstyrene Chemical compound CC(=C)C1=CC=CC=C1 XYLMUPLGERFSHI-UHFFFAOYSA-N 0.000 description 1
- 150000003863 ammonium salts Chemical class 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 229910052728 basic metal Inorganic materials 0.000 description 1
- 239000007844 bleaching agent Substances 0.000 description 1
- 125000000484 butyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 229910052791 calcium Inorganic materials 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 125000002843 carboxylic acid group Chemical group 0.000 description 1
- 125000002091 cationic group Chemical group 0.000 description 1
- 238000012512 characterization method Methods 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 239000000460 chlorine Substances 0.000 description 1
- 229910052801 chlorine Inorganic materials 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 125000000422 delta-lactone group Chemical group 0.000 description 1
- 230000008021 deposition Effects 0.000 description 1
- 239000000975 dye Substances 0.000 description 1
- 230000032050 esterification Effects 0.000 description 1
- 238000005886 esterification reaction Methods 0.000 description 1
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 239000004744 fabric Substances 0.000 description 1
- 235000013305 food Nutrition 0.000 description 1
- 239000008233 hard water Substances 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 125000004435 hydrogen atom Chemical class [H]* 0.000 description 1
- 239000003112 inhibitor Substances 0.000 description 1
- 239000003999 initiator Substances 0.000 description 1
- 229910003002 lithium salt Inorganic materials 0.000 description 1
- 159000000002 lithium salts Chemical class 0.000 description 1
- 229950007687 macrogol ester Drugs 0.000 description 1
- 229910052749 magnesium Inorganic materials 0.000 description 1
- FPYJFEHAWHCUMM-UHFFFAOYSA-N maleic anhydride Chemical compound O=C1OC(=O)C=C1 FPYJFEHAWHCUMM-UHFFFAOYSA-N 0.000 description 1
- FQPSGWSUVKBHSU-UHFFFAOYSA-N methacrylamide Chemical compound CC(=C)C(N)=O FQPSGWSUVKBHSU-UHFFFAOYSA-N 0.000 description 1
- 125000005395 methacrylic acid group Chemical group 0.000 description 1
- YPHQUSNPXDGUHL-UHFFFAOYSA-N n-methylprop-2-enamide Chemical class CNC(=O)C=C YPHQUSNPXDGUHL-UHFFFAOYSA-N 0.000 description 1
- 230000003287 optical effect Effects 0.000 description 1
- 235000006408 oxalic acid Nutrition 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 150000003009 phosphonic acids Chemical class 0.000 description 1
