EP0625567A2 - Agent de nettoyage sous phosphate pour le lavage de la vaisselle en machine - Google Patents
Agent de nettoyage sous phosphate pour le lavage de la vaisselle en machine Download PDFInfo
- Publication number
- EP0625567A2 EP0625567A2 EP94105346A EP94105346A EP0625567A2 EP 0625567 A2 EP0625567 A2 EP 0625567A2 EP 94105346 A EP94105346 A EP 94105346A EP 94105346 A EP94105346 A EP 94105346A EP 0625567 A2 EP0625567 A2 EP 0625567A2
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- EP
- European Patent Office
- Prior art keywords
- weight
- formulations according
- contained
- formulations
- phosphate
- 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.)
- Granted
Links
- 238000004851 dishwashing Methods 0.000 title claims abstract description 14
- 239000003599 detergent Substances 0.000 title claims description 15
- 239000000203 mixture Substances 0.000 claims abstract description 41
- 238000009472 formulation Methods 0.000 claims abstract description 33
- 229920001577 copolymer Polymers 0.000 claims abstract description 21
- 239000003513 alkali Substances 0.000 claims abstract description 11
- 239000002270 dispersing agent Substances 0.000 claims abstract description 8
- 239000008139 complexing agent Substances 0.000 claims abstract description 7
- 239000004094 surface-active agent Substances 0.000 claims abstract description 7
- 239000000654 additive Substances 0.000 claims abstract description 6
- 238000005187 foaming Methods 0.000 claims abstract description 6
- 239000000178 monomer Substances 0.000 claims description 23
- 239000000126 substance Substances 0.000 claims description 9
- 150000003839 salts Chemical class 0.000 claims description 5
- 150000001991 dicarboxylic acids Chemical class 0.000 claims description 4
- 238000007127 saponification reaction Methods 0.000 claims description 4
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical group [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 3
- 230000007062 hydrolysis Effects 0.000 claims description 3
- 238000006460 hydrolysis reaction Methods 0.000 claims description 3
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims description 3
- 150000002763 monocarboxylic acids Chemical class 0.000 claims description 3
- 238000006116 polymerization reaction Methods 0.000 claims description 3
- 239000000047 product Substances 0.000 description 11
- 229910019142 PO4 Inorganic materials 0.000 description 9
- 235000021317 phosphate Nutrition 0.000 description 9
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 description 7
- NIXOWILDQLNWCW-UHFFFAOYSA-N 2-Propenoic acid Natural products OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 7
- 238000004140 cleaning Methods 0.000 description 7
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 description 7
- 239000010452 phosphate Substances 0.000 description 7
- -1 alkali metal triphosphate Chemical class 0.000 description 6
- 229920005646 polycarboxylate Polymers 0.000 description 6
- VZCYOOQTPOCHFL-UHFFFAOYSA-N trans-butenedioic acid Natural products OC(=O)C=CC(O)=O VZCYOOQTPOCHFL-UHFFFAOYSA-N 0.000 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 description 5
- OFOBLEOULBTSOW-UHFFFAOYSA-N Propanedioic acid Natural products OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 0.000 description 5
- 239000012459 cleaning agent Substances 0.000 description 5
- VZCYOOQTPOCHFL-UPHRSURJSA-N maleic acid Chemical compound OC(=O)\C=C/C(O)=O VZCYOOQTPOCHFL-UPHRSURJSA-N 0.000 description 5
- HEMHJVSKTPXQMS-UHFFFAOYSA-M sodium hydroxide Inorganic materials [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 5
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 5
- 102000004190 Enzymes Human genes 0.000 description 4
- 108090000790 Enzymes Proteins 0.000 description 4
- ABLZXFCXXLZCGV-UHFFFAOYSA-N Phosphorous acid Chemical class OP(O)=O ABLZXFCXXLZCGV-UHFFFAOYSA-N 0.000 description 4
- 150000003863 ammonium salts Chemical class 0.000 description 4
- 239000003795 chemical substances by application Substances 0.000 description 4
- 230000000052 comparative effect Effects 0.000 description 4
- 229940088598 enzyme Drugs 0.000 description 4
- 239000006260 foam Substances 0.000 description 4
