EP2367920A1 - Détergent pour lave-vaisselle - Google Patents
Détergent pour lave-vaisselleInfo
- Publication number
- EP2367920A1 EP2367920A1 EP09795392A EP09795392A EP2367920A1 EP 2367920 A1 EP2367920 A1 EP 2367920A1 EP 09795392 A EP09795392 A EP 09795392A EP 09795392 A EP09795392 A EP 09795392A EP 2367920 A1 EP2367920 A1 EP 2367920A1
- Authority
- EP
- European Patent Office
- Prior art keywords
- weight
- dishwashing detergent
- detergent according
- carbonate
- machine dishwashing
- 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 106
- VKZRWSNIWNFCIQ-WDSKDSINSA-N (2s)-2-[2-[[(1s)-1,2-dicarboxyethyl]amino]ethylamino]butanedioic acid Chemical compound OC(=O)C[C@@H](C(O)=O)NCCN[C@H](C(O)=O)CC(O)=O VKZRWSNIWNFCIQ-WDSKDSINSA-N 0.000 claims abstract description 41
- BVKZGUZCCUSVTD-UHFFFAOYSA-N carbonic acid Chemical compound OC(O)=O BVKZGUZCCUSVTD-UHFFFAOYSA-N 0.000 claims abstract description 39
- 238000004140 cleaning Methods 0.000 claims abstract description 35
- KRKNYBCHXYNGOX-UHFFFAOYSA-K Citrate Chemical compound [O-]C(=O)CC(O)(CC([O-])=O)C([O-])=O KRKNYBCHXYNGOX-UHFFFAOYSA-K 0.000 claims abstract description 13
- 238000004851 dishwashing Methods 0.000 claims description 93
- 239000002736 nonionic surfactant Substances 0.000 claims description 57
- 125000004432 carbon atom Chemical group C* 0.000 claims description 40
- 239000003795 chemical substances by application Substances 0.000 claims description 40
- 239000000178 monomer Substances 0.000 claims description 31
- 102000004190 Enzymes Human genes 0.000 claims description 23
- 108090000790 Enzymes Proteins 0.000 claims description 23
- 238000000034 method Methods 0.000 claims description 16
- 239000007788 liquid Substances 0.000 claims description 13
- 229920006395 saturated elastomer Polymers 0.000 claims description 13
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 13
- 108091005804 Peptidases Proteins 0.000 claims description 11
- 150000001735 carboxylic acids Chemical class 0.000 claims description 10
- 229920001577 copolymer Polymers 0.000 claims description 10
- 108010065511 Amylases Proteins 0.000 claims description 9
- 102000013142 Amylases Human genes 0.000 claims description 9
- 235000019418 amylase Nutrition 0.000 claims description 9
- UEZVMMHDMIWARA-UHFFFAOYSA-M phosphonate Chemical compound [O-]P(=O)=O UEZVMMHDMIWARA-UHFFFAOYSA-M 0.000 claims description 8
- HZAXFHJVJLSVMW-UHFFFAOYSA-N 2-Aminoethan-1-ol Chemical compound NCCO HZAXFHJVJLSVMW-UHFFFAOYSA-N 0.000 claims description 7
- 229910019142 PO4 Inorganic materials 0.000 claims description 7
- 150000003460 sulfonic acids Chemical class 0.000 claims description 7
- 102100037486 Reverse transcriptase/ribonuclease H Human genes 0.000 claims description 6
- 150000001412 amines Chemical class 0.000 claims description 6
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 claims description 6
- 239000010452 phosphate Substances 0.000 claims description 6
- 238000002360 preparation method Methods 0.000 claims description 6
- 239000004382 Amylase Substances 0.000 claims description 5