- 150000003016 phosphoric acids Chemical class 0.000 description 1
- 239000000049 pigment Substances 0.000 description 1
- 230000000379 polymerizing effect Effects 0.000 description 1
- 125000001436 propyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 150000003254 radicals Chemical class 0.000 description 1
- FSYKKLYZXJSNPZ-UHFFFAOYSA-N sarcosine Chemical compound C[NH2+]CC([O-])=O FSYKKLYZXJSNPZ-UHFFFAOYSA-N 0.000 description 1
- 150000003333 secondary alcohols Chemical class 0.000 description 1
- 239000002002 slurry Substances 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 compound [Na+].[O-]OC([O-])=O MWNQXXOSWHCCOZ-UHFFFAOYSA-L 0.000 description 1
- 239000000243 solution Substances 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- BDHFUVZGWQCTTF-UHFFFAOYSA-M sulfonate Chemical group [O-]S(=O)=O BDHFUVZGWQCTTF-UHFFFAOYSA-M 0.000 description 1
- 238000006277 sulfonation reaction Methods 0.000 description 1
- 125000001273 sulfonato group Chemical group [O-]S(*)(=O)=O 0.000 description 1
- 239000004094 surface-active agent Substances 0.000 description 1
- 239000002562 thickening agent Substances 0.000 description 1
- OYLNLYLCJAXYAI-UHFFFAOYSA-K trisodium 2-(methylamino)acetate oxalate Chemical compound [Na+].[Na+].[Na+].C(C(=O)[O-])(=O)[O-].CNCC(=O)[O-] OYLNLYLCJAXYAI-UHFFFAOYSA-K 0.000 description 1
- 229920001567 vinyl ester resin Polymers 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
-
- 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
- C11D3/3776—Heterocyclic compounds, e.g. lactam
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F2/00—Processes of polymerisation
- C08F2/38—Polymerisation using regulators, e.g. chain terminating agents, e.g. telomerisation
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F8/00—Chemical modification by after-treatment
- C08F8/14—Esterification
- C08F8/16—Lactonisation
-
- 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
- C11D3/26—Organic compounds containing nitrogen
- C11D3/33—Amino carboxylic acids
-
- 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
-
- 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
- C11D7/00—Compositions of detergents based essentially on non-surface-active compounds
- C11D7/22—Organic compounds
- C11D7/32—Organic compounds containing nitrogen
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F2810/00—Chemical modification of a polymer