- 239000011976 maleic acid Substances 0.000 description 4
- 229920000058 polyacrylate Polymers 0.000 description 4
- 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 4
- JAHNSTQSQJOJLO-UHFFFAOYSA-N 2-(3-fluorophenyl)-1h-imidazole Chemical compound FC1=CC=CC(C=2NC=CN=2)=C1 JAHNSTQSQJOJLO-UHFFFAOYSA-N 0.000 description 3
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 3
- CERQOIWHTDAKMF-UHFFFAOYSA-N Methacrylic acid Chemical compound CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 description 3
- 239000012190 activator Substances 0.000 description 3
- 229910052910 alkali metal silicate Inorganic materials 0.000 description 3
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 3
- 239000007844 bleaching agent Substances 0.000 description 3
- 239000000460 chlorine Substances 0.000 description 3
- 229910052801 chlorine Inorganic materials 0.000 description 3
- LVHBHZANLOWSRM-UHFFFAOYSA-N methylenebutanedioic acid Natural products OC(=O)CC(=C)C(O)=O LVHBHZANLOWSRM-UHFFFAOYSA-N 0.000 description 3
- MGFYIUFZLHCRTH-UHFFFAOYSA-N nitrilotriacetic acid Chemical compound OC(=O)CN(CC(O)=O)CC(O)=O MGFYIUFZLHCRTH-UHFFFAOYSA-N 0.000 description 3
- 229910052760 oxygen Inorganic materials 0.000 description 3
- 239000001301 oxygen Substances 0.000 description 3
- 239000002245 particle Substances 0.000 description 3
- 229920000642 polymer Polymers 0.000 description 3
- CDBYLPFSWZWCQE-UHFFFAOYSA-L sodium carbonate Substances [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 3
- 102000013142 Amylases Human genes 0.000 description 2
- 108010065511 Amylases Proteins 0.000 description 2
- 239000004606 Fillers/Extenders Substances 0.000 description 2
- VZCYOOQTPOCHFL-OWOJBTEDSA-N Fumaric acid Chemical compound OC(=O)\C=C\C(O)=O VZCYOOQTPOCHFL-OWOJBTEDSA-N 0.000 description 2
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 2
- 102000035195 Peptidases Human genes 0.000 description 2
- 108091005804 Peptidases Proteins 0.000 description 2
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 description 2
- 239000004365 Protease Substances 0.000 description 2
- 244000269722 Thea sinensis Species 0.000 description 2
- XTXRWKRVRITETP-UHFFFAOYSA-N Vinyl acetate Chemical compound CC(=O)OC=C XTXRWKRVRITETP-UHFFFAOYSA-N 0.000 description 2
- 229910052783 alkali metal Inorganic materials 0.000 description 2
- 150000001447 alkali salts Chemical class 0.000 description 2
- XXROGKLTLUQVRX-UHFFFAOYSA-N allyl alcohol Chemical compound OCC=C XXROGKLTLUQVRX-UHFFFAOYSA-N 0.000 description 2
- 235000019418 amylase Nutrition 0.000 description 2
- 229940025131 amylases Drugs 0.000 description 2
- 239000007864 aqueous solution Substances 0.000 description 2
- 230000015556 catabolic process Effects 0.000 description 2
- 150000001860 citric acid derivatives Chemical class 0.000 description 2
- 150000001875 compounds Chemical class 0.000 description 2
- 239000000470 constituent Substances 0.000 description 2
- 238000006731 degradation reaction Methods 0.000 description 2
- 239000010794 food waste Substances 0.000 description 2
- 239000008187 granular material Substances 0.000 description 2
- 229920001519 homopolymer Polymers 0.000 description 2
- 239000007788 liquid Substances 0.000 description 2
- FPYJFEHAWHCUMM-UHFFFAOYSA-N maleic anhydride Chemical compound O=C1OC(=O)C=C1 FPYJFEHAWHCUMM-UHFFFAOYSA-N 0.000 description 2
- 239000002736 nonionic surfactant Substances 0.000 description 2
- 150000003013 phosphoric acid derivatives Chemical class 0.000 description 2
- 229910052700 potassium Inorganic materials 0.000 description 2
- 239000011591 potassium Substances 0.000 description 2
- 238000010526 radical polymerization reaction Methods 0.000 description 2
- 229910052708 sodium Inorganic materials 0.000 description 2
- 239000011734 sodium Substances 0.000 description 2
- 229910000029 sodium carbonate Inorganic materials 0.000 description 2
- 239000001509 sodium citrate Substances 0.000 description 2
- 229960001922 sodium perborate Drugs 0.000 description 2
- YKLJGMBLPUQQOI-UHFFFAOYSA-M sodium;oxidooxy(oxo)borane Chemical compound [Na+].[O-]OB=O YKLJGMBLPUQQOI-UHFFFAOYSA-M 0.000 description 2
- 238000001694 spray drying Methods 0.000 description 2
