EP2126032A1 - Compositions de détergent enrobées et procédé de fabrication - Google Patents
Compositions de détergent enrobées et procédé de fabricationInfo
- Publication number
- EP2126032A1 EP2126032A1 EP07818237A EP07818237A EP2126032A1 EP 2126032 A1 EP2126032 A1 EP 2126032A1 EP 07818237 A EP07818237 A EP 07818237A EP 07818237 A EP07818237 A EP 07818237A EP 2126032 A1 EP2126032 A1 EP 2126032A1
- Authority
- EP
- European Patent Office
- Prior art keywords
- composition
- detergent
- water
- coating
- 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.)
- Granted
Links
- 239000003599 detergent Substances 0.000 title claims abstract description 82
- 239000000203 mixture Substances 0.000 title claims abstract description 82
- 238000000034 method Methods 0.000 title claims abstract description 14
- 230000008569 process Effects 0.000 title claims abstract description 12
- 238000004519 manufacturing process Methods 0.000 title claims abstract description 9
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 63
- 239000000463 material Substances 0.000 claims abstract description 51
- 238000004851 dishwashing Methods 0.000 claims abstract description 18
- 238000000576 coating method Methods 0.000 claims description 40
- 239000011248 coating agent Substances 0.000 claims description 38
- -1 alkylene glycol mono alkyl ethers Chemical class 0.000 claims description 34
- 150000001875 compounds Chemical class 0.000 claims description 20
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 claims description 17
- 150000001413 amino acids Chemical class 0.000 claims description 13
- 239000001828 Gelatine Substances 0.000 claims description 9
- 229920000159 gelatin Polymers 0.000 claims description 9
- 235000019322 gelatine Nutrition 0.000 claims description 9
- 239000004014 plasticizer Substances 0.000 claims description 9
- 102000004169 proteins and genes Human genes 0.000 claims description 9
- 108090000623 proteins and genes Proteins 0.000 claims description 9
- LYCAIKOWRPUZTN-UHFFFAOYSA-N ethylene glycol Natural products OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 claims description 8
- 108090000765 processed proteins & peptides Proteins 0.000 claims description 8
- 229920001223 polyethylene glycol Polymers 0.000 claims description 7
- 239000002736 nonionic surfactant Substances 0.000 claims description 6
- DNIAPMSPPWPWGF-UHFFFAOYSA-N Propylene glycol Chemical class CC(O)CO DNIAPMSPPWPWGF-UHFFFAOYSA-N 0.000 claims description 5
- 229920001800 Shellac Polymers 0.000 claims description 5
- 239000006185 dispersion Substances 0.000 claims description 5
- 239000004208 shellac Substances 0.000 claims description 5
- ZLGIYFNHBLSMPS-ATJNOEHPSA-N shellac Chemical compound OCCCCCC(O)C(O)CCCCCCCC(O)=O.C1C23[C@H](C(O)=O)CCC2[C@](C)(CO)[C@@H]1C(C(O)=O)=C[C@@H]3O ZLGIYFNHBLSMPS-ATJNOEHPSA-N 0.000 claims description 5
- 229940113147 shellac Drugs 0.000 claims description 5
- 235000013874 shellac Nutrition 0.000 claims description 5
- 150000002314 glycerols Chemical class 0.000 claims description 4
- 150000004702 methyl esters Chemical class 0.000 claims description 4
- 150000005846 sugar alcohols Polymers 0.000 claims description 4
- URAYPUMNDPQOKB-UHFFFAOYSA-N triacetin Chemical compound CC(=O)OCC(OC(C)=O)COC(C)=O URAYPUMNDPQOKB-UHFFFAOYSA-N 0.000 claims description 4
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 claims description 3
- 239000005977 Ethylene Substances 0.000 claims description 3
- 150000001408 amides Chemical class 0.000 claims description 3
- 235000013772 propylene glycol Nutrition 0.000 claims description 3
- 238000007598 dipping method Methods 0.000 claims description 2
- 235000013773 glyceryl triacetate Nutrition 0.000 claims description 2
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 claims description 2
- 239000000155 melt Substances 0.000 claims description 2
- QQONPFPTGQHPMA-UHFFFAOYSA-N propylene Natural products CC=C QQONPFPTGQHPMA-UHFFFAOYSA-N 0.000 claims description 2
- 125000004805 propylene group Chemical group [H]C([H])([H])C([H])([*:1])C([H])([H])[*:2] 0.000 claims description 2
- 238000005507 spraying Methods 0.000 claims description 2
- 229960002622 triacetin Drugs 0.000 claims description 2
- ZOXJGFHDIHLPTG-UHFFFAOYSA-N Boron Chemical compound [B] ZOXJGFHDIHLPTG-UHFFFAOYSA-N 0.000 claims 1
- 229910052796 boron Inorganic materials 0.000 claims 1
- 239000000654 additive Substances 0.000 abstract description 15
- 230000000996 additive effect Effects 0.000 abstract description 13
- 229920001577 copolymer Polymers 0.000 description 20
- 229920000642 polymer Polymers 0.000 description 20
- 235000000346 sugar Nutrition 0.000 description 13
- 239000004615 ingredient Substances 0.000 description 11
- 239000002689 soil Substances 0.000 description 10
- 229920002678 cellulose Polymers 0.000 description 9
- 239000001913 cellulose Substances 0.000 description 9
- 235000010980 cellulose Nutrition 0.000 description 9
- 239000003795 chemical substances by application Substances 0.000 description 9
- 239000000178 monomer Substances 0.000 description 9
- 238000005406 washing Methods 0.000 description 9
- 229920003169 water-soluble polymer Polymers 0.000 description 9
- JNYAEWCLZODPBN-JGWLITMVSA-N (2r,3r,4s)-2-[(1r)-1,2-dihydroxyethyl]oxolane-3,4-diol Chemical compound OC[C@@H](O)[C@H]1OC[C@H](O)[C@H]1O JNYAEWCLZODPBN-JGWLITMVSA-N 0.000 description 8
- 125000004432 carbon atom Chemical group C* 0.000 description 8
- 150000001735 carboxylic acids Chemical class 0.000 description 8
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 7
- GOOHAUXETOMSMM-UHFFFAOYSA-N Propylene oxide Chemical group CC1CO1 GOOHAUXETOMSMM-UHFFFAOYSA-N 0.000 description 7
- 239000000975 dye Substances 0.000 description 7
- 150000002148 esters Chemical class 0.000 description 7
- 150000002191 fatty alcohols Chemical class 0.000 description 7
- NIXOWILDQLNWCW-UHFFFAOYSA-N 2-Propenoic acid Natural products OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 6
- 239000002253 acid Substances 0.000 description 6
- 125000000217 alkyl group Chemical group 0.000 description 6
- 125000002947 alkylene group Chemical group 0.000 description 6
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 description 6
- 235000014113 dietary fatty acids Nutrition 0.000 description 6
- 239000000194 fatty acid Substances 0.000 description 6
- 229930195729 fatty acid Natural products 0.000 description 6
- 239000002245 particle Substances 0.000 description 6
- 229940100515 sorbitan Drugs 0.000 description 6
- 239000004094 surface-active agent Substances 0.000 description 6
- LDHQCZJRKDOVOX-UHFFFAOYSA-N trans-crotonic acid Natural products CC=CC(O)=O LDHQCZJRKDOVOX-UHFFFAOYSA-N 0.000 description 6
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 description 5
- 229920002126 Acrylic acid copolymer Polymers 0.000 description 5
- 102000004190 Enzymes Human genes 0.000 description 5
- 108090000790 Enzymes Proteins 0.000 description 5
- CERQOIWHTDAKMF-UHFFFAOYSA-N Methacrylic acid Chemical compound CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 description 5
- 239000004372 Polyvinyl alcohol Substances 0.000 description 5
- 150000001298 alcohols Chemical class 0.000 description 5