- C08F2810/40—Chemical modification of a polymer taking place solely at one end or both ends of the polymer backbone, i.e. not in the side or lateral chains
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Abstract
包含至少两种组分的自动洗盘洗涤剂组合物。第一种组分是一种聚合物，该聚合物包含至少一种C3-C6羧酸单体的聚合残基以及内酯端基。第二种组分是一种可生物降解的助洗剂，其选自次氨基三乙酸，乙二胺四乙酸，二亚乙基三胺五乙酸，甘氨酸-N，N-二乙酸，甲基甘氨酸-N，N-二乙酸，2-羟乙基亚氨基二乙酸，谷氨酸-N，N-二乙酸，3-羟基-2，2’-亚氨基二丁二酸盐，S，S-乙二胺二丁二酸盐天冬氨酸-二乙酸，N，N’-乙二胺二丁二酸，亚氨基二丁二酸，天冬氨酸，天冬氨酸-N，N-二乙酸盐，β-丙氨酸二乙酸，聚天冬氨酸，它们的盐和它们的组合。
Description
技术领域
本发明一般涉及能够将非磷酸盐或低磷酸盐自动洗盘系统中的混合无机沉积物减至最少的配制物。
背景技术
通常认为自动洗盘洗涤剂是完全不同于织物洗涤或水处理所用的洗涤剂的一类洗涤剂组合物。人们要求自动洗盘洗涤剂能够在完成清洁周期之后，在洗涤过的物品上获得极其清洁而且无膜的外观。无磷酸盐或低磷酸盐的组合物依赖于非磷酸盐的助洗剂，例如柠檬酸盐、碳酸盐、硅酸盐、焦硅酸盐、碳酸氢盐、氨基羧酸盐等，和与来自硬水中的钙和镁鳌合的其他试剂，在干燥的时候会留下不溶性的可见的沉积物。已知由(甲基)丙烯酸和马来酸制备的聚合物可用于抑制由非磷酸盐助洗剂产生的积垢或者其它不溶性沉积。例如，WO 2009/123322揭示了在包含可生物降解的助洗剂的组合物中使用由丙烯酸、马来酸和磺化单体制备的聚合物。但是，该参考文献没有揭示包含具有内酯端基的聚合物的组合物。
本发明所要解决的问题是找到一种能够减少混合无机沉积物的形成的组合物。
发明内容
本发明涉及一种自动洗盘洗涤剂组合物，该组合物包含：(a)一种聚合物，其包含至少一种C3-C6羧酸单体的聚合残基和内酯端基；(b)可生物降解的助洗剂，其选自下组：次氨基三乙酸，乙二胺四乙酸，二亚乙基三胺五乙酸，甘氨酸-N，N-二乙酸，甲基甘氨酸-N，N-二乙酸，2-羟乙基亚氨基二乙酸，谷氨酸-N，N-二乙酸，3-羟基-2，2’-亚氨基二丁二酸盐，S，S-乙二胺二丁二酸盐天冬氨酸-二乙 酸，N，N’-乙二胺二丁二酸，亚氨基二丁二酸，天冬氨酸，天冬氨酸-N，N-二乙酸盐，β-丙氨酸二乙酸，聚天冬氨酸，它们的盐和它们的组合。
具体实施方式
除非另外说明，否则，所有的百分数都是重量百分数(重量％)，所有的温度单位都是℃。本领域已知，重均分子量Mw是通过凝胶渗透色谱法(GPC)、使用聚丙烯酸标样测定的。GPC技术的详细讨论参见以下文献：《现代尺寸排阻色谱(Modern Size Exclusion Chromatography)》.W.W.Yau.J.J Kirkland.D.D.Bly；Wiley-Interscience.1979，以及《材料表征和化学分析指南(A Guide to Materials Characterization and Chemical Analysis)》，J.P.Sibilia；VCH，1988，第81-84页。本文报道的分子量的单位为道尔顿。在本文中，术语“(甲基)丙烯酸类”表示丙烯酸类或甲基丙烯酸类。较佳的是，所述可生物降解的助洗剂以钠盐、钾盐或锂盐的形式存在，优选是钠盐或钾盐，优选是钠盐。优选的可生物降解的助洗剂包括甘氨酸-N，N-二乙酸，甲基甘氨酸-N，N-二乙酸，2-羟乙基亚氨基二乙酸，聚天冬氨酸，亚氨基二丁二酸，3-羟基-2，2’-亚氨基二丁二酸盐，谷氨酸-N，N-二乙酸及其盐。较佳的是，所述组合物是“无磷的”，也就是说，所述组合物中的磷含量小于0.5重量％(以元素磷计)，优选小于0.2重量％，优选小于0.1重量％，优选无可检测到的磷。较佳的是，所述组合物是“低磷磷酸盐”，也就是说，该组合物中的磷含量为0.5-3重量％(以元素磷计)，优选为0.5-1.5重量％。较佳的是，所述组合物包含小于2重量％的低分子量(小于1,000)膦酸类化合物(phosphonate compounds)(例如1-羟基亚乙基-1，1-二膦酸(HEDP)，及其盐)，优选小于1重量％，优选小于0.5重量％，优选小于0.2重量％，优选小于0.1重量％。“C3-C6羧酸单体”是一种包含一个或两个羧酸基的单烯键式不饱和化合物，例如，(甲基)丙烯酸，马来酸，富马酸，衣康酸，马来酸酐，巴豆酸等。较佳的是，所述聚合物包含至少50重量％的至少一种C3-C6羧酸单体的聚合残基，优选至少60重量％，优选至少70重量％，优选至少80重量％，优选至少85重量％，优选至少90重量％，优选至少95重量％，优选至少98重量％，优选至少99重量％。较佳的是，所述C3-C6羧酸单体选自(甲基)丙 烯酸和马来酸，优选(甲基)丙烯酸，优选丙烯酸。
较佳的是，所述内酯端基是通过聚合的羧酸单体残基上的羧酸取代基与源自链转移剂的端羟基之间的内部酯化反应形成的，最经常是γ-内酯，如以下通式所示
式中A是包含(甲基)丙烯酸的聚合残基的聚合物链；R1和R2独立地可以是氢、甲基、乙基、丙基或丁基；前提是R1和R2总共包含至少两个碳原子。例如，当在丙烯酸聚合反应中将异丙醇用作链转移剂的时候，会在聚丙烯酸链上形成端羟基，该端羟基可以与羧酸反应，形成γ-内酯端基，如以下通式所示
较佳的是，对于聚丙烯酸，使用仲醇作为链转移剂，结果得到以下通式所示的一般γ-内酯端基。
使用大于异丙醇的醇作为链转移剂，可能会导致在不含羟基的碳原子上形成自由基而得到另外的结构，可能包含δ-内酯。