- HRXKRNGNAMMEHJ-UHFFFAOYSA-K trisodium citrate Chemical compound [Na+].[Na+].[Na+].[O-]C(=O)CC(O)(CC([O-])=O)C([O-])=O HRXKRNGNAMMEHJ-UHFFFAOYSA-K 0.000 description 2
- 238000005406 washing Methods 0.000 description 2
- REWARORKCPYWIH-UHFFFAOYSA-N 1-(prop-2-enoylamino)butan-2-ylphosphonic acid Chemical compound CCC(P(O)(O)=O)CNC(=O)C=C REWARORKCPYWIH-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
- KEZYHIPQRGTUDU-UHFFFAOYSA-N 2-[dithiocarboxy(methyl)amino]acetic acid Chemical compound SC(=S)N(C)CC(O)=O KEZYHIPQRGTUDU-UHFFFAOYSA-N 0.000 description 1
- VUIWJRYTWUGOOF-UHFFFAOYSA-N 2-ethenoxyethanol Chemical compound OCCOC=C VUIWJRYTWUGOOF-UHFFFAOYSA-N 0.000 description 1
- WROUWQQRXUBECT-UHFFFAOYSA-N 2-ethylacrylic acid Chemical compound CCC(=C)C(O)=O WROUWQQRXUBECT-UHFFFAOYSA-N 0.000 description 1
- PSZAEHPBBUYICS-UHFFFAOYSA-N 2-methylidenepropanedioic acid Chemical compound OC(=O)C(=C)C(O)=O PSZAEHPBBUYICS-UHFFFAOYSA-N 0.000 description 1
- AGBXYHCHUYARJY-UHFFFAOYSA-N 2-phenylethenesulfonic acid Chemical compound OS(=O)(=O)C=CC1=CC=CC=C1 AGBXYHCHUYARJY-UHFFFAOYSA-N 0.000 description 1
- YYPNJNDODFVZLE-UHFFFAOYSA-N 3-methylbut-2-enoic acid Chemical compound CC(C)=CC(O)=O YYPNJNDODFVZLE-UHFFFAOYSA-N 0.000 description 1
- OFNISBHGPNMTMS-UHFFFAOYSA-N 3-methylideneoxolane-2,5-dione Chemical compound C=C1CC(=O)OC1=O OFNISBHGPNMTMS-UHFFFAOYSA-N 0.000 description 1
- BUPLCMMXKFWTTA-UHFFFAOYSA-N 4-methylidene-1,3-dioxetan-2-one Chemical compound C=C1OC(=O)O1 BUPLCMMXKFWTTA-UHFFFAOYSA-N 0.000 description 1
- XSVSPKKXQGNHMD-UHFFFAOYSA-N 5-bromo-3-methyl-1,2-thiazole Chemical compound CC=1C=C(Br)SN=1 XSVSPKKXQGNHMD-UHFFFAOYSA-N 0.000 description 1
- 241000894006 Bacteria Species 0.000 description 1
- GAWIXWVDTYZWAW-UHFFFAOYSA-N C[CH]O Chemical group C[CH]O GAWIXWVDTYZWAW-UHFFFAOYSA-N 0.000 description 1
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 description 1
- HETCEOQFVDFGSY-UHFFFAOYSA-N Isopropenyl acetate Chemical compound CC(=C)OC(C)=O HETCEOQFVDFGSY-UHFFFAOYSA-N 0.000 description 1
- 102000004882 Lipase Human genes 0.000 description 1
- 108090001060 Lipase Proteins 0.000 description 1
- 239000004367 Lipase Substances 0.000 description 1
- 238000012356 Product development Methods 0.000 description 1
- 229920002125 Sokalan® Polymers 0.000 description 1
- 244000300264 Spinacia oleracea Species 0.000 description 1
- 235000009337 Spinacia oleracea Nutrition 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 229910001854 alkali hydroxide Inorganic materials 0.000 description 1
- 150000008044 alkali metal hydroxides Chemical class 0.000 description 1
- 229910001420 alkaline earth metal ion Inorganic materials 0.000 description 1
- 125000000217 alkyl group Chemical group 0.000 description 1
- 150000008064 anhydrides Chemical class 0.000 description 1
- 239000012736 aqueous medium Substances 0.000 description 1
- 229920002988 biodegradable polymer Polymers 0.000 description 1
- 239000004621 biodegradable polymer Substances 0.000 description 1
- 238000004061 bleaching Methods 0.000 description 1
- PVEOYINWKBTPIZ-UHFFFAOYSA-N but-3-enoic acid Chemical compound OC(=O)CC=C PVEOYINWKBTPIZ-UHFFFAOYSA-N 0.000 description 1
- 150000004649 carbonic acid derivatives Chemical class 0.000 description 1
- 230000000536 complexating effect Effects 0.000 description 1
- 238000007334 copolymerization reaction Methods 0.000 description 1
- MSJMDZAOKORVFC-UAIGNFCESA-L disodium maleate Chemical compound [Na+].[Na+].[O-]C(=O)\C=C/C([O-])=O MSJMDZAOKORVFC-UAIGNFCESA-L 0.000 description 1
- VTIIJXUACCWYHX-UHFFFAOYSA-L disodium;carboxylatooxy carbonate Chemical compound [Na+].[Na+].[O-]C(=O)OOC([O-])=O VTIIJXUACCWYHX-UHFFFAOYSA-L 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- 230000035622 drinking Effects 0.000 description 1
- 239000003651 drinking water Substances 0.000 description 1
- 235000020188 drinking water Nutrition 0.000 description 1
- 239000000975 dye Substances 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- UIWXSTHGICQLQT-UHFFFAOYSA-N ethenyl propanoate Chemical compound CCC(=O)OC=C UIWXSTHGICQLQT-UHFFFAOYSA-N 0.000 description 1
- 229940071106 ethylenediaminetetraacetate Drugs 0.000 description 1
- 238000012851 eutrophication Methods 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 150000002191 fatty alcohols Chemical class 0.000 description 1