- 125000002091 cationic group Chemical group 0.000 description 5
- 239000008199 coating composition Substances 0.000 description 5
- 150000002194 fatty esters Chemical class 0.000 description 5
- 229920002451 polyvinyl alcohol Polymers 0.000 description 5
- 235000019422 polyvinyl alcohol Nutrition 0.000 description 5
- 239000007787 solid Substances 0.000 description 5
- 150000008163 sugars Chemical class 0.000 description 5
- 229940117958 vinyl acetate Drugs 0.000 description 5
- VBICKXHEKHSIBG-UHFFFAOYSA-N 1-monostearoylglycerol Chemical compound CCCCCCCCCCCCCCCCCC(=O)OCC(O)CO VBICKXHEKHSIBG-UHFFFAOYSA-N 0.000 description 4
- WHNWPMSKXPGLAX-UHFFFAOYSA-N N-Vinyl-2-pyrrolidone Chemical compound C=CN1CCCC1=O WHNWPMSKXPGLAX-UHFFFAOYSA-N 0.000 description 4
- SMWDFEZZVXVKRB-UHFFFAOYSA-N Quinoline Chemical compound N1=CC=CC2=CC=CC=C21 SMWDFEZZVXVKRB-UHFFFAOYSA-N 0.000 description 4
- 229920002472 Starch Polymers 0.000 description 4
- XTXRWKRVRITETP-UHFFFAOYSA-N Vinyl acetate Chemical compound CC(=O)OC=C XTXRWKRVRITETP-UHFFFAOYSA-N 0.000 description 4
- AEMOLEFTQBMNLQ-BKBMJHBISA-N alpha-D-galacturonic acid Chemical compound O[C@H]1O[C@H](C(O)=O)[C@H](O)[C@H](O)[C@H]1O AEMOLEFTQBMNLQ-BKBMJHBISA-N 0.000 description 4
- 230000008901 benefit Effects 0.000 description 4
- 238000004140 cleaning Methods 0.000 description 4
- 239000007859 condensation product Substances 0.000 description 4
- LDHQCZJRKDOVOX-NSCUHMNNSA-N crotonic acid Chemical compound C\C=C\C(O)=O LDHQCZJRKDOVOX-NSCUHMNNSA-N 0.000 description 4
- UKMSUNONTOPOIO-UHFFFAOYSA-N docosanoic acid Chemical compound CCCCCCCCCCCCCCCCCCCCCC(O)=O UKMSUNONTOPOIO-UHFFFAOYSA-N 0.000 description 4
- 238000001035 drying Methods 0.000 description 4
- 150000004665 fatty acids Chemical class 0.000 description 4
- IPCSVZSSVZVIGE-UHFFFAOYSA-N hexadecanoic acid Chemical compound CCCCCCCCCCCCCCCC(O)=O IPCSVZSSVZVIGE-UHFFFAOYSA-N 0.000 description 4
- 150000002430 hydrocarbons Chemical group 0.000 description 4
- 238000004806 packaging method and process Methods 0.000 description 4
- 238000006116 polymerization reaction Methods 0.000 description 4
- 239000008107 starch Substances 0.000 description 4
- 235000019698 starch Nutrition 0.000 description 4
- 229920001567 vinyl ester resin Polymers 0.000 description 4
- 125000003903 2-propenyl group Chemical group [H]C([*])([H])C([H])=C([H])[H] 0.000 description 3
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 3
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 3
- IAYPIBMASNFSPL-UHFFFAOYSA-N Ethylene oxide Chemical compound C1CO1 IAYPIBMASNFSPL-UHFFFAOYSA-N 0.000 description 3
- 229920000881 Modified starch Polymers 0.000 description 3
- 229920003171 Poly (ethylene oxide) Polymers 0.000 description 3
- 229920000289 Polyquaternium Polymers 0.000 description 3
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 description 3
- 150000005215 alkyl ethers Chemical class 0.000 description 3
- 239000002585 base Substances 0.000 description 3
- 238000007046 ethoxylation reaction Methods 0.000 description 3
- 239000000945 filler Substances 0.000 description 3
- 239000011888 foil Substances 0.000 description 3
- 239000008187 granular material Substances 0.000 description 3
- 230000002209 hydrophobic effect Effects 0.000 description 3
- KQNPFQTWMSNSAP-UHFFFAOYSA-N isobutyric acid Chemical compound CC(C)C(O)=O KQNPFQTWMSNSAP-UHFFFAOYSA-N 0.000 description 3
- 229920003145 methacrylic acid copolymer Polymers 0.000 description 3
- 235000019426 modified starch Nutrition 0.000 description 3
- 125000006353 oxyethylene group Chemical group 0.000 description 3
- 229920002689 polyvinyl acetate Polymers 0.000 description 3
- 239000011118 polyvinyl acetate Substances 0.000 description 3
- 229920000036 polyvinylpyrrolidone Polymers 0.000 description 3
- 235000013855 polyvinylpyrrolidone Nutrition 0.000 description 3
- 229920005989 resin Polymers 0.000 description 3
- 239000011347 resin Substances 0.000 description 3
- 229920006395 saturated elastomer Polymers 0.000 description 3
- 150000003384 small molecules Chemical class 0.000 description 3
- 239000000243 solution Substances 0.000 description 3
- 229920001897 terpolymer Polymers 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
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 description 3
- WRIDQFICGBMAFQ-UHFFFAOYSA-N (E)-8-Octadecenoic acid Natural products CCCCCCCCCC=CCCCCCCC(O)=O WRIDQFICGBMAFQ-UHFFFAOYSA-N 0.000 description 2
- QHZLMUACJMDIAE-UHFFFAOYSA-N 1-monopalmitoylglycerol Chemical compound CCCCCCCCCCCCCCCC(=O)OCC(O)CO QHZLMUACJMDIAE-UHFFFAOYSA-N 0.000 description 2
- LQJBNNIYVWPHFW-UHFFFAOYSA-N 20:1omega9c fatty acid Natural products CCCCCCCCCCC=CCCCCCCCC(O)=O LQJBNNIYVWPHFW-UHFFFAOYSA-N 0.000 description 2
- NKVJCKOMRJVZLO-UHFFFAOYSA-N 3,6,7-trioxabicyclo[7.2.2]trideca-1(11),9,12-triene-2,8-dione Chemical compound O=C1OCCOOC(=O)C2=CC=C1C=C2 NKVJCKOMRJVZLO-UHFFFAOYSA-N 0.000 description 2
- QSBYPNXLFMSGKH-UHFFFAOYSA-N 9-Heptadecensaeure Natural products CCCCCCCC=CCCCCCCCC(O)=O QSBYPNXLFMSGKH-UHFFFAOYSA-N 0.000 description 2
- HRPVXLWXLXDGHG-UHFFFAOYSA-N Acrylamide Chemical compound NC(=O)C=C HRPVXLWXLXDGHG-UHFFFAOYSA-N 0.000 description 2
- QEWLHSNMEXFSCI-UHFFFAOYSA-N Alloclamide hydrochloride Chemical compound Cl.CCN(CC)CCNC(=O)C1=CC=C(Cl)C=C1OCC=C QEWLHSNMEXFSCI-UHFFFAOYSA-N 0.000 description 2
- UIERETOOQGIECD-UHFFFAOYSA-N Angelic acid Natural products CC=C(C)C(O)=O UIERETOOQGIECD-UHFFFAOYSA-N 0.000 description 2
- 235000021357 Behenic acid Nutrition 0.000 description 2
- FERIUCNNQQJTOY-UHFFFAOYSA-N Butyric acid Chemical compound CCCC(O)=O FERIUCNNQQJTOY-UHFFFAOYSA-N 0.000 description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 2
- SRBFZHDQGSBBOR-IOVATXLUSA-N D-xylopyranose Chemical compound O[C@@H]1COC(O)[C@H](O)[C@H]1O SRBFZHDQGSBBOR-IOVATXLUSA-N 0.000 description 2
- PIICEJLVQHRZGT-UHFFFAOYSA-N Ethylenediamine Chemical compound NCCN PIICEJLVQHRZGT-UHFFFAOYSA-N 0.000 description 2
- AEMRFAOFKBGASW-UHFFFAOYSA-N Glycolic acid Chemical compound OCC(O)=O AEMRFAOFKBGASW-UHFFFAOYSA-N 0.000 description 2
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 2
- CERQOIWHTDAKMF-UHFFFAOYSA-M Methacrylate Chemical compound CC(=C)C([O-])=O CERQOIWHTDAKMF-UHFFFAOYSA-M 0.000 description 2
- 239000005642 Oleic acid Substances 0.000 description 2
- ZQPPMHVWECSIRJ-UHFFFAOYSA-N Oleic acid Natural products CCCCCCCCC=CCCCCCCCC(O)=O ZQPPMHVWECSIRJ-UHFFFAOYSA-N 0.000 description 2
- 235000021314 Palmitic acid Nutrition 0.000 description 2
- OFOBLEOULBTSOW-UHFFFAOYSA-N Propanedioic acid Natural products OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 0.000 description 2
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 2
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 description 2
- 235000021355 Stearic acid Nutrition 0.000 description 2
- CZMRCDWAGMRECN-UGDNZRGBSA-N Sucrose Chemical compound O[C@H]1[C@H](O)[C@@H](CO)O[C@@]1(CO)O[C@@H]1[C@H](O)[C@@H](O)[C@H](O)[C@@H](CO)O1 CZMRCDWAGMRECN-UGDNZRGBSA-N 0.000 description 2
- 229930006000 Sucrose Natural products 0.000 description 2
- TVXBFESIOXBWNM-UHFFFAOYSA-N Xylitol Natural products OCCC(O)C(O)C(O)CCO TVXBFESIOXBWNM-UHFFFAOYSA-N 0.000 description 2
- 150000007513 acids Chemical class 0.000 description 2