聚合物中可能存在的其它聚合单体残基包括例如非离子(甲基)丙烯酸酯，阳离子单体，单不饱和二羧酸盐/酯，饱和(甲基)丙烯酰胺，乙烯基酯，乙烯基酰胺(包括例如N-乙烯基吡咯烷酮)，磺化丙烯酸类单体，苯乙烯和 α-甲基苯乙烯。
所述组合物中的可生物降解的助洗剂的总重量占所述组合物总重量的2-40重量％。较佳的是，可生物降解的助洗剂的总重量至少为5重量％，优选至少为7重量％，优选至少为8重量％，优选至少为9重量％，优选至少为10重量％。较佳的是，所述可生物降解的助洗剂的总重量不大于35重量％，优选不大于30重量％，优选不大于25重量％，优选不大于20重量％，优选不大于17重量％，优选不大于15重量％，优选不大于14重量％，优选不大于13重量％，优选不大于12重量％。较佳的是，所述组合物还包含碱金属柠檬酸盐，碱金属碳酸盐，碱金属碳酸氢盐和/或碱金属氨基羧酸盐。较佳的是，所述碱金属柠檬酸盐的含量为0.01-40重量％，优选不大于35重量％，优选不大于30重量％，优选不大于25重量％，优选不大于20重量％。
较佳的是，所述聚合物包含不大于40重量％的丙烯酸酯或甲基丙烯酸酯的聚合残基，优选不大于30重量％，优选不大于20重量％，优选不大于10重量％，优选不大于5重量％，优选不大于2重量％，优选不大于1重量％，优选不大于0.5重量％。较佳的是，所述聚合物包含至少70重量％的选自(甲基)丙烯酸、马来酸、富马酸和衣康酸的单体的聚合残基，而且包含不大于30重量％的丙烯酸酯或甲基丙烯酸酯的聚合残基；优选包含至少80重量％的选自(甲基)丙烯酸、马来酸、富马酸和衣康酸的单体的聚合残基，而且包含不大于20重量％的丙烯酸酯或者甲基丙烯酸酯的聚合残基。较佳的是，所述聚合物包含不大于30摩尔％的2-丙烯酰氨-2-甲基丙磺酸(AMPS)(包括金属盐或铵盐)或者其它的磺酸丙烯酸类单体(例如烯丙氧基苯磺酸，甲代烯丙基磺酸和(甲基)烯丙氧基苯磺酸)，优选不大于20摩尔％，优选不大于10摩尔％，优选不大于5摩尔％，优选不大于2摩尔％，优选不大于1摩尔％，优选不大于0.5摩尔％。
较佳的是，所述聚合物的Mw为1,000-90,000。较佳的是，Mw至少为2,000，优选至少为3,000，优选至少为4,000，优选至少为5,000，优选至少为6,000。较佳的是，Mw不大于70,000，优选不大于50,000，优选不大于40,000，优选不大于30,000，优选不大于20,000，优选不大于15,000，优选不大于10,000。
所述聚合物可以与其它的可用来控制自动洗盘机中不溶性沉积物的聚合物结合使用，例如包含以下单体的残基的组合的聚合物：丙烯酸、甲基丙烯酸、 马来酸或其它二酸单体，包括聚乙二醇酯的丙烯酸酯或甲基丙烯酸酯，苯乙烯单体，AMPS和其它磺酸单体，以及取代的丙烯酰胺或甲基丙烯酰胺。
本发明的聚合物可以通过任何已知的用于丙烯酸类单体聚合的技术制备，例如溶液聚合和乳液聚合；优选溶液聚合。较佳的是，引发剂不含磷。较佳的是，所述聚合物的磷含量小于1重量％，优选小于0.5重量％，优选小于0.1重量％，优选所述聚合物不含磷。所述链转移剂包括醇，优选异丙醇。所述聚合物可以是以下的形式：水溶性溶液聚合物，浆液，干粉末或者颗粒或其它固体形式。
所述自动洗盘洗涤剂组合物的其它组分可以包括例如表面活性剂，氧和/或氯漂白剂，漂白活化剂，酶，消泡剂，颜料，香料，抗菌剂和填料。常规的表面活性剂含量取决于所用的具体表面活性剂，通常为0.1-10重量％，优选为0.5-5重量％。片状或粉末中的填料是惰性的水溶性物质，通常是钠盐或钾盐，例如硫酸钠或硫酸钾以及/或者氯化钠或氯化钾，通常含量为0-75重量％，优选为5-50重量％，优选为10-40重量％。凝胶配制物中的填料可以包括上述的那些以及水。香料、染料、消泡剂、酶、腐蚀抑制剂和抗菌剂的总量通常不大于组合物的5重量％。
较佳的是，所述组合物包含5-20重量％的过碳酸盐，优选8-15重量％，优选10-15重量％。较佳的是，所述组合物的pH值(在水中的含量为1重量％)至少为9，优选至少为10.5；优选pH值不大于12.5，优选不大于11.5。
所述组合物可以以任意常规的形式，例如小片，粉末，单剂量，多组分单剂量，小袋，糊料，液体或凝胶按配方配制。对于任何常规自动洗盘机所述组合物可以常规操作条件下使用。通常在洗涤过程中的水温优选为20℃至85℃，优选为30℃至70℃。组合物在洗盘机中占全部液体的浓度百分数优选为0.1-1重量％，优选为0.2-0.7重量％。通过选择合适的产品形式和加入时间，所述组合物可以在以下情况下存在：预洗，主要洗涤，倒数第二次漂洗，最后漂洗，或者这些周期的任意组合。在所述洗盘洗涤剂中，本发明的聚合物可以以很多的方式配制。例如，可以用无机助洗剂、可生物降解的助洗剂、填料、表面活性剂、漂白剂、酶等配制所述聚合物。或者，例如，所述聚合物可以用表面活性剂、柠檬酸、溶剂和其它任选的组分配制。 另外，所述聚合物可以位于设计的单元剂量产品中的一个或多个间隔部分中，以便在洗涤周期的过程中在与可生物降解的助洗剂不同的时间释放。
较佳的是，所述组合物包含0.5-12重量％的所述聚合物。较佳的是，所述组合物包含至少1重量％的聚合物，优选至少1.5重量％，优选至少2重量％，优选至少2.5重量％。较佳的是，所述组合物包含不大于10重量％的所述聚合物，优选不大于8重量％，优选不大于6重量％，优选不大于5重量％，优选不大于4重量％。本发明的聚合物可以与由磺酸单体制备的聚合物掺混。
实施例
聚合物测试-通过以下方式测定所有聚合物减少积垢的性质：如下文所述将这些聚合物与下文所述的“Prototype1F”混合，在KENMORE QUIETGUARD洗盘机(在主要洗涤周期加入固体)中，使用硬度为400ppm(2∶1 Ca+2∶Mg+2)的水，在130℉(54.4℃)、无食物污渍的条件下对玻璃洗涤五个周期。根据ASTM方法3556-85的标准，在3个周期和5个周期之后对玻璃进行评价(1＝清洁，5＝厚膜)。