- XINQFOMFQFGGCQ-UHFFFAOYSA-L (2-dodecoxy-2-oxoethyl)-[6-[(2-dodecoxy-2-oxoethyl)-dimethylazaniumyl]hexyl]-dimethylazanium;dichloride Chemical compound [Cl-].[Cl-].CCCCCCCCCCCCOC(=O)C[N+](C)(C)CCCCCC[N+](C)(C)CC(=O)OCCCCCCCCCCCC XINQFOMFQFGGCQ-UHFFFAOYSA-L 0.000 claims description 4
- LOTBYPQQWICYBB-UHFFFAOYSA-N methyl n-hexyl-n-[2-(hexylamino)ethyl]carbamate Chemical compound CCCCCCNCCN(C(=O)OC)CCCCCC LOTBYPQQWICYBB-UHFFFAOYSA-N 0.000 claims description 2
- 241001122767 Theaceae Species 0.000 abstract 1
- -1 alkali metal salts Chemical class 0.000 description 52
- IAYPIBMASNFSPL-UHFFFAOYSA-N Ethylene oxide Chemical compound C1CO1 IAYPIBMASNFSPL-UHFFFAOYSA-N 0.000 description 43
- 239000000203 mixture Substances 0.000 description 39
- 229940088598 enzyme Drugs 0.000 description 20
- 239000002253 acid Substances 0.000 description 18
- 150000003839 salts Chemical class 0.000 description 17
- 239000004094 surface-active agent Substances 0.000 description 17
- 239000007844 bleaching agent Substances 0.000 description 14
- 150000003254 radicals Chemical class 0.000 description 14
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 13
- 150000001298 alcohols Chemical class 0.000 description 11
- ABLZXFCXXLZCGV-UHFFFAOYSA-N Phosphorous acid Chemical class OP(O)=O ABLZXFCXXLZCGV-UHFFFAOYSA-N 0.000 description 9
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 description 9
- 238000009472 formulation Methods 0.000 description 9
- DBVJJBKOTRCVKF-UHFFFAOYSA-N Etidronic acid Chemical compound OP(=O)(O)C(O)(C)P(O)(O)=O DBVJJBKOTRCVKF-UHFFFAOYSA-N 0.000 description 8
- GOOHAUXETOMSMM-UHFFFAOYSA-N Propylene oxide Chemical group CC1CO1 GOOHAUXETOMSMM-UHFFFAOYSA-N 0.000 description 8
- 150000001875 compounds Chemical class 0.000 description 8
- 230000000694 effects Effects 0.000 description 8
- 239000003960 organic solvent Substances 0.000 description 8
- 239000004365 Protease Substances 0.000 description 7
- 150000007513 acids Chemical class 0.000 description 7
- 239000012459 cleaning agent Substances 0.000 description 7
- 238000005406 washing Methods 0.000 description 7
- CIEZZGWIJBXOTE-UHFFFAOYSA-N 2-[bis(carboxymethyl)amino]propanoic acid Chemical compound OC(=O)C(C)N(CC(O)=O)CC(O)=O CIEZZGWIJBXOTE-UHFFFAOYSA-N 0.000 description 6
- 239000004615 ingredient Substances 0.000 description 6
- 239000012071 phase Substances 0.000 description 6
- 235000021317 phosphate Nutrition 0.000 description 6
- 229920001451 polypropylene glycol Polymers 0.000 description 6
- 239000007787 solid Substances 0.000 description 6
- 102000035195 Peptidases Human genes 0.000 description 5
- 125000002947 alkylene group Chemical group 0.000 description 5
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 5
- LYCAIKOWRPUZTN-UHFFFAOYSA-N ethylene glycol Natural products OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 5
- 150000002191 fatty alcohols Chemical class 0.000 description 5
- 229920000642 polymer Polymers 0.000 description 5
- 235000018102 proteins Nutrition 0.000 description 5
- 102000004169 proteins and genes Human genes 0.000 description 5
- 108090000623 proteins and genes Proteins 0.000 description 5
- 239000000126 substance Substances 0.000 description 5
- 125000000542 sulfonic acid group Chemical group 0.000 description 5