- 239000000945 filler Substances 0.000 description 1
- 239000003205 fragrance Substances 0.000 description 1
- 239000001530 fumaric acid Substances 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- 150000002334 glycols Chemical class 0.000 description 1
- 159000000011 group IA salts Chemical class 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
- 239000004615 ingredient Substances 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- 235000021190 leftovers Nutrition 0.000 description 1
- 235000019421 lipase Nutrition 0.000 description 1
- 239000012669 liquid formulation Substances 0.000 description 1
- 239000012263 liquid product Substances 0.000 description 1
- 229910052749 magnesium Inorganic materials 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 239000003264 margarine Substances 0.000 description 1
- 235000013310 margarine Nutrition 0.000 description 1
- 235000013372 meat Nutrition 0.000 description 1
- 229910021645 metal ion Inorganic materials 0.000 description 1
- MYWUZJCMWCOHBA-VIFPVBQESA-N methamphetamine Chemical compound CN[C@@H](C)CC1=CC=CC=C1 MYWUZJCMWCOHBA-VIFPVBQESA-N 0.000 description 1
- XJRBAMWJDBPFIM-UHFFFAOYSA-N methyl vinyl ether Chemical compound COC=C XJRBAMWJDBPFIM-UHFFFAOYSA-N 0.000 description 1
- 235000013336 milk Nutrition 0.000 description 1
- 239000008267 milk Substances 0.000 description 1
- 210000004080 milk Anatomy 0.000 description 1
- 235000011837 pasties Nutrition 0.000 description 1
- HVAMZGADVCBITI-UHFFFAOYSA-N pent-4-enoic acid Chemical compound OC(=O)CCC=C HVAMZGADVCBITI-UHFFFAOYSA-N 0.000 description 1
- 229920001515 polyalkylene glycol Chemical class 0.000 description 1
- 229920001521 polyalkylene glycol ether Polymers 0.000 description 1
- 230000008092 positive effect Effects 0.000 description 1
- UIIIBRHUICCMAI-UHFFFAOYSA-N prop-2-ene-1-sulfonic acid Chemical compound OS(=O)(=O)CC=C UIIIBRHUICCMAI-UHFFFAOYSA-N 0.000 description 1
- VEYCPJGKKJULEP-UHFFFAOYSA-N prop-2-enoic acid sulfuric acid Chemical class OC(=O)C=C.OS(O)(=O)=O VEYCPJGKKJULEP-UHFFFAOYSA-N 0.000 description 1
- RZKYDQNMAUSEDZ-UHFFFAOYSA-N prop-2-enylphosphonic acid Chemical compound OP(O)(=O)CC=C RZKYDQNMAUSEDZ-UHFFFAOYSA-N 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 239000010865 sewage Substances 0.000 description 1
- 150000004760 silicates Chemical class 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
- 229960000999 sodium citrate dihydrate Drugs 0.000 description 1
- 229940045872 sodium percarbonate Drugs 0.000 description 1
- 229910052938 sodium sulfate Inorganic materials 0.000 description 1
- 235000011152 sodium sulphate Nutrition 0.000 description 1
- 239000002689 soil Substances 0.000 description 1
- 239000007921 spray Substances 0.000 description 1
- 238000005507 spraying Methods 0.000 description 1
- QAOWNCQODCNURD-UHFFFAOYSA-L sulfate group Chemical group S(=O)(=O)([O-])[O-] QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 description 1
- 125000001174 sulfone group Chemical group 0.000 description 1
- 239000002352 surface water Substances 0.000 description 1
- 150000003892 tartrate salts Chemical class 0.000 description 1
- 239000001226 triphosphate Substances 0.000 description 1
- 235000011178 triphosphate Nutrition 0.000 description 1
- 229940038773 trisodium citrate Drugs 0.000 description 1
- ZTWTYVWXUKTLCP-UHFFFAOYSA-N vinylphosphonic acid Chemical compound OP(O)(=O)C=C ZTWTYVWXUKTLCP-UHFFFAOYSA-N 0.000 description 1
- NLVXSWCKKBEXTG-UHFFFAOYSA-N vinylsulfonic acid Chemical compound OS(=O)(=O)C=C NLVXSWCKKBEXTG-UHFFFAOYSA-N 0.000 description 1
- 239000002351 wastewater Substances 0.000 description 1
- 239000001993 wax Substances 0.000 description 1
- 238000009736 wetting Methods 0.000 description 1
- 239000010457 zeolite Substances 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
- C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
- C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
- C11D3/16—Organic compounds
- C11D3/37—Polymers
- C11D3/3746—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
Definitions
- the invention relates to phosphate-free cleaning agents with improved biodegradability for machine dishwashing.