结果-在各个实验中，将3.2克活性甲基甘氨酸二乙酸三钠盐与28克配制物Prototype1F一起加入。
TRILON M是购自巴斯夫公司(BASF Corp.)的甲基甘氨酸二乙酸三钠盐的水溶液
聚合物样品：
比较聚合物A(Mw＝2220)＝90％丙烯酸/10％马来酸，钠盐膦酰端基。
比较聚合物B(Mw＝7,201)100％的包含磺酸盐端基的丙烯酸聚合物。
ANTIPREX A(购自希巴公司(Ciba Corp.))(Mw＝6,877)100％的丙烯酸聚合物，其包含具有成对甲基的γ-内酯端基。
比较聚合物C(Mw 22,974)70％的丙烯酸/30％的包含磺酸盐端基的2-丙烯酰氨-2-甲基-1-丙磺酸钠盐。
比较聚合物A在50％固体＝0.8克活性物质的条件以湿的1.6克/周期的量加入，
比较聚合物B在45.53％固体＝0.8克活性物质的条件以湿的1.78克/周期的量加入
聚合物A在39.7％固体＝0.8克活性物质的条件以湿的2.02克/周期的量加入
比较聚合物C在37％固体＝0.8克活性物质的条件以湿的2.16克/周期的量加入。
Claims (10)
1.一种自动洗盘洗涤剂组合物，其包含：(a)一种聚合物，其包含至少一种C3-C6羧酸单体的聚合残基和内酯端基；(b)可生物降解的助洗剂，其选自下组：次氨基三乙酸，乙二胺四乙酸，二亚乙基三胺五乙酸，甘氨酸-N，N-二乙酸，甲基甘氨酸-N，N-二乙酸，2-羟乙基亚氨基二乙酸，谷氨酸-N，N-二乙酸，3-羟基-2，2’-亚氨基二丁二酸盐，S，S-乙二胺二丁二酸盐天冬氨酸-二乙酸，N，N’-乙二胺二丁二酸，亚氨基二丁二酸，天冬氨酸，天冬氨酸-N，N-二乙酸盐，β-丙氨酸二乙酸，聚天冬氨酸，它们的盐和它们的组合。
2.如权利要求1所述的组合物，其中，所述聚合物包含至少50重量％的至少一种C3-C6羧酸单体的聚合残基。
3.如权利要求2所述的组合物，其中，所述内酯端基是γ-内酯。
4.如权利要求3所述的组合物，其中，所述聚合物的Mw为2,000-40,000。
5.如权利要求4所述的组合物，其中，该组合物包含1-8重量％的所述聚合物。
6.如权利要求5所述的组合物，其中，所述聚合物的化学式为
式中，A是包含至少一种C3-C6羧酸单体的聚合残基的聚合物链；R1和R2是甲基。
7.如权利要求6所述的组合物，其中，所述组合物包含5-20重量％的可生物降解的助洗剂。
8.如权利要求7所述的组合物，其中，所述聚合物包含至少70重量％的选自(甲基)丙烯酸和马来酸的至少一种单体的聚合残基。
9.如权利要求8所述的组合物，其中，所述聚合物的Mw为4,000-30,000。
10.如权利要求9所述的组合物，其中，所述组合物包含甲基甘氨酸-N，N-二乙酸，甘氨酸-N，N-二乙酸，谷氨酸-N，N-二乙酸，它们的盐或者它们的组合。
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| US31192010P | 2010-03-09 | 2010-03-09 | |
| US61/311,920 | 2010-03-09 |
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| CN102220186A true CN102220186A (zh) | 2011-10-19 |
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| CN201110063246XA Pending CN102220186A (zh) | 2010-03-09 | 2011-03-07 | 用于自动洗盘系统的减少积垢的添加剂 |
Country Status (12)
| Country | Link |
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| US (1) | US8283301B2 (zh) |
| EP (1) | EP2366768B1 (zh) |
| JP (1) | JP5377536B2 (zh) |
| KR (1) | KR101275641B1 (zh) |
| CN (1) | CN102220186A (zh) |
| AR (1) | AR080440A1 (zh) |
| AU (1) | AU2011200671B2 (zh) |
| BR (1) | BRPI1101075A2 (zh) |
| CA (1) | CA2731831C (zh) |
| MX (1) | MX2011001861A (zh) |
| TW (1) | TWI438272B (zh) |
| ZA (1) | ZA201101767B (zh) |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2014063359A1 (en) * | 2012-10-26 | 2014-05-01 | Rohm And Haas Company | Dissolvable aqueous gels with high chelant loading |
| CN111032844A (zh) * | 2017-08-30 | 2020-04-17 | 陶氏环球技术有限责任公司 | 含分散剂聚合物的自动洗碗组合物 |
| CN111278959A (zh) * | 2017-11-15 | 2020-06-12 | 陶氏环球技术有限责任公司 | 用于自动餐具配制物的分散剂聚合物 |