- 229920006322 acrylamide copolymer Polymers 0.000 description 2
- 229910052783 alkali metal Inorganic materials 0.000 description 2
- 150000001340 alkali metals Chemical class 0.000 description 2
- 150000003863 ammonium salts Chemical class 0.000 description 2
- 125000000129 anionic group Chemical group 0.000 description 2
- PYMYPHUHKUWMLA-UHFFFAOYSA-N arabinose Natural products OCC(O)C(O)C(O)C=O PYMYPHUHKUWMLA-UHFFFAOYSA-N 0.000 description 2
- 229940116226 behenic acid Drugs 0.000 description 2
- SRBFZHDQGSBBOR-UHFFFAOYSA-N beta-D-Pyranose-Lyxose Natural products OC1COC(O)C(O)C1O SRBFZHDQGSBBOR-UHFFFAOYSA-N 0.000 description 2
- 239000011230 binding agent Substances 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 239000007844 bleaching agent Substances 0.000 description 2
- 229920001400 block copolymer Polymers 0.000 description 2
- 229920003086 cellulose ether Polymers 0.000 description 2
- 239000007795 chemical reaction product Substances 0.000 description 2
- 238000007334 copolymerization reaction Methods 0.000 description 2
- RXKJFZQQPQGTFL-UHFFFAOYSA-N dihydroxyacetone Chemical compound OCC(=O)CO RXKJFZQQPQGTFL-UHFFFAOYSA-N 0.000 description 2
- XBDQKXXYIPTUBI-UHFFFAOYSA-N dimethylselenoniopropionate Natural products CCC(O)=O XBDQKXXYIPTUBI-UHFFFAOYSA-N 0.000 description 2
- 238000004090 dissolution Methods 0.000 description 2
- POULHZVOKOAJMA-UHFFFAOYSA-N dodecanoic acid Chemical compound CCCCCCCCCCCC(O)=O POULHZVOKOAJMA-UHFFFAOYSA-N 0.000 description 2
- 239000011521 glass Substances 0.000 description 2
- YQEMORVAKMFKLG-UHFFFAOYSA-N glycerine monostearate Natural products CCCCCCCCCCCCCCCCCC(=O)OC(CO)CO YQEMORVAKMFKLG-UHFFFAOYSA-N 0.000 description 2
- SVUQHVRAGMNPLW-UHFFFAOYSA-N glycerol monostearate Natural products CCCCCCCCCCCCCCCCC(=O)OCC(O)CO SVUQHVRAGMNPLW-UHFFFAOYSA-N 0.000 description 2
- 229920001519 homopolymer Polymers 0.000 description 2
- QXJSBBXBKPUZAA-UHFFFAOYSA-N isooleic acid Natural products CCCCCCCC=CCCCCCCCCC(O)=O QXJSBBXBKPUZAA-UHFFFAOYSA-N 0.000 description 2
- JVTAAEKCZFNVCJ-UHFFFAOYSA-N lactic acid Chemical compound CC(O)C(O)=O JVTAAEKCZFNVCJ-UHFFFAOYSA-N 0.000 description 2
- VZCYOOQTPOCHFL-UPHRSURJSA-N maleic acid Chemical compound OC(=O)\C=C/C(O)=O VZCYOOQTPOCHFL-UPHRSURJSA-N 0.000 description 2
- 239000011976 maleic acid Substances 0.000 description 2
- HEBKCHPVOIAQTA-UHFFFAOYSA-N meso ribitol Natural products OCC(O)C(O)C(O)CO HEBKCHPVOIAQTA-UHFFFAOYSA-N 0.000 description 2
- NYGZLYXAPMMJTE-UHFFFAOYSA-M metanil yellow Chemical group [Na+].[O-]S(=O)(=O)C1=CC=CC(N=NC=2C=CC(NC=3C=CC=CC=3)=CC=2)=C1 NYGZLYXAPMMJTE-UHFFFAOYSA-M 0.000 description 2
- 125000005394 methallyl group Chemical group 0.000 description 2
- UQDUPQYQJKYHQI-UHFFFAOYSA-N methyl laurate Chemical compound CCCCCCCCCCCC(=O)OC UQDUPQYQJKYHQI-UHFFFAOYSA-N 0.000 description 2
- JGHZJRVDZXSNKQ-UHFFFAOYSA-N methyl octanoate Chemical compound CCCCCCCC(=O)OC JGHZJRVDZXSNKQ-UHFFFAOYSA-N 0.000 description 2
- XJRBAMWJDBPFIM-UHFFFAOYSA-N methyl vinyl ether Chemical compound COC=C XJRBAMWJDBPFIM-UHFFFAOYSA-N 0.000 description 2
- 239000003607 modifier Substances 0.000 description 2
- WQEPLUUGTLDZJY-UHFFFAOYSA-N n-Pentadecanoic acid Natural products CCCCCCCCCCCCCCC(O)=O WQEPLUUGTLDZJY-UHFFFAOYSA-N 0.000 description 2
- QIQXTHQIDYTFRH-UHFFFAOYSA-N octadecanoic acid Chemical compound CCCCCCCCCCCCCCCCCC(O)=O QIQXTHQIDYTFRH-UHFFFAOYSA-N 0.000 description 2
- OQCDKBAXFALNLD-UHFFFAOYSA-N octadecanoic acid Natural products CCCCCCCC(C)CCCCCCCCC(O)=O OQCDKBAXFALNLD-UHFFFAOYSA-N 0.000 description 2
- ZQPPMHVWECSIRJ-KTKRTIGZSA-N oleic acid Chemical compound CCCCCCCC\C=C/CCCCCCCC(O)=O ZQPPMHVWECSIRJ-KTKRTIGZSA-N 0.000 description 2
- 235000021313 oleic acid Nutrition 0.000 description 2
- 125000001117 oleyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])/C([H])=C([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])[H] 0.000 description 2
- 239000002304 perfume Substances 0.000 description 2
- 229920001451 polypropylene glycol Polymers 0.000 description 2
- 239000001267 polyvinylpyrrolidone Substances 0.000 description 2
- 102000004196 processed proteins & peptides Human genes 0.000 description 2
- 239000000047 product Substances 0.000 description 2
- 150000003839 salts Chemical class 0.000 description 2
- 229910052709 silver Inorganic materials 0.000 description 2
- 239000004332 silver Substances 0.000 description 2
- 239000002904 solvent Substances 0.000 description 2
- 239000008117 stearic acid Substances 0.000 description 2
- KDYFGRWQOYBRFD-UHFFFAOYSA-N succinic acid Chemical compound OC(=O)CCC(O)=O KDYFGRWQOYBRFD-UHFFFAOYSA-N 0.000 description 2
- 229960004793 sucrose Drugs 0.000 description 2
- UIERETOOQGIECD-ONEGZZNKSA-N tiglic acid Chemical compound C\C=C(/C)C(O)=O UIERETOOQGIECD-ONEGZZNKSA-N 0.000 description 2
- 125000005208 trialkylammonium group Chemical group 0.000 description 2
- 239000001993 wax Substances 0.000 description 2
- 239000000811 xylitol Substances 0.000 description 2
- HEBKCHPVOIAQTA-SCDXWVJYSA-N xylitol Chemical compound OC[C@H](O)[C@@H](O)[C@H](O)CO HEBKCHPVOIAQTA-SCDXWVJYSA-N 0.000 description 2
- 235000010447 xylitol Nutrition 0.000 description 2
- 229960002675 xylitol Drugs 0.000 description 2
- BJEPYKJPYRNKOW-REOHCLBHSA-N (S)-malic acid Chemical compound OC(=O)[C@@H](O)CC(O)=O BJEPYKJPYRNKOW-REOHCLBHSA-N 0.000 description 1
- ZORQXIQZAOLNGE-UHFFFAOYSA-N 1,1-difluorocyclohexane Chemical compound FC1(F)CCCCC1 ZORQXIQZAOLNGE-UHFFFAOYSA-N 0.000 description 1
- OKMWKBLSFKFYGZ-UHFFFAOYSA-N 1-behenoylglycerol Chemical compound CCCCCCCCCCCCCCCCCCCCCC(=O)OCC(O)CO OKMWKBLSFKFYGZ-UHFFFAOYSA-N 0.000 description 1
- QIZPVNNYFKFJAD-UHFFFAOYSA-N 1-chloro-2-prop-1-ynylbenzene Chemical compound CC#CC1=CC=CC=C1Cl QIZPVNNYFKFJAD-UHFFFAOYSA-N 0.000 description 1
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- 239000007788 liquid Substances 0.000 description 1
- 239000000314 lubricant Substances 0.000 description 1
- FPYJFEHAWHCUMM-UHFFFAOYSA-N maleic anhydride Chemical compound O=C1OC(=O)C=C1 FPYJFEHAWHCUMM-UHFFFAOYSA-N 0.000 description 1
- 239000001630 malic acid Substances 0.000 description 1
- 235000011090 malic acid Nutrition 0.000 description 1
- 239000002609 medium Substances 0.000 description 1
- 238000002844 melting Methods 0.000 description 1
- 230000008018 melting Effects 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- RUAIJHHRCIHFEV-UHFFFAOYSA-N methyl 4-amino-5-chlorothiophene-2-carboxylate Chemical compound COC(=O)C1=CC(N)=C(Cl)S1 RUAIJHHRCIHFEV-UHFFFAOYSA-N 0.000 description 1
- 229940017219 methyl propionate Drugs 0.000 description 1
- 239000004200 microcrystalline wax Substances 0.000 description 1
- 235000019808 microcrystalline wax Nutrition 0.000 description 1
- 238000003801 milling Methods 0.000 description 1
- XFHJDMUEHUHAJW-UHFFFAOYSA-N n-tert-butylprop-2-enamide Chemical compound CC(C)(C)NC(=O)C=C XFHJDMUEHUHAJW-UHFFFAOYSA-N 0.000 description 1
- 231100000252 nontoxic Toxicity 0.000 description 1
- 230000003000 nontoxic effect Effects 0.000 description 1
- 231100000956 nontoxicity Toxicity 0.000 description 1
- 229920001542 oligosaccharide Polymers 0.000 description 1
- 150000002482 oligosaccharides Chemical class 0.000 description 1