- Machine dishwashers have the task of cleaning leftovers from dishes, cutlery, glasses, kitchen appliances, etc. to remove.
- the cleaning agent must promote wetting of the surfaces to be cleaned and water-insoluble dirt particles must be dispersed and emulsified in the washing liquor.
- the cleaner must suppress the foam caused by food residues, largely prevent visible stains from remaining on the wash ware, remove coffee and tea stains, prevent the build-up of dirt films on the surface of dishes and glassware, bind the water hardness-forming substances from water and food residues and Destroy bacteria.
- Conventional detergents for dishwashers are strongly alkaline agents and essentially consist of the components alkali metal triphosphate, alkali metal silicate and alkali carbonate.
- non-foaming surfactants, fillers and chlorine releasers are used.
- Such cleaning agents are described, for example, in the Tensid paperback, published by H. Stache, Carl Hanser Verlag, Kunststoff, Vienna (1981).
- phosphate-free dishwashing detergents with reduced alkalinity has recently been developed, which often also does without the use of chlorine-releasing substances.
- These "mild" dishwashing detergents are usually based on trisodium citrate combined with polycarboxylates as the most important phosphate substitute.
- the products contain low-foaming nonionic surfactants, enzymes, oxygen-based bleaches (e.g. sodium perborate) and bleach activators such as.
- B. Tetraacetylethylenediamine Tetraacetylethylenediamine.
- phosphate substitutes did not show sufficient cleanability, other substances, such as. B. EDTA, are used little for ecological reasons.
- polycarboxylates in particular homopolymers of acrylic acid and copolymers of acrylic acid and maleic acid, have proven to be suitable phosphate substitutes and are used today in commercially available cleaning agents.
- dishwashing detergents containing polycarboxylates have only a low biodegradability and are therefore only mineralized to a small extent in the sewage treatment plant.
- the formulations contain component a, the copolymers, to 1 to 60% by weight, preferably to 2 to 30% by weight, proportions of 2 to 15% by weight being very particularly preferably set.
- Monomers of group A are monoethylenically unsaturated C4-C8 dicarboxylic acids, their anhydrides or their alkali and / or ammonium salts and / or amine salts.
- Suitable dicarboxylic acids are, for example, maleic acid, fumaric acid, itaconic acid and methylene malonic acid.
- Maleic acid, maleic anhydride, itaconic acid, itaconic anhydride and the corresponding sodium, potassium or ammonium salts of maleic or itaconic acid are preferably used.
- the group A monomers are preferably present in the monomer mixture in an amount of 10 to 70% by weight, more preferably 20 to 60% by weight and very particularly preferably 25 to 55% by weight.
- Monomers of group B are monoethylenically unsaturated C3-C10 monocarboxylic acids and their alkali and / or ammonium salts and / or amine salts. These monomers include, for example, acrylic acid, methacrylic acid, dimethylacrylic acid, ethyl acrylic acid, vinyl acetic acid and allylacetic acid. From this group of monomers, preference is given to using acrylic acid, methacrylic acid, their mixtures and the sodium, potassium or ammonium salts or mixtures thereof.
- the group B monomers are preferably 20 to 85% by weight, particularly preferably 25 up to 60% by weight and very particularly preferably 30 to 60% by weight, are present in the monomer mixture.