Families Citing this family (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105992813B (zh) * | 2014-02-20 | 2019-01-29 | 荷兰联合利华有限公司 | 机洗餐具组合物 |
| US9920288B2 (en) | 2014-07-11 | 2018-03-20 | Diversey, Inc. | Tablet dishwashing detergent and methods for making and using the same |
| US9139799B1 (en) | 2014-07-11 | 2015-09-22 | Diversey, Inc. | Scale-inhibition compositions and methods of making and using the same |
| CA3192947C (en) | 2015-04-29 | 2025-08-05 | Shutterfly, Llc | CREATION OF IMAGE PRODUCTS BASED ON GROUPED FACE IMAGES USING IMAGE PRODUCT STATISTICS |
| EP3790951B1 (en) * | 2018-05-09 | 2022-04-13 | Dow Global Technologies, LLC | Automatic dishwashing composition with dispersant polymer |
| JP2023533444A (ja) * | 2020-06-24 | 2023-08-03 | ダウ グローバル テクノロジーズ エルエルシー | 生分解性再付着防止剤を含む洗濯洗剤配合物 |
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| US3579455A (en) * | 1968-08-02 | 1971-05-18 | Grace W R & Co | Machine dishwashing compositions containing sodium polyacrylate |
| US4176059A (en) * | 1978-06-08 | 1979-11-27 | Quatic Chemicals Limited | Anti-corrosion composition for use in aqueous systems |
| CN101018849A (zh) * | 2004-09-14 | 2007-08-15 | 巴斯福股份公司 | 用于洗碟机的含有疏水改性聚羧酸盐的洗涤剂配料 |
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| GB771791A (en) * | 1952-01-23 | 1957-04-03 | Diversey Corp | Improvements in or relating to a washing method |
| DE3720806C2 (de) * | 1986-07-03 | 1997-08-21 | Clariant Finance Bvi Ltd | Verwendung eines Stabilisators in Peroxydbleichverfahren |
| FR2613736A1 (fr) * | 1987-04-09 | 1988-10-14 | Sandoz Sa | Procede de lavage des matieres textiles |
| JPH0826349B2 (ja) * | 1989-06-20 | 1996-03-13 | 日華化学株式会社 | 洗浄性向上剤 |
| JPH108092A (ja) * | 1996-06-21 | 1998-01-13 | Mitsubishi Paper Mills Ltd | 過酸化物漂白用安定化剤及びそれを用いた繊維系物質の漂白方法 |
| JP2006183024A (ja) * | 2004-11-30 | 2006-07-13 | Kumano Yushi Kk | 自動食器洗い機用洗浄剤 |
| DE102005041347A1 (de) * | 2005-08-31 | 2007-03-01 | Basf Ag | Reinigungsformulierungen für die maschinelle Geschirrreinigung enthaltend hydrophil modifizierte Polycarboxylate |
| CA2660193A1 (en) * | 2006-08-10 | 2008-02-14 | Basf Se | Detergent formulation for machine dishwashers |
| US8389458B2 (en) | 2008-03-31 | 2013-03-05 | The Procter & Gamble Company | Automatic dishwashing composition containing a sulfonated copolymer |
-
2011
- 2011-02-10 JP JP2011026961A patent/JP5377536B2/ja not_active Expired - Fee Related
- 2011-02-14 EP EP11154273.4A patent/EP2366768B1/en active Active