- 239000004006 olive oil Substances 0.000 description 1
- 235000008390 olive oil Nutrition 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- 125000005702 oxyalkylene group Chemical group 0.000 description 1
- 239000005022 packaging material Substances 0.000 description 1
- 238000010422 painting Methods 0.000 description 1
- 239000002540 palm oil Substances 0.000 description 1
- 125000000913 palmityl group Chemical group [H]C([*])([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])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 239000012188 paraffin wax Substances 0.000 description 1
- 239000000312 peanut oil Substances 0.000 description 1
- 229920001277 pectin Polymers 0.000 description 1
- 235000010987 pectin Nutrition 0.000 description 1
- 229940059574 pentaerithrityl Drugs 0.000 description 1
- WXZMFSXDPGVJKK-UHFFFAOYSA-N pentaerythritol Chemical compound OCC(CO)(CO)CO WXZMFSXDPGVJKK-UHFFFAOYSA-N 0.000 description 1
- PNJWIWWMYCMZRO-UHFFFAOYSA-N pent‐4‐en‐2‐one Natural products CC(=O)CC=C PNJWIWWMYCMZRO-UHFFFAOYSA-N 0.000 description 1
- 239000012169 petroleum derived wax Substances 0.000 description 1
- 235000019381 petroleum wax Nutrition 0.000 description 1
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 description 1
- 239000010452 phosphate Substances 0.000 description 1
- 239000001007 phthalocyanine dye Substances 0.000 description 1
- 239000000049 pigment Substances 0.000 description 1
- 229920003023 plastic Polymers 0.000 description 1
- 239000004033 plastic Substances 0.000 description 1
- 229920001983 poloxamer Polymers 0.000 description 1
- 229920000233 poly(alkylene oxides) Polymers 0.000 description 1
- 229920001515 polyalkylene glycol Polymers 0.000 description 1
- 229920005646 polycarboxylate Polymers 0.000 description 1
- 229920001282 polysaccharide Polymers 0.000 description 1
- 229920001296 polysiloxane Polymers 0.000 description 1
- 229920001290 polyvinyl ester Polymers 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 230000002265 prevention Effects 0.000 description 1
- 235000019260 propionic acid Nutrition 0.000 description 1
- IUVKMZGDUIUOCP-BTNSXGMBSA-N quinbolone Chemical compound O([C@H]1CC[C@H]2[C@H]3[C@@H]([C@]4(C=CC(=O)C=C4CC3)C)CC[C@@]21C)C1=CCCC1 IUVKMZGDUIUOCP-BTNSXGMBSA-N 0.000 description 1
- 239000004172 quinoline yellow Substances 0.000 description 1
- 229940051201 quinoline yellow Drugs 0.000 description 1
- 235000012752 quinoline yellow Nutrition 0.000 description 1
- IZMJMCDDWKSTTK-UHFFFAOYSA-N quinoline yellow Chemical compound C1=CC=CC2=NC(C3C(C4=CC=CC=C4C3=O)=O)=CC=C21 IZMJMCDDWKSTTK-UHFFFAOYSA-N 0.000 description 1
- 229920005604 random copolymer Polymers 0.000 description 1
- 239000000985 reactive dye Substances 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 235000005713 safflower oil Nutrition 0.000 description 1
- 239000003813 safflower oil Substances 0.000 description 1
- 229930195734 saturated hydrocarbon Natural products 0.000 description 1
- 239000000377 silicon dioxide Substances 0.000 description 1
- 235000012239 silicon dioxide Nutrition 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- 239000013042 solid detergent Substances 0.000 description 1
- 239000002195 soluble material Substances 0.000 description 1
- 229940035044 sorbitan monolaurate Drugs 0.000 description 1
- 239000001593 sorbitan monooleate Substances 0.000 description 1
- 235000011069 sorbitan monooleate Nutrition 0.000 description 1
- 229940035049 sorbitan monooleate Drugs 0.000 description 1
- 239000001587 sorbitan monostearate Substances 0.000 description 1
- 235000011076 sorbitan monostearate Nutrition 0.000 description 1
- 229940035048 sorbitan monostearate Drugs 0.000 description 1
- 229950003429 sorbitan palmitate Drugs 0.000 description 1
- 239000000600 sorbitol Substances 0.000 description 1
- 229960002920 sorbitol Drugs 0.000 description 1
- 239000003549 soybean oil Substances 0.000 description 1
- 235000012424 soybean oil Nutrition 0.000 description 1
- 241000894007 species Species 0.000 description 1
- 230000000087 stabilizing effect Effects 0.000 description 1
- 229910052682 stishovite Inorganic materials 0.000 description 1
- 125000001424 substituent group Chemical group 0.000 description 1
- 239000001384 succinic acid Substances 0.000 description 1
- 239000005720 sucrose Substances 0.000 description 1
- 229940035023 sucrose monostearate Drugs 0.000 description 1
- 125000000542 sulfonic acid group Chemical group 0.000 description 1
- 239000002600 sunflower oil Substances 0.000 description 1
- 230000001629 suppression Effects 0.000 description 1
- 230000008961 swelling Effects 0.000 description 1
- 239000003760 tallow Substances 0.000 description 1
- KKEYFWRCBNTPAC-UHFFFAOYSA-L terephthalate(2-) Chemical compound [O-]C(=O)C1=CC=C(C([O-])=O)C=C1 KKEYFWRCBNTPAC-UHFFFAOYSA-L 0.000 description 1
- 229920006029 tetra-polymer Polymers 0.000 description 1
- TUNFSRHWOTWDNC-HKGQFRNVSA-N tetradecanoic acid Chemical compound CCCCCCCCCCCCC[14C](O)=O TUNFSRHWOTWDNC-HKGQFRNVSA-N 0.000 description 1
- ODBLHEXUDAPZAU-UHFFFAOYSA-N threo-D-isocitric acid Natural products OC(=O)C(O)C(C(O)=O)CC(O)=O ODBLHEXUDAPZAU-UHFFFAOYSA-N 0.000 description 1
- 150000003626 triacylglycerols Chemical class 0.000 description 1
- 229910052905 tridymite Inorganic materials 0.000 description 1
- JSPLKZUTYZBBKA-UHFFFAOYSA-N trioxidane Chemical class OOO JSPLKZUTYZBBKA-UHFFFAOYSA-N 0.000 description 1
- 239000010981 turquoise Substances 0.000 description 1
- 235000013799 ultramarine blue Nutrition 0.000 description 1
- 235000015112 vegetable and seed oil Nutrition 0.000 description 1
- 239000008158 vegetable oil Substances 0.000 description 1
- 235000013311 vegetables Nutrition 0.000 description 1
- 239000004034 viscosity adjusting agent 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
- C11D17/00—Detergent materials or soaps characterised by their shape or physical properties
- C11D17/0039—Coated compositions or coated components in the compositions, (micro)capsules
-
- 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
- C11D17/00—Detergent materials or soaps characterised by their shape or physical properties
- C11D17/0047—Detergents in the form of bars or tablets
- C11D17/0065—Solid detergents containing builders
- C11D17/0073—Tablets
- C11D17/0082—Coated tablets
-
- 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
- C11D3/20—Organic compounds containing oxygen
- C11D3/22—Carbohydrates or derivatives thereof
- C11D3/221—Mono, di- or trisaccharides or derivatives thereof
-
- 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
- C11D3/20—Organic compounds containing oxygen
- C11D3/22—Carbohydrates or derivatives thereof
- C11D3/222—Natural or synthetic polysaccharides, e.g. cellulose, starch, gum, alginic acid or cyclodextrin
-
- 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
- C11D3/38—Products with no well-defined composition, e.g. natural products
Definitions
- the present invention relates to a coated detergent and/or additive composition e.g. for the dish washing or laundry machine or water softener tablets coated with a water or temperature dissolvable material and a process of manufacturing thereof.