- the group C monomers include those which, after copolymerization and subsequent hydrolysis or saponification of the polymer, release one or more hydroxyl groups which are covalently bonded directly to the C-C polymer carbon chain. Examples include: vinyl acetate, vinyl propionate, methyl vinyl acetate, methyl vinyl ether, ethylene glycol monovinyl ether and vinylidene carbonate.
- the group C monomers are preferably present in the monomer mixture in an amount of 1 to 50% by weight, particularly preferably 4 to 40% by weight and very particularly preferably 8 to 30% by weight.
- group D monomers that can be used to modify the copolymers are, for. B. sulfone groups and sulfate group-containing monomers, such as meth (allylsulfonic acid), vinylsulfonic acid, styrene sulfonic acid, acrylamidomethylpropanesulfonic acid and monomers containing phosphonic acid groups, such as vinylphosphonic acid, allylphosphonic acid and acrylamidomethylpropanephosphonic acid and their salts, and hydroxyethyl (meth) acrylate sulfates, allyl sulfates.
- sulfone groups and sulfate group-containing monomers such as meth (allylsulfonic acid), vinylsulfonic acid, styrene sulfonic acid, acrylamidomethylpropanesulfonic acid and monomers containing phosphonic acid groups, such as vinylphosphonic acid, allylphosphonic acid and acrylamidomethylpropan
- group D monomers it is also possible - because of the required solubility, but only in a limited amount - to use double-ethylenically unsaturated non-conjugated compounds and polyalkylene glycol esters of (meth) acrylic acid and polyalkylene glycol ether with (meth) allyl alcohol, which may or may not be end-capped.
- the group D monomers are optionally present in the monomer mixture up to 15% by weight, preferably up to 10% by weight.
- the copolymers can be prepared by radical polymerization in an aqueous medium. Such a polymerization is described for example in the German patent application with the file number P 43 00 772.4.
- the copolymers act as dispersants and complexing agents. With them polyvalent metal ions, e.g. B. Ca, Mg and Fe ions, bound in water-soluble complexes.
- the copolymers disperse precipitated ones Water hardness and dirt particles.
- the products are characterized by good environmental compatibility.
- complexing and dispersing agents such as. B. phosphates, phosphonates, non-degradable polyacrylates, nitrilotriacetic acid (NTA), ethylenediaminetetraacetic acid (EDTA), which have ecological disadvantages, can usually be dispensed with or the amounts of the abovementioned agents can be reduced.
- the copolymers are biodegradable if they are used in the modified OECD Sturm test (EC Directive 84/449 / EEC C 5 and OECD Guideline 301 B) (see, for example, soap-oil-fat waxes 117 (1991), 740 to 744), have a degree of degradation of ⁇ 60%.
- the formulations also contain alkali formers b.
- alkali formers such as alkali metal silicates, alkali disilicates and crystalline alkali layer silicates are particularly suitable.
- the group of alkali formers also includes alkaline salts, such as alkali hydroxides and alkali carbonates. The amount of these alkali-forming substances used is between 3 and 90% by weight, preferably between 5 and 70% by weight.
- the formulations can also contain dispersing and complexing agents c.
- Suitable products are, for example, citrates, phosphonates, homopolymers and copolymers of acrylic acid, isoserinediacetic acid, ethylenediaminetetraacetic acid and nitrilotriacetic acid and the alkali metal salts of the aforementioned substances.
- Such agents if included in the recipes, contain up to 60% by weight, preferably in concentrations of 5 to 50% by weight. The use of sodium citrate in concentrations of 10 to 40% by weight is particularly preferred.
- the formulations can also contain 0 to 10% by weight of low-foaming surfactants d, preferably in amounts of 0.5 to 5% by weight.
- Low-foam nonionic surfactants such as, for example, fatty alcohol-ethylene oxide-propylene oxide addition products or fatty alcohol ethoxylates sealed with alkyl groups, are usually used.
- formulations generally contain further additives in amounts of 0 to 50% by weight, preferably 0 to 25% by weight.
- Such additives are e.g. B. oxygen-based bleaches, such as sodium perborate or sodium percarbonate, which are generally metered in amounts of 5 to 15 wt .-%. Since dishwashers usually work in the temperature range of 40 - 65 ° C, the oxygen bleaching can be activated by activators such. B. Tetraacetylethylenediamine (TAED) can be improved. The bleach activator TAED is usually used in amounts of 0 to 10% by weight.
- TAED Tetraacetylethylenediamine
- additives can also be chlorine-releasing substances, such as dichloroisocyanurates, which also act as bleaching agents. Products of this type are usually used in concentrations of 0 to 5% by weight.