- 2011-02-16 CA CA2731831A patent/CA2731831C/en active Active
- 2011-02-16 AU AU2011200671A patent/AU2011200671B2/en not_active Ceased
- 2011-02-17 MX MX2011001861A patent/MX2011001861A/es active IP Right Grant
- 2011-02-24 TW TW100106147A patent/TWI438272B/zh not_active IP Right Cessation
- 2011-03-02 AR ARP110100637A patent/AR080440A1/es active IP Right Grant
- 2011-03-04 BR BRPI1101075-4A patent/BRPI1101075A2/pt not_active IP Right Cessation
- 2011-03-07 CN CN201110063246XA patent/CN102220186A/zh active Pending
- 2011-03-08 ZA ZA2011/01767A patent/ZA201101767B/en unknown
- 2011-03-08 KR KR1020110020334A patent/KR101275641B1/ko not_active Expired - Fee Related
- 2011-03-08 US US12/932,860 patent/US8283301B2/en active Active
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3579455A (en) * | 1968-08-02 | 1971-05-18 | Grace W R & Co | Machine dishwashing compositions containing sodium polyacrylate |
| US4176059A (en) * | 1978-06-08 | 1979-11-27 | Quatic Chemicals Limited | Anti-corrosion composition for use in aqueous systems |
| CN101018849A (zh) * | 2004-09-14 | 2007-08-15 | 巴斯福股份公司 | 用于洗碟机的含有疏水改性聚羧酸盐的洗涤剂配料 |
Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2014063359A1 (en) * | 2012-10-26 | 2014-05-01 | Rohm And Haas Company | Dissolvable aqueous gels with high chelant loading |
| CN104937091A (zh) * | 2012-10-26 | 2015-09-23 | 罗门哈斯公司 | 具有高螯合剂负载的可溶性含水凝胶 |
| CN104937091B (zh) * | 2012-10-26 | 2017-10-20 | 罗门哈斯公司 | 具有高螯合剂负载的可溶性含水凝胶 |
| CN111032844A (zh) * | 2017-08-30 | 2020-04-17 | 陶氏环球技术有限责任公司 | 含分散剂聚合物的自动洗碗组合物 |
| CN111032844B (zh) * | 2017-08-30 | 2021-08-03 | 陶氏环球技术有限责任公司 | 含分散剂聚合物的自动洗碗组合物 |
| CN111278959A (zh) * | 2017-11-15 | 2020-06-12 | 陶氏环球技术有限责任公司 | 用于自动餐具配制物的分散剂聚合物 |
Also Published As
| Publication number | Publication date |
|---|---|
| AU2011200671A1 (en) | 2011-09-22 |
| AU2011200671B2 (en) | 2015-02-26 |
| JP2011190435A (ja) | 2011-09-29 |
| US8283301B2 (en) | 2012-10-09 |
| CA2731831C (en) | 2013-12-03 |
| MX2011001861A (es) | 2011-09-21 |
| US20110224119A1 (en) | 2011-09-15 |
| ZA201101767B (en) | 2011-11-30 |
| CA2731831A1 (en) | 2011-09-09 |
| KR20110102214A (ko) | 2011-09-16 |
| EP2366768B1 (en) | 2013-08-07 |
| KR101275641B1 (ko) | 2013-06-17 |
| EP2366768A1 (en) | 2011-09-21 |
| AR080440A1 (es) | 2012-04-11 |
| JP5377536B2 (ja) | 2013-12-25 |
| BRPI1101075A2 (pt) | 2012-11-27 |
| TW201132753A (en) | 2011-10-01 |
| TWI438272B (zh) | 2014-05-21 |
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