- the traditional form of detergent and/or additive compositions for use in dish washing or washing machines is granules or non particulate solids such as bars or tablets or briquettes.
- the term tablet will refer to any form of non particulate solids.
- said detergent and/or additive tablets or granules are respectively placed or poured in the dispenser located in said machine or in an adequate dispensing device which is then placed in said machine.
- EP-A 700 989 describes a unit packaged detergent.
- Said unit packaged detergent is a detergent packaged in a water soluble polymer film or sheet in such a form that it is suitable for one wash. This unit packaged detergent is placed in the detergent disperser of the machine without unwrapping the contained detergent from the packaging.
- said unit packaged detergent prevents wasting through spillage of the detergent and/or additive composition.
- said unit packaged detergent eliminates the need for the user to estimate the dosage of said composition required and ensures that the correct dosage of said composition per wash cycle is used by the user.
- the fingers of a user do not come in contact with the wrapped detergent composition.
- WO 04/20509 describes a water soluble non-homogenous polymer containing water soluble fillers for wrapping detergent compositions. The polymer is used in an injection moulding process using a water soluble resin comprising a water soluble polymer and a water soluble filler.
- Residues of the film or foil used as soluble wrapping material may soil e.g. the dish washing machines, dependent from the used film or foils or reaction products of the soil with the solved coating.
- the process of manufacture Independent from the solubility of the films or foils used for wrapping / packaging of the detergent particles the process of manufacture has to include a wrapping / packaging step, which affects the speed of the manufacture process.
- Unwrapped tablets having a coating primarily are provided for laundry dishwashing compositions, particularly for increasing mechanical resistance of the tablet and for stabilise them.
- WO00/66701 describe shaped detergent tablets coated with several types of water soluble polymers, particularly with (co)polymers comprising acid monomers and/or unsaturated monomers.
- US 6,576,599 discloses dishwashing tablets having a water insoluble coating for improving mechanical stability of the tablets.
- WO 04/ 20569 A1 describes a detergent particle having a base layer of a fine powder dispersed in a binder on the surface of the particle, said base layer is coated with a surface modifier.
- the object of the present invention was to provide a detergent composition providing safe and easy handling for the user and a fast and easy production process for said composition.
- a unit coated detergent composition wherein the detergent composition is coated with a water dissolvable or dispersible coating comprising at least one compound, selected from cellulose, starch or starch derivatives, pectine, proteins or peptides, particularly gelatine, sugar(s) or amino acid(s).
- a detergent and/or additive compositions will be encompassed by the term "detergent”.
- This detergent composition may be in the form of granules or of any non particulate solids such as bars or tablets or briquettes.
- the word “tablet” encompasses in the following any form of non particulate solids. Said tablet may have any shape.
- said solid detergent tablet is formed in a shape to ensure the uniform dissolution of the tablet in the wash liquor.
- the detergent and/or additive composition may comprise any ingredients known in the art for dish washing, laundry or water softening. Such ingredients may include for example surfactants, suds suppressers, bleach systems, chelating agents, builders, enzymes, fillers and perfumes, however, is not limited to these.
- One particular preferred embodiment of the present invention is a shaped body for automatic dishwashing formed of a particulate detergent composition , wherein the detergent composition comprises any of the ingredients which are typical for such compositions.
- the detergent composition comprises any of the ingredients which are typical for such compositions.
- Such ingredients are not limiting the invention, however, examples of suitable ingredients are listed below.
- a predosed quantity of detergent is coated with a water soluble or dissolvable material to provide a coated detergent particle as a "unit coated detergent".
- unit coated detergent means an amount of detergent suitable for one wash. Nevertheless, two or more unit coated detergents according to the present invention may be used in a single wash to meet different washing conditions, like dirtiness of washing, amount of washing, volume of washing machine, hardness of water, temperature of water and type of detergent. Said coating is made of a water or temperature dissolvable material.
- the unit coated detergent according to the present invention may contain between 5 grams and 60 grams of detergent.
- This unit coated detergent of the present invention is placed in the machine without any further handling step. This is possible, since said coating is made of a water solvable, dissolvable or dispersible material.
- Providing the detergent in coated form has several advantages. First, said unit coated detergent prevents wasting through spillage of the detergent and/or additive composition. Spillage may occur during the measuring and/or dispensing into the dispenser of the washing machine or into a dispensing device. Second, said unit coated detergent eliminates the need for the user to estimate the dosage of said composition required and ensures that the correct dosage of said composition per wash cycle is used by the user. Therefore, separate measuring and/or dosing devices are superfluous. Third, the fingers of a user do not come in contact with the detergent composition, which means that the user avoids to soil its fingers and/or hands. Either in case of water solvable films wrapped around the detergent unit people may be confused and try to open said wrapping.
- the coating of the unit coated detergent is made of a material which is water soluble or dissolves in water or is dispersible in water, is harmless for the user and can be processed at high speed during manufacture of the coating of detergent compositions.
- said coating material comprises A.) at least one water soluble or dissolvable polymer selected from:
- A1 a protein (more than 100 amino acids up to "full length proteins” e.g. up to 2500 amino acids) or a peptide having at least 10, preferably at least 50, more preferred at least 80, most preferred at least 100 amino acids, alternatively a protein or peptide having a molecular weight of 20,000 to 350,000 g/mol, preferably from 100,000 to 300,000 g/mol
- the most preferred protein is gelatine or a peptide thereof. Enzymes in their active form are not preferred.
- the coating may consist essentially of one of these polymers or of a mixture of at least two of these.
- the coating may consist essentially of these compounds.
- compositions mentioned under items A.) to F.) optionally can comprise a binder material.
- compositions A.) to C. may comprise at least 1 % by weight or at least 5% by weight, preferably at least 15 % by weight, more preferably at least 35 % by weight, most preferably at least 50 % by weight and up to 100% by weight, or up to 99 % by weight, up to 95 % by weight, up to 90% by weight or maybe up to 75 % by weight of the materials mentioned in A.) to C), preferred of the materials mentioned in A.) or B), particularly preferred the materials mentioned in A1 ).
- compositions D.) to F.) may comprise at least 1% by weight or at least 5% by weight, preferably at least 15 % by weight, more preferably at least 35 % by weight, most preferably at least 50 % by weight of the compounds mentioned in A.) to C.) and1 to 99, or 5 to 95, preferably 10 to 75, more preferably 15 to 50 % by weight of at least one of the compounds mentioned in D.) to F.) as further compounds.
- a preferred water soluble low molecular weight compound is any type of sugar, amino acid or other low molecular acids, e.g. citric acid or the like.