- the formulations can also contain enzymes, in particular proteases, amylases and lipases. These enzymes are typically dosed in amounts of 0 to 5% by weight.
- the usual ingredients for such formulations such as. B. fragrances and dyes, defoamers, flow aids, extenders and extenders, the agents according to the invention can be added without problems. However, they do not contribute to the cleaning effect, but can improve the storage stability of the formulation or have a positive effect on the acceptance of the products by the consumer.
- the dishwashing detergents according to the invention can be liquid products, powdery types and granules or products pressed into blocks or tablets.
- the liquid formulations can be prepared by mixing the components.
- the powdery products are usually produced by mixing the powdery constituents and, if appropriate, by spraying on the liquid constituents or by spray-drying an aqueous, liquid to pasty batch of the starting components.
- the raw materials can first be mixed and / or pre-processed in spray mixing devices and then pressed in tabletting machines.
- the formulations according to the invention can be used as dishwashing detergents in the household and in the commercial sector.
- the copolymers a contained in the formulations have a good binding capacity for alkaline earth metal ions and an excellent dispersing and dirt-carrying capacity.
- the effectiveness of the cleaner is improved by the use of these polymers.
- the cleaning agents according to the invention bring about good dirt detachment and dirt dispersion and reduce deposits of water hardness deposits on the items to be washed and the machine parts.
- formulations according to the invention are better or at least equally good in their action.
- the formulations now claimed also have improved biodegradability.
- a copolymer with an average molar mass of approximately 15,000 g / mol is obtained by radical polymerization of 35% by weight of maleic anhydride in the form of sodium maleate, 45% by weight of acrylic acid and 20% by weight of vinyl acetate in aqueous solution and saponification .
- the copolymer obtained in aqueous solution is converted into a powdery product by spray drying.
- the biodegradability of the copolymers is tested in accordance with the modified OECD Sturm test in accordance with EC Directive 84/449 / EEC C 5 and OECD Guideline 301 B.
- a degree of degradation of over 60% is determined for the substance mentioned in Example 1.
- polycarboxylates such as. B. homopolyacrylates and copolymers of acrylic acid and maleic acid, on the other hand, have lower biodegradability.
- Machine dishwashing detergents of the following composition are produced from the copolymer from Example 1 (data in% by weight) Machine dish detergent, powdered 1 % 2% 3% Surfactant (low foam, MARLOX® MO 154) * 2.0 2.0 2.0 Copolymer, powdery 10.0 8.0 10.0 Sodium citrate dihydrate - 35.0 - Sodium metasilicate pentahydrate 50.0 - 50.0 Sodium disilicate granules - 20.0 - Sodium hydroxide 10.0 - - Sodium carbonate calc.
- MARLOX® MO 154 is a C12-C14 fatty alcohol alkylene oxide addition product from Hüls AG.
- Comparative formulation A comparative formulation V1 is prepared using a commercially available powdered polycarboxylate (polyacrylate, average molecular weight approx. 4,000 g / mol): Comparative formulation V1% Surfactant (low foam, MARLOX® MO 154) 2.0 Polyacrylate (molecular weight approx. 4,000 g / mol) 10.0 Sodium metasilicate pentahydrate 50.0 Sodium hydroxide 10.0 Sodium carbonate calc. 28.0
- formulation 1 The rinsing performance of formulation 1 according to the invention was tested in comparison to comparative formulation V1 in a commercially available dishwasher according to DIN 44 990. Minced meat, spinach, oatmeal, tea, egg, drinking milk and margarine were used as test soils. The dishwasher was operated with drinking water at 13 ° dH. The residues of soiling were evaluated in accordance with the DIN standard and the cleaning index R was calculated as the test result: 1 V1 Cleaning index R (according to DIN 44 990) 4.5 4.2
- dishwashing detergent formulations according to the invention It is found to be particularly advantageous in the dishwashing detergent formulations according to the invention that they have a very good cleaning performance and at the same time prevent deposits on items to be washed and machine parts contain biodegradable polymers as dispersing and complexing agents.