- 239000004215 Carbon black (E152) Substances 0.000 description 4
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 4
- VZCYOOQTPOCHFL-OWOJBTEDSA-N Fumaric acid Chemical compound OC(=O)\C=C\C(O)=O VZCYOOQTPOCHFL-OWOJBTEDSA-N 0.000 description 4
- 108090000854 Oxidoreductases Proteins 0.000 description 4
- 102000004316 Oxidoreductases Human genes 0.000 description 4
- 229920003171 Poly (ethylene oxide) Polymers 0.000 description 4
- 108010056079 Subtilisins Proteins 0.000 description 4
- 102000005158 Subtilisins Human genes 0.000 description 4
- 239000013543 active substance Substances 0.000 description 4
- WNLRTRBMVRJNCN-UHFFFAOYSA-N adipic acid Chemical compound OC(=O)CCCCC(O)=O WNLRTRBMVRJNCN-UHFFFAOYSA-N 0.000 description 4
- 150000001338 aliphatic hydrocarbons Chemical class 0.000 description 4
- 125000000217 alkyl group Chemical group 0.000 description 4
- 229940025131 amylases Drugs 0.000 description 4
- 239000003054 catalyst Substances 0.000 description 4
- 239000001913 cellulose Substances 0.000 description 4
- 229920002678 cellulose Polymers 0.000 description 4
- 238000011109 contamination Methods 0.000 description 4
- 229930195733 hydrocarbon Natural products 0.000 description 4
- 239000002904 solvent Substances 0.000 description 4
- 238000003860 storage Methods 0.000 description 4
- VZCYOOQTPOCHFL-UHFFFAOYSA-N trans-butenedioic acid Natural products OC(=O)C=CC(O)=O VZCYOOQTPOCHFL-UHFFFAOYSA-N 0.000 description 4
- BVKZGUZCCUSVTD-UHFFFAOYSA-M Bicarbonate Chemical class OC([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-M 0.000 description 3
- LSNNMFCWUKXFEE-UHFFFAOYSA-M Bisulfite Chemical compound OS([O-])=O LSNNMFCWUKXFEE-UHFFFAOYSA-M 0.000 description 3
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Natural products CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 3
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 description 3
- 108090001060 Lipase Proteins 0.000 description 3
- 102000004882 Lipase Human genes 0.000 description 3
- 239000004367 Lipase Substances 0.000 description 3
- 239000004480 active ingredient Substances 0.000 description 3
- 229910000318 alkali metal phosphate Inorganic materials 0.000 description 3
- 150000003973 alkyl amines Chemical group 0.000 description 3
- 108090000637 alpha-Amylases Proteins 0.000 description 3
- 239000007864 aqueous solution Substances 0.000 description 3
- 238000004061 bleaching Methods 0.000 description 3
- 229920001400 block copolymer Polymers 0.000 description 3
- 150000004649 carbonic acid derivatives Chemical class 0.000 description 3
- 150000001860 citric acid derivatives Chemical class 0.000 description 3
- 239000011248 coating agent Substances 0.000 description 3
- 238000000576 coating method Methods 0.000 description 3
- 239000000470 constituent Substances 0.000 description 3
- 238000009826 distribution Methods 0.000 description 3
- DUYCTCQXNHFCSJ-UHFFFAOYSA-N dtpmp Chemical compound OP(=O)(O)CN(CP(O)(O)=O)CCN(CP(O)(=O)O)CCN(CP(O)(O)=O)CP(O)(O)=O DUYCTCQXNHFCSJ-UHFFFAOYSA-N 0.000 description 3
- 238000007046 ethoxylation reaction Methods 0.000 description 3
- 239000008187 granular material Substances 0.000 description 3