- water-soluble/dissolvable/dispersible is herein defined when more than 99% of a coating (layer) of such material dissolves within 15 minutes, preferably within 5 min in a beaker containing 1 L of deionised water at 40° C which is stirred with a stirrer revolving at 200 r. p.m. It is pointed out that materials can be used as ingredients for the coating which itself may not be soluble, but e.g. dispersible, as long as the coating comprising said material is dissolved by water.
- the preferred water soluble / dissolvable / dispersible materials are cellulose, particularly preferred cellulose fibres or microcristalline cellulose with an average particle size in dry state of below 1000 ⁇ m, preferably below 500 ⁇ m, more preferred 250 ⁇ m or smaller and particularly preferred of between 20 and 150 ⁇ m; starch or starch derivatives, pectine like glycogene or - most preferred - proteins or peptides (at least 10mer), particularly gelatine or derivatives or peptide fragments thereof.
- Another suitable and preferred material is shellac, which preferably is used in degreased form.
- Suitable compounds are "low molecular weight compounds" like C 3 -C 6 sugars in aldose or ketose form like allose, altrose, glucose, mannose, gulose, idose, galactose, talose, psicose, fructose, sorbose, tagatose, xylulose, ribulose, ribose, arabinose, xylose, lyxose, threose, erythrose, erythrulose, dihydroxy acetone or glycerol aldehyde or disaccharides like for example saccharose, lactose, maltose or lsomalt or oligosaccharides comprising 3 to 10 sugar units or amino acids, preferably natural amino acids (commonly contained in natural proteins) without being restricted to the mentioned examples.
- One particularly preferred low molecular weight compound is the sugar lsomalt ST, comprising 6-O- ⁇ -D-glucopyranosyl-D- sorbite and 1-O- ⁇ -D-glucopyranosyl-D-mannite dihydrate units. Further information about said sugar is available under www.chemistryworld.de/schene/prs-html/analvsen/2444- spz.htm.
- Said materials can be used solely each or as a mixture of the single materials.
- the mentioned material(s) of A.) to F.) can form one layer on the surface of the unit composition
- the unit composition comprises at least two layers of the above mentioned materials, wherein the layers can comprise different material selected from A.) to F.) , as well as different combinations of the material(s) of A.) to F.) as mentioned above.
- polymorphic SiO2 e.g.of theAerosil type from Degussa, Germany
- water soluble / dissolvable / dispersible compounds are used in combination with an additional water soluble or dispersible polymer.
- water soluble/dispersible polymer it will be appreciated that the water soluble polymer may comprise a homopolymer or a copolymer.
- the copolymer may be a random or block copolymer.
- a suitable additional water soluble polymer may comprise a cellulose derivative such as a cellulose ether e.g. hydroxypropyl cellulose, carboxymethyl cellulose, or the polymer comprises monomers of polyvinyl alcohol, polyvinyl pyrrolidone, partially hydrolysed polyvinyl acetate, polyvinyl acetate, modified acrylic, fumaric, maleic, itaconic, aconitic, mesaconic, citraconic and methylenemalonic acid or their salts, maleic anhydride, acrylamide, alkylene, vinylmethyl ether or styrene.
- Such polymers can either be homo- or copolymers of the mentioned monomer units.
- polyvinyl pyrrolidone homopolymers or copolymers of polyvinylalcohol preferably copolymers of polyvinylalcohol and polycarboxylates, most preferred are copolymers of polyvinylalcohol with maleic acid or (meth)acrylic acid.
- the water soluble polymer preferably has dispersant, anti-redeposition, soil releasing or other detergency properties.
- the additional water soluble polymer may further be a polymer comprising sulfonic acid groups like e.g. the polymers described in EP-A 1 299 513, EP-A 1 363 986, WO 95/12654 or EP-A 0 877 002
- the water soluble polymer system may comprise a soil release agent.
- polymeric soil release agents include those having: (a) one or more nonionic hydrophile components consisting essentially of (i) polyoxyethylene segments with a degree of polymerization of at least 2, or (ii) oxypropylene or polyoxypropylene segments with a degree of polymerization of from 2 to 10, wherein said hydrophile segment does not encompass any oxypropylene unit unless it is bonded to adjacent moieties at each end by ether linkages, or (iii) a mixture of oxyalkylene units comprising oxyethylene and from 1 to 30 oxypropylene units, said hydrophile segments preferably comprising at least 25% oxyethylene units and more preferably, especially for such components having 20 to 30 oxypropylene units, at least 50% oxyethylene units; or (b) one or more hydrophobe components comprising (i) C3 oxyalkylene terephthalate segments, wherein, if said hydrophobe components also comprise oxyethylene terephthalate, the ratio of oxyethylene terephthalate:
- the polyoxyethylene segments of (a)(i) will have a degree of polymerization of from 1 to 200, although higher levels can be used, preferably from 3 to 150, more preferably from 6 to 100.
- Suitable oxy C4-C6 alkylene hydrophobe segments include, but are not limited to, end-caps of polymeric soil release agents such as MO 3 S(CH:)nOCH:CH 2 O-, where M is sodium and n is an integer from 4-6.
- Other soil release agents useful herein also include cellulosic derivatives such as hydroxyether cellulosic polymers, copolymeric blocks of ethylene terephthalate or propylene terephthalate with polyethylene oxide or polypropylene oxide terephthalate, and the like.
- Such agents are commercially available and include hydroxyethers of cellulose such as METHOCEL (Dow).
- Cellulosic soil release agents for use herein also include those selected from the group consisting of Ct-C4 alkyl and C4 hydroxyalkyl cellulose.
- Further suitable surfactants include water-soluble cationic ethoxylated amine compounds with particulate soil/claysoil removal and/or anti-redeposition properties. Particularly preferred of these cationic compounds are ethoxylated cationic monoamines, diamines or triamines.
- a preferred coating system in accordance with the invention meets one or more of the following physical parameters:
- a) High suitability for coated materials such as providing an effective barrier to the materials coated therewith and displaying compatibility with hydroscopic and caustic materials.
- b) High solubility in water for example a 0.1 -1g of the coating composition material of the present invention dissolves within 10 minutes in a 1 L beaker of water at 40° C when stirred at 200 r.p.m and within 20 minutes at 20° C under the same conditions.
- the material may include a dissolubility modifying additive.
- Preferred examples of such additives include plasticizers.
- any additives are substantially water soluble or dispersible so that the overall system retains its water solubility / water dispersibility.
- the water soluble coating system may contain a plasticizer with a content of more than 0.01%, preferably more than 0.1%, more preferred more than 0.5% and most preferred 1 % or more and up to 30%, preferably less than 30 wt %, more preferably 10% or less than 10%.
- Suitable types of plasticizers include solvents.
- solvents include water, alkylene glycol mono lower alkyl ethers, glycerol, polyalcohols, propylene glycols, ethoxylated or propoxylated ethylene or propylene, glycerol esters, glycerol triacetate, polyethylene glycols, methyl esters and amides.
- plasticizers comprises the medium molecular weight polyethylene glycols (PEGs). Such materials preferably have molecular weights of at least 150. PEGs of molecular weight ranging from 200 to 3000 are most preferred. Yet another preferred type of plasticizers comprises lower molecular weight methyl esters. Such materials are those of the general formula: R-C(O)- OCH 3 wherein R ranges from 1 to 18. Examples of suitable lower molecular weight methyl esters include methyl acetate, methyl propionate, methyl octanoate, and methyl dodecanoate.
- Suitable types of plasticisers also include nonionic surfactants.
- Preferred nonionic surfactants incorporated into the resin provide a suds suppression benefit.
- the alkyl ethoxylate condensation products of an alcohol with from 1 to 80 moles of an alkylene (liner/branched aliphatic / aromatic optionally subsituted C 2 to C- 20 alkylene) oxide are suitable for this use.
- the alkyl chain of the alcohol can either be straight or branched, primary or secondary, and generally contains from 6 to 22 carbon atoms.
- Particularly preferred are the condensation products of alcohols having an alkyl group containing from 8 to 20 carbon atoms with from 2 to 10 moles of ethylene oxide per mole of alcohol.
- Suitable surfactants include POLY-TERGENT(R) SLF-18B nonionic surfactants by ONn Corporation.
- Ethoxylated Ce-C 18 fatty alcohols and C ⁇ -Ci ⁇ mixed ethoxylated/propoxylated fatty alcohols are suitable surfactants for use herein.
- the ethoxylated fatty alcohols are the C 10 -Ci 8 ethoxylated fatty alcohols with a degree of ethoxylation of from 3 to 50, most preferably these are the C- 12 -C 18 ethoxylated fatty alcohols with a degree of ethoxylation from 3 to 40.