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- Chemical & Material Sciences (AREA)
- Life Sciences & Earth Sciences (AREA)
- Engineering & Computer Science (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Oil, Petroleum & Natural Gas (AREA)
- Wood Science & Technology (AREA)
- Organic Chemistry (AREA)
- Detergent Compositions (AREA)
- Centrifugal Separators (AREA)
- Control And Other Processes For Unpacking Of Materials (AREA)
- Biological Depolymerization Polymers (AREA)
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| DE4316745A DE4316745A1 (de) | 1993-05-19 | 1993-05-19 | Phosphatfreie Maschinengeschirreinigungsmittel |
| DE4316745 | 1993-05-19 |
Publications (3)
| Publication Number | Publication Date |
|---|---|
| EP0625567A2 true EP0625567A2 (fr) | 1994-11-23 |
| EP0625567A3 EP0625567A3 (fr) | 1995-05-31 |
| EP0625567B1 EP0625567B1 (fr) | 2001-01-17 |
Family
ID=6488460
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| EP94105346A Expired - Lifetime EP0625567B1 (fr) | 1993-05-19 | 1994-04-07 | Agent de nettoyage pour le lavage de la vaisselle en machine |
Country Status (3)
| Country | Link |
|---|---|
| EP (1) | EP0625567B1 (fr) |
| AT (1) | ATE198763T1 (fr) |
| DE (2) | DE4316745A1 (fr) |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP0774507A3 (fr) * | 1995-11-20 | 1998-07-15 | Rohm And Haas Company | Concentrés nettoyant et procédé de préparation |
| US6207780B1 (en) | 1995-05-12 | 2001-03-27 | Rohm & Haas Company | Interpolymers of unsaturated carboxylic acids and unsaturated sulfur acids |
| WO2007025955A1 (fr) * | 2005-08-31 | 2007-03-08 | Basf Aktiengesellschaft | Preparations detergentes pour lavage en lave-vaisselle contenant des polycarboxylates a modification hydrophile |
| US10781399B2 (en) | 2016-12-16 | 2020-09-22 | Dow Global Technologies Llc | Additive for controlling spotting in automatic dishwashing systems |
Family Cites Families (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE4008696A1 (de) * | 1990-03-17 | 1991-09-19 | Basf Ag | Verfahren zur herstellung von homo- und copolymerisaten monoethylenisch ungesaettigter dicarbonsaeuren und ihre verwendung |
| US5191048A (en) * | 1991-02-01 | 1993-03-02 | Rohm & Haas Company | Biodegradable free-radical addition polymers |
| EP0510944B1 (fr) * | 1991-04-22 | 1998-04-15 | Colgate-Palmolive Company | Compositions à visco-élasticité linéaire pour lave-vaisselle automatique |
| DE4300772C2 (de) * | 1993-01-14 | 1997-03-27 | Stockhausen Chem Fab Gmbh | Wasserlösliche, biologisch abbaubare Copolymere auf Basis von ungesättigten Mono- und Dicarbonsäuren, Verfahren zu ihrer Herstellung und ihre Verwendung |
| DE4313908A1 (de) * | 1993-04-28 | 1994-11-03 | Huels Chemische Werke Ag | Wasserenthärtende Formulierungen |
| DE4316741A1 (de) * | 1993-05-19 | 1994-11-24 | Huels Chemische Werke Ag | Universalreinigungsmittel mit biologisch abbaubaren Polymeren |
-
1993
- 1993-05-19 DE DE4316745A patent/DE4316745A1/de not_active Withdrawn
-
1994
- 1994-04-07 AT AT94105346T patent/ATE198763T1/de not_active IP Right Cessation
- 1994-04-07 EP EP94105346A patent/EP0625567B1/fr not_active Expired - Lifetime
- 1994-04-07 DE DE59409637T patent/DE59409637D1/de not_active Expired - Fee Related
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US6207780B1 (en) | 1995-05-12 | 2001-03-27 | Rohm & Haas Company | Interpolymers of unsaturated carboxylic acids and unsaturated sulfur acids |
| EP0774507A3 (fr) * | 1995-11-20 | 1998-07-15 | Rohm And Haas Company | Concentrés nettoyant et procédé de préparation |
| WO2007025955A1 (fr) * | 2005-08-31 | 2007-03-08 | Basf Aktiengesellschaft | Preparations detergentes pour lavage en lave-vaisselle contenant des polycarboxylates a modification hydrophile |
| US8093196B2 (en) | 2005-08-31 | 2012-01-10 | Basf Se | Cleaning formulations for machine dishwashing comprising hydrophilically modified polycarboxylates |
| US10781399B2 (en) | 2016-12-16 | 2020-09-22 | Dow Global Technologies Llc | Additive for controlling spotting in automatic dishwashing systems |
Also Published As
| Publication number | Publication date |
|---|---|
| EP0625567A3 (fr) | 1995-05-31 |
| DE59409637D1 (de) | 2001-02-22 |
| DE4316745A1 (de) | 1994-11-24 |
| ATE198763T1 (de) | 2001-02-15 |
| EP0625567B1 (fr) | 2001-01-17 |
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