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 description 3
- 239000010410 layer Substances 0.000 description 3
- 235000019421 lipase Nutrition 0.000 description 3
- 238000002844 melting Methods 0.000 description 3
- 230000008018 melting Effects 0.000 description 3
- 159000000000 sodium salts Chemical class 0.000 description 3
- 239000000243 solution Substances 0.000 description 3
- 125000006850 spacer group Chemical group 0.000 description 3
- 239000003381 stabilizer Substances 0.000 description 3
- 239000003760 tallow Substances 0.000 description 3
- VQJMAIZOEPPELO-KYGIZGOZSA-N (1S,2S,6R,14R,15R,16R)-5-(cyclopropylmethyl)-16-(2-hydroxy-5-methylhexan-2-yl)-15-methoxy-13-oxa-5-azahexacyclo[13.2.2.12,8.01,6.02,14.012,20]icosa-8(20),9,11-trien-11-ol hydrochloride Chemical compound Cl.CO[C@]12CC[C@@]3(C[C@@H]1C(C)(O)CCC(C)C)[C@H]1Cc4ccc(O)c5O[C@@H]2[C@]3(CCN1CC1CC1)c45 VQJMAIZOEPPELO-KYGIZGOZSA-N 0.000 description 2
- ALSTYHKOOCGGFT-KTKRTIGZSA-N (9Z)-octadecen-1-ol Chemical compound CCCCCCCC\C=C/CCCCCCCCO ALSTYHKOOCGGFT-KTKRTIGZSA-N 0.000 description 2
- AFFLGGQVNFXPEV-UHFFFAOYSA-N 1-decene Chemical compound CCCCCCCCC=C AFFLGGQVNFXPEV-UHFFFAOYSA-N 0.000 description 2
- CRSBERNSMYQZNG-UHFFFAOYSA-N 1-dodecene Chemical compound CCCCCCCCCCC=C CRSBERNSMYQZNG-UHFFFAOYSA-N 0.000 description 2
- GQEZCXVZFLOKMC-UHFFFAOYSA-N 1-hexadecene Chemical compound CCCCCCCCCCCCCCC=C GQEZCXVZFLOKMC-UHFFFAOYSA-N 0.000 description 2
- LIKMAJRDDDTEIG-UHFFFAOYSA-N 1-hexene Chemical compound CCCCC=C LIKMAJRDDDTEIG-UHFFFAOYSA-N 0.000 description 2
- CTMHWPIWNRWQEG-UHFFFAOYSA-N 1-methylcyclohexene Chemical compound CC1=CCCCC1 CTMHWPIWNRWQEG-UHFFFAOYSA-N 0.000 description 2
- RTBFRGCFXZNCOE-UHFFFAOYSA-N 1-methylsulfonylpiperidin-4-one Chemical compound CS(=O)(=O)N1CCC(=O)CC1 RTBFRGCFXZNCOE-UHFFFAOYSA-N 0.000 description 2
- KWKAKUADMBZCLK-UHFFFAOYSA-N 1-octene Chemical compound CCCCCCC=C KWKAKUADMBZCLK-UHFFFAOYSA-N 0.000 description 2
- IGGDKDTUCAWDAN-UHFFFAOYSA-N 1-vinylnaphthalene Chemical compound C1=CC=C2C(C=C)=CC=CC2=C1 IGGDKDTUCAWDAN-UHFFFAOYSA-N 0.000 description 2
- WWUVJRULCWHUSA-UHFFFAOYSA-N 2-methyl-1-pentene Chemical compound CCCC(C)=C WWUVJRULCWHUSA-UHFFFAOYSA-N 0.000 description 2
- MHNNAWXXUZQSNM-UHFFFAOYSA-N 2-methylbut-1-ene Chemical compound CCC(C)=C MHNNAWXXUZQSNM-UHFFFAOYSA-N 0.000 description 2
- SVTBMSDMJJWYQN-UHFFFAOYSA-N 2-methylpentane-2,4-diol Chemical compound CC(O)CC(C)(C)O SVTBMSDMJJWYQN-UHFFFAOYSA-N 0.000 description 2
- XEEYSDHEOQHCDA-UHFFFAOYSA-N 2-methylprop-2-ene-1-sulfonic acid Chemical compound CC(=C)CS(O)(=O)=O XEEYSDHEOQHCDA-UHFFFAOYSA-N 0.000 description 2
- YEYKMVJDLWJFOA-UHFFFAOYSA-N 2-propoxyethanol Chemical group CCCOCCO YEYKMVJDLWJFOA-UHFFFAOYSA-N 0.000 description 2
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 description 2
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- ROSDSFDQCJNGOL-UHFFFAOYSA-N Dimethylamine Chemical compound CNC ROSDSFDQCJNGOL-UHFFFAOYSA-N 0.000 description 2
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- VQTUBCCKSQIDNK-UHFFFAOYSA-N Isobutene Chemical compound CC(C)=C VQTUBCCKSQIDNK-UHFFFAOYSA-N 0.000 description 2
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- BAPJBEWLBFYGME-UHFFFAOYSA-N Methyl acrylate Chemical compound COC(=O)C=C BAPJBEWLBFYGME-UHFFFAOYSA-N 0.000 description 2
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- YDONNITUKPKTIG-UHFFFAOYSA-N [Nitrilotris(methylene)]trisphosphonic acid Chemical compound OP(O)(=O)CN(CP(O)(O)=O)CP(O)(O)=O YDONNITUKPKTIG-UHFFFAOYSA-N 0.000 description 2
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- 102000004139 alpha-Amylases Human genes 0.000 description 2
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- 125000002347 octyl 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])[H] 0.000 description 1
- 239000003921 oil Substances 0.000 description 1
- 238000006384 oligomerization reaction Methods 0.000 description 1
- 150000007524 organic acids Chemical class 0.000 description 1
- 235000005985 organic acids Nutrition 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 230000001590 oxidative effect Effects 0.000 description 1
- 108010087558 pectate lyase Proteins 0.000 description 1
- 108020004410 pectinesterase Proteins 0.000 description 1
- RGSFGYAAUTVSQA-UHFFFAOYSA-N pentamethylene Natural products C1CCCC1 RGSFGYAAUTVSQA-UHFFFAOYSA-N 0.000 description 1
- DPBLXKKOBLCELK-UHFFFAOYSA-N pentan-1-amine Chemical compound CCCCCN DPBLXKKOBLCELK-UHFFFAOYSA-N 0.000 description 1
- HWGNBUXHKFFFIH-UHFFFAOYSA-I pentasodium;[oxido(phosphonatooxy)phosphoryl] phosphate Chemical compound [Na+].[Na+].[Na+].[Na+].[Na+].[O-]P([O-])(=O)OP([O-])(=O)OP([O-])([O-])=O HWGNBUXHKFFFIH-UHFFFAOYSA-I 0.000 description 1
- YWAKXRMUMFPDSH-UHFFFAOYSA-N pentene Chemical compound CCCC=C YWAKXRMUMFPDSH-UHFFFAOYSA-N 0.000 description 1
- ULDDEWDFUNBUCM-UHFFFAOYSA-N pentyl prop-2-enoate Chemical compound CCCCCOC(=O)C=C ULDDEWDFUNBUCM-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
- 239000002304 perfume Substances 0.000 description 1
- 150000004965 peroxy acids Chemical class 0.000 description 1
- 150000003013 phosphoric acid derivatives Chemical class 0.000 description 1
- 239000000049 pigment Substances 0.000 description 1
- 229920005646 polycarboxylate Polymers 0.000 description 1
- 229920002959 polymer blend Polymers 0.000 description 1
- 229920005862 polyol Polymers 0.000 description 1
- 150000003077 polyols Chemical class 0.000 description 1
- 229920002503 polyoxyethylene-polyoxypropylene Polymers 0.000 description 1
- TYJJADVDDVDEDZ-UHFFFAOYSA-M potassium hydrogencarbonate Chemical compound [K+].OC([O-])=O TYJJADVDDVDEDZ-UHFFFAOYSA-M 0.000 description 1
- 159000000001 potassium salts Chemical class 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 239000002243 precursor Substances 0.000 description 1
- 150000003138 primary alcohols Chemical class 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
- BDERNNFJNOPAEC-UHFFFAOYSA-N propan-1-ol Chemical compound CCCO BDERNNFJNOPAEC-UHFFFAOYSA-N 0.000 description 1
- ULWHHBHJGPPBCO-UHFFFAOYSA-N propane-1,1-diol Chemical compound CCC(O)O ULWHHBHJGPPBCO-UHFFFAOYSA-N 0.000 description 1
- PNXMTCDJUBJHQJ-UHFFFAOYSA-N propyl prop-2-enoate Chemical compound CCCOC(=O)C=C PNXMTCDJUBJHQJ-UHFFFAOYSA-N 0.000 description 1
- WGYKZJWCGVVSQN-UHFFFAOYSA-N propylamine Chemical compound CCCN WGYKZJWCGVVSQN-UHFFFAOYSA-N 0.000 description 1
- 239000011241 protective layer Substances 0.000 description 1
- 230000006337 proteolytic cleavage Effects 0.000 description 1
- 238000011084 recovery Methods 0.000 description 1
- 230000002829 reductive effect Effects 0.000 description 1
- 230000002441 reversible effect Effects 0.000 description 1
- 238000005096 rolling process Methods 0.000 description 1
- 125000002914 sec-butyl group Chemical group [H]C([H])([H])C([H])([H])C([H])(*)C([H])([H])[H] 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- 235000012217 sodium aluminium silicate Nutrition 0.000 description 1
- 229910001415 sodium ion Inorganic materials 0.000 description 1
- 235000019832 sodium triphosphate Nutrition 0.000 description 1
- 239000002689 soil Substances 0.000 description 1
- 239000007909 solid dosage form Substances 0.000 description 1
- 239000007790 solid phase Substances 0.000 description 1
- 239000004334 sorbic acid Substances 0.000 description 1
- 229940075582 sorbic acid Drugs 0.000 description 1
- 235000010199 sorbic acid Nutrition 0.000 description 1
- 238000001694 spray drying Methods 0.000 description 1
- 239000008107 starch Substances 0.000 description 1
- 235000019698 starch Nutrition 0.000 description 1
- 150000005846 sugar alcohols Polymers 0.000 description 1
- 229920001059 synthetic polymer Polymers 0.000 description 1
- 239000007885 tablet disintegrant Substances 0.000 description 1
- 235000002906 tartaric acid Nutrition 0.000 description 1
- 239000011975 tartaric acid Substances 0.000 description 1
- 239000004753 textile Substances 0.000 description 1
- 108010031354 thermitase Proteins 0.000 description 1
- LDHQCZJRKDOVOX-UHFFFAOYSA-N trans-crotonic acid Natural products CC=CC(O)=O LDHQCZJRKDOVOX-UHFFFAOYSA-N 0.000 description 1
- 150000004072 triols Chemical class 0.000 description 1
- JSPLKZUTYZBBKA-UHFFFAOYSA-N trioxidane Chemical compound OOO JSPLKZUTYZBBKA-UHFFFAOYSA-N 0.000 description 1
- 239000001226 triphosphate Substances 0.000 description 1
- 235000013311 vegetables Nutrition 0.000 description 1
- NLVXSWCKKBEXTG-UHFFFAOYSA-N vinylsulfonic acid Chemical compound OS(=O)(=O)C=C NLVXSWCKKBEXTG-UHFFFAOYSA-N 0.000 description 1
- 230000000007 visual effect Effects 0.000 description 1
- 239000002351 wastewater Substances 0.000 description 1
- 239000003643 water by type Substances 0.000 description 1
- 108010068608 xanthan lyase Proteins 0.000 description 1
- 108010083879 xyloglucan endo(1-4)-beta-D-glucanase Proteins 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
- C11D3/02—Inorganic compounds ; Elemental compounds
- C11D3/04—Water-soluble compounds
- C11D3/10—Carbonates ; Bicarbonates
-
- 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
- C11D3/2075—Carboxylic acids-salts thereof
- C11D3/2086—Hydroxy carboxylic acids-salts 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
- C11D3/26—Organic compounds containing nitrogen
- C11D3/33—Amino carboxylic acids
Definitions
- the present application describes automatic dishwashing detergents, automatic dishwashing processes using these dishwashing detergents and the use of these dishwashing detergents for improving the machine dishwashing cleaning performance.
- automatic dishwasher detergents In order to obtain spotless dishes, bleaching agents are used in automatic dishwashing detergents. In order to activate these bleaching agents and to achieve an improved bleaching effect during cleaning at temperatures of 60 ° C. and below, automatic dishwasher detergents generally also contain bleach activators or bleach catalysts, with the bleach catalysts in particular having proven to be particularly effective.
- bleaches are limited due to incompatibilities with other detergent or cleaning active ingredients, such as enzymes, or because of stability issues in the storage of bleach-containing detergents and cleaners. This is especially true for liquid detergents or cleaning agents.
- the automatic dishwashing detergents intended for the private end user contain builders as the essential ingredient for the cleaning and rinse aid success.
- these builders increase the alkalinity of the cleaning liquor, whereby fats and oils are emulsified and saponified with increasing alkalinity, and on the other hand reduce the water hardness of the cleaning liquor by complexing the calcium ions contained in the aqueous liquor.
- Particularly effective builders have proved to be the alkali metal phosphates which, for this reason, form the main constituent of the vast majority of commercially available automatic dishwashing detergents.
- phosphates are highly valued for their beneficial effect as a component of automatic dishwashing detergents
- their use is not unproblematical from the environmental point of view since a substantial portion of the phosphate is present in household wastewater the waters get and especially in stagnant water (lakes, barrages) plays a critical role in their over-fertilization.
- eutrophication the use of pentasodium triphosphate in laundry detergents in a number of countries, eg USA, Canada, Italy, Sweden, Norway, has been considerably reduced by law and regulations. completely prohibited in Switzerland. In Germany, detergents since 1984 may contain no more than 20% of this builder.
- nitrilotriacetic acid especially sodium aluminosilicates (zeolites) are used as phosphate substitutes or substitutes in textile detergents.
- these substances are not suitable for use in automatic dishwashing detergents for various reasons.
- alkali metal phosphates in automatic dishwashing detergents therefore, a number of substitutes are discussed in the literature, of which the citrates are particularly noteworthy.
- Phosphate-free automatic dishwashing detergents which, in addition to a citrate, furthermore contain carbonates, bleaches and enzymes are described, for example, in European patents EP 662 117 B1 (Henkel KGaA) and EP 692 020 B1 (Henkel KGaA).
- MGDA methylglycine diacetic acid
- Machine dishwashing detergents containing MGDA are described, for example, in European patent EP 906 407 B1 (Reckitt Benckiser) or in European patent application EP 1 113 070 A2 (Reckitt Benckiser).
- automatic dishwasher detergents In order to activate these bleaching agents and to achieve an improved bleaching effect during cleaning at temperatures of 60 ° C. and below, automatic dishwasher detergents generally also contain bleach activators or Bleach catalysts, in particular, the bleach catalysts have been found to be particularly effective.
- bleaches are limited due to incompatibilities with other detergent or cleaning active ingredients, such as enzymes, or because of stability issues in the storage of bleach-containing detergents and cleaners. This is especially true for liquid detergents or cleaning agents.
- a first subject of the present application is therefore a phosphate and bleach-free machine dishwashing detergent, comprising: a) 5 to 60 wt .-% citrate b) (hydrogen) carbonate c) 2 to 40 wt .-% ethylenediamine disuccinic acid, characterized in that the weight ratio of components b) and c) is between 1: 5 and 10: 1.
- the automatic dishwashing compositions according to the invention are of low alkalinity.
- Preferred automatic dishwashing agents according to the invention are characterized in that the machine dishwashing detergents have a pH value (10% solution; 2O 0 C) between 9 and 11 5, preferably between 9.5 and 11; 5.
- a first essential ingredient of the composition of the invention is the citrate.
- the term "citrate” also encompasses citric acid as well as its salts, in particular their alkali metal salts
- Particularly preferred machine dishwashing agents according to the invention contain, based on their total weight, 5 to 50% by weight, preferably 5 to 40% by weight and in particular 5 to 30% by weight of citrate.
- the dishwasher detergents according to the invention contain, in addition to the citrates, additional carbonates and / or bicarbonates as additional builders. The group of carbonates and bicarbonates is summarized in the context of this application by the name (hydrogen) carbonate