- the mixed ethoxylated/propoxylated fatty alcohols have an alkyl chain length of from 10 to 18 carbon atoms, a degree of ethoxylation of from 3 to 30 and a degree of propoxylation of from 1 to 10.
- the condensation products of ethylene oxide with a hydrophobic base formed by the condensation of propylene oxide with propylene glycol are suitable for use herein.
- the hydrophobic portion of these compounds preferably has a molecular weight of from 1500 to 1800 and exhibits water insolubility.
- Examples of compounds of this type include certain of the commercially-available Pluronic (TM) surfactants, marketed by BASF.
- condensation products of ethylene oxide with the product resulting from the reaction of propylene oxide and ethylenediamine are suitable for use herein.
- the hydrophobic moiety of these products consists of the reaction product of ethylenediamine and excess propylene oxide, and generally has a molecular weight of from 2500 to 3000.
- this type of nonionic surfactant include certain of the commercially available Tetronic(TM) compounds, marketed by BASF.
- the polymer system may comprises a mixed nonionic surfactant system.
- Suitable compounds include fatty esters of mono- or polyhydric alcohols having from 1 to 40 carbon atoms in the hydrocarbon chain.
- the fatty acid portion of the fatty ester can be obtained from mono- or poly-carboxylic acids having from 1 to 40 carbon atoms in the hydrocarbon chain.
- monocarboxylic fatty acids include behenic acid, stearic acid, oleic acid, palmitic acid, myristic acid, lauric acid, acetic acid, propionic acid, butyric acid, isobutyric acid, Valerie acid, lactic acid, glycolic acid and beta.beta'-dihydroxyisobutyric acid.
- Suitable polycarboxylic acids include: n-butyl-malonic acid, isocitric acid, citric acid, maleic acid, malic acid and succinic acid.
- the fatty alcohol radical in the fatty ester can be represented by mono- or polyhydric alcohols having from 1 to 40 carbon atoms in the hydrocarbon chain.
- suitable fatty alcohols include; behenyl, arachidyl, cocoyl, oleyl and lauryl alcohol, ethylene glycol, glycerol, ethanol, isopropanol, vinyl alcohol, diglycerol, xylitol, sucrose, erythritol, pentaerythritol, sorbitol or sorbitan.
- the fatty acid and/or fatty alcohol group of the fatty ester adjunct material has from 1 to 24 carbon atoms in the alkyl chain.
- Preferred fatty esters herein are ethylene glycol, glycerol and sorbitan esters wherein the fatty acid portion of the ester normally comprises a species selected from behenic acid, stearic acid, oleic acid, palmitic acid or myristic acid.
- the glycerol esters are also highly preferred.
- Specific examples of fatty alcohol esters for use herein include: stearyl acetate, palmityl all- lactate, cocoyl isobutyrate, oleyl maleate, oleyl dimaleate, and tallowyl proprionate.
- Fatty acid esters useful herein include: xylitol monopalmitate, pentaerythritol monostearate, sucrose monostearate, glycerol mono stearate, ethylene glycol mono stearate, sorbitan esters.
- Suitable sorbitan esters include sorbitan monostearate, sorbitan palmitate, sorbitan monolaurate, sorbitan monomyristate, sorbitan monobehenate, sorbitan mono-oleate, sorbitan dilaurate, sorbitan distearate, sorbitan dibehenate, sorbitan dioleate, and also mixed tallow alkyl sorbitan mono- and all- esters.
- Glycerol monostearate, glycerol mono-oleate, glycerol monopalmitate, glycerol monobehenate, and glycerol distearate are preferred glycerol esters herein.
- Further suitable agents include triglycerides, mono or diglycerides, and wholly or partially hydrogenated derivatives thereof, and any mixtures thereof.
- Suitable sources of fatty acid esters include vegetable and fish oils and animal fats. Suitable vegetable oils include soy bean oil, cotton seed oil, castor oil, olive oil, peanut oil, safflower oil, sunflower oil, rapeseed oil, grapeseed oil, palm oil and corn oil.
- Waxes including microcrystalline waxes are possible lubricants, although much less preferred in the present invention due to their poor solubility in water.
- Preferred waxes have a melting point in the range from 35° C to 110° C and comprise generally from 12 to 70 carbon atoms.
- Preferred are petroleum waxes of the paraffin and microcrystalline type which are composed of long-chain saturated hydrocarbon compounds.
- a platicizing agent allows the reduction of the water content in the coating composition before/during the application of the composition to the detergent tablet. Since the detergent tablet consists itself of water dissolvable/dispersible components it is not desirable to apply a high water amount to the tablet during the coating process. Further the plasicizer provides the coating after drying with an increased smoothness and elasticity, resulting in less brittleness and more comfortable handling of the tablet.
- the coating may include a colourant.
- Colourant when present as a component in the resin is preferably present at a level of from 0.001 wt % to 1.5wt %, preferably from 0.01 wt % to 1.Owt %, most preferably from 0.1 wt % to 0.3wt %.
- the colourant may comprise a dye or a pigment.
- suitable dyes include reactive dyes, direct dyes, azo dyes.
- Preferred dyes include phthalocyanine dyes, anthraquinone dye, quinoline dyes, monoazo, disazo and polyazo. More preferred dyes include anthraquinone, quinoline and monoazo dyes.
- Preferred dyes include SANDOLAN E-HRL 180% (tradename), SANDOLAN MILLING BLUE (tradename), TURQUOISE ACID BLUE (tradename) and SANDOLAN BRILLIANT GREEN (tradename) all available from Clariant UK, HEXACOL QUINOLINE YELLOW (tradename) and HEXACOL BRILLIANT BLUE (tradename) both available from Paintings, UK 1 ULTRA MARINE BLUE (tradename) available from Holliday or LEVAFIX TURQUISE BLUE EBA (tradename) available from Bayer, USA and liquid colourants e.g. of the type Liquitit ® of Miliken
- the article preferably comprises a cleaning composition or a water softener composition.
- the cleaning composition may be an automatic dishwashing detergent or additive, a laundry detergent or additive, a hard surface cleaning composition (such as an all-purpose cleaner) or a toilet reservoir cleaner.
- Such a coated article has been found to be particularly suitable since the coating material is formed of components allowing a fast decomposition of the coating; in use the article has been found to overcome the problem of residue formation on items being cleaned, said residue being formed of packaging material having poor solubility.
- the cleaning composition may comprise of among others a builder system, a bleach system, a silver protecting system, a protecting system for glass (against glass corrosion), an enzyme system, a viscosity modifier, a perfume or odor control system, one or more colourants, an acidity modifier, a bactericide / fungicide, a surfactant system, and a polymer system comprising a polymer supporting spotting characteristics and/or a polymer supporting filming characteristics (like for example discussed in EP-A 1299 513, 1 363 986, WO 95/12654 or EP-A 0 877 002) and a tablet disintegrate without being limited to these ingredients.
- a builder system a bleach system, a silver protecting system, a protecting system for glass (against glass corrosion), an enzyme system, a viscosity modifier, a perfume or odor control system, one or more colourants, an acidity modifier, a bactericide / fungicide, a surfactant system, and a poly
- ingredients of the composition do not limit the present invention and any suitable detergent composition for different purposes can be used.
- Typical components of automatic dishwashing compositions are disclosed for example in EP-A 1 268 729, EP-A 1 299 513, EP-A 1 571 198, EP-A 1 520 908 and EP-A 1 524 313. All the components described therein may be part of the compositions coated according to the present invention..
- the composition may be formulated having regard to the fact that the user will not come into contact with the composition, whether by inhalation or by skin contact.
- the composition may include an enzyme, without concern about physical contact between the composition containing the enzyme, and the user.
- dishwashing compositions particularly preferred dishwashing compositions comprising silver protection systems, low phosphate content and a polymer system providing good spotting and filming characteristics.
- a fast dissolving rate is achieved by a thin coating of said water dissolvable material.
- the present invention uses coatings of water dissolvable materials with thicknesses between 5 ⁇ m and 1000 ⁇ m, more preferably between 20 ⁇ m and 600 ⁇ m.
- the coating corresponds to about 0.1 % by weight to 10 % by weight of the total amount of the detergent unit.
- said unit coated detergent may be provided in a bag which contains substantially in a loose manner the detergent particles.
- said unit packaged detergents are delivered in a container made of any material, like carton, plastic or metal if required supplied with a coating.
- said unit coated detergent may comprise an additive which provides an unbearable bitter taste, particularly in case the coating comprises any sugar.
- This additive may be coated onto said detergent composition, either as part of the water soluble coating or as a separate coating . This improves the prevention that children may accidentally ingest the complete detergent.
- the unit coated detergent according to the present invention may be manufactured in the following way:
- the detergent composition is prepared in its granular or particulate form; the granular or particulate detergent composition may be formed into a tablet of the desired shape and size by any of the methods known in the art, for example selected from the group of: compression, extrusion and casting, whereas said detergent composition is homogeneously distributed throughout the tablet or comprises different layers or phases of certain detergent ingredients; a water dissolvable or dispersible material is prepared as an aqueous or organic solution or dispersion (which means that the material is solved or dispersed in an aqueous system or a system comprising at least one organic solvent like alcohol or similar) or a melt (e.g.
- said detergent in granular or tablet form is coated with said solution, dispersion or melt of the water soluble or dissolvable material to form the unit coated detergent; optionally the unit coated detergent passes a drying step and/or a stabilizing / solidifying step, the last two mentioned steps (coating and drying) optionally can be repeated to provide more than one, preferably at least two layers of the water dissolvable or dispersible material.
- the water soluble material prepared as a solution, melt or dispersion comprising all components desired to be in the coating, is coated onto the material by any suitable method.
- the material is coated by spraying, dipping, immersing or similar.
- a coating composition is prepared by combining 33% by weight of limed bone Gelatine 120 bloom (corresponds to 80,000 to 150,000 g/mol gelatine)
- the composition is heated in a water bath to about 60 0 C to 95°C and applied to a detergent tablet by means of a brush. After drying the composition resulted in a stabile coating on the tablet.
- the detergent tablet didn't show any swelling or damaging, since only very less water is delivered from the coating. Most of the water is absorbed by the gelatine and lsomalt, resulting in a stabile and uniform coating on the tablet without affecting the detergent .
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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)
- Health & Medical Sciences (AREA)
- Molecular Biology (AREA)
- Emergency Medicine (AREA)
- Detergent Compositions (AREA)
Abstract
Priority Applications (2)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
PL07818237T PL2126032T3 (pl) | 2006-09-22 | 2007-09-19 | Powlekane kompozycje detergentowe i sposoby wytwarzania |
EP07818237A EP2126032B1 (fr) | 2006-09-22 | 2007-09-19 | Compositions de détergent enrobées et procédé de fabrication |
Applications Claiming Priority (3)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
EP06019837A EP1903099A1 (fr) | 2006-09-22 | 2006-09-22 | Compositions détergentes enrobées et leur procédé de fabrication |
PCT/EP2007/008137 WO2008034594A1 (fr) | 2006-09-22 | 2007-09-19 | Compositions de détergent enrobées et procédé de fabrication |
EP07818237A EP2126032B1 (fr) | 2006-09-22 | 2007-09-19 | Compositions de détergent enrobées et procédé de fabrication |
Publications (2)
Publication Number | Publication Date |
---|---|
EP2126032A1 true EP2126032A1 (fr) | 2009-12-02 |
EP2126032B1 EP2126032B1 (fr) | 2013-03-06 |
Family
ID=37686043
Family Applications (2)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
EP06019837A Withdrawn EP1903099A1 (fr) | 2006-09-22 | 2006-09-22 | Compositions détergentes enrobées et leur procédé de fabrication |
EP07818237A Active EP2126032B1 (fr) | 2006-09-22 | 2007-09-19 | Compositions de détergent enrobées et procédé de fabrication |
Family Applications Before (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
EP06019837A Withdrawn EP1903099A1 (fr) | 2006-09-22 | 2006-09-22 | Compositions détergentes enrobées et leur procédé de fabrication |
Country Status (8)
Country | Link |
---|---|
EP (2) | EP1903099A1 (fr) |
ES (1) | ES2406068T3 (fr) |
ME (1) | MEP8609A (fr) |
NO (1) | NO20091206L (fr) |
PL (1) | PL2126032T3 (fr) |
RU (1) | RU2462508C2 (fr) |
UA (1) | UA98942C2 (fr) |
WO (1) | WO2008034594A1 (fr) |
Families Citing this family (11)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
ES2523029T3 (es) | 2008-12-05 | 2014-11-20 | Dalli-Werke Gmbh & Co. Kg | Pastilla de detergente revestida de polímero |
BE1020860A3 (nl) * | 2012-08-09 | 2014-06-03 | Ecover Co Ordination Ct Nv | Tablet coating. |
EP3334816B1 (fr) | 2015-08-11 | 2019-01-23 | Unilever Plc. | Emballage hydrosoluble |
FR3044678B1 (fr) * | 2015-12-04 | 2017-12-08 | Eurotab | Tablette detergente enrobee |
ITUB20159349A1 (it) * | 2015-12-18 | 2017-06-18 | Deoflor Spa | Processo per ricoprire prodotti per la cura dei vasi sanitari con un rivestimento idrosolubile. |
WO2017137225A1 (fr) | 2016-02-09 | 2017-08-17 | Unilever Plc | Emballage hydrosoluble |
EP3694965A1 (fr) | 2017-10-13 | 2020-08-19 | Unilever PLC | Composition de pulvérisation aqueuse |
EP3694964A1 (fr) | 2017-10-13 | 2020-08-19 | Unilever PLC | Composition aqueuse en aérosol |
WO2019072643A1 (fr) | 2017-10-13 | 2019-04-18 | Unilever Plc | Composition aqueuse de pulvérisation |
CN111971375A (zh) | 2017-10-13 | 2020-11-20 | 荷兰联合利华有限公司 | 织物喷雾组合物 |
FR3113065A1 (fr) * | 2020-07-31 | 2022-02-04 | Eurotab Operations | Nouvelle tablette détergente enrobée |
Family Cites Families (7)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US3297535A (en) * | 1963-02-28 | 1967-01-10 | Hoffmann La Roche | Shellac tablet coating compositions and methods of preparation |
US5133892A (en) * | 1990-10-17 | 1992-07-28 | Lever Brothers Company, Division Of Conopco, Inc. | Machine dishwashing detergent tablets |
GB9422924D0 (en) * | 1994-11-14 | 1995-01-04 | Unilever Plc | Detergent compositions |
BR9909359A (pt) * | 1998-04-02 | 2000-12-12 | Genencor Int | Revestimento, grânulo, composição, composição de limpeza, forma de dosagem farmacêutica revestida, semente revestida, composição têxtil, e, composição de alimentação |
ATE250661T1 (de) * | 1998-07-17 | 2003-10-15 | Procter & Gamble | Waschmitteltablette |
GB0004805D0 (en) * | 2000-03-01 | 2000-04-19 | Procter & Gamble | Solid bodies |
DE10125441A1 (de) * | 2001-05-25 | 2002-12-05 | Henkel Kgaa | Verfahren und benötigte Zusätze zur Erhöhung der Stabilität von Tabletten |
-
2006
- 2006-09-22 EP EP06019837A patent/EP1903099A1/fr not_active Withdrawn
-
2007
- 2007-09-19 WO PCT/EP2007/008137 patent/WO2008034594A1/fr active Application Filing
- 2007-09-19 PL PL07818237T patent/PL2126032T3/pl unknown
- 2007-09-19 RU RU2009115207/04A patent/RU2462508C2/ru not_active IP Right Cessation
- 2007-09-19 ME MEP-86/09A patent/MEP8609A/xx unknown
- 2007-09-19 ES ES07818237T patent/ES2406068T3/es active Active
- 2007-09-19 EP EP07818237A patent/EP2126032B1/fr active Active
- 2007-09-19 UA UAA200903929A patent/UA98942C2/ru unknown
-
2009
- 2009-03-23 NO NO20091206A patent/NO20091206L/no not_active Application Discontinuation
Non-Patent Citations (1)
Title |
---|
See references of WO2008034594A1 * |
Also Published As
Publication number | Publication date |
---|---|
PL2126032T3 (pl) | 2013-08-30 |
ES2406068T3 (es) | 2013-06-05 |
RU2462508C2 (ru) | 2012-09-27 |
UA98942C2 (ru) | 2012-07-10 |
WO2008034594A1 (fr) | 2008-03-27 |
NO20091206L (no) | 2009-04-22 |
RU2009115207A (ru) | 2010-10-27 |
MEP8609A (en) | 2011-12-20 |
EP1903099A1 (fr) | 2008-03-26 |
EP2126032B1 (fr) | 2013-03-06 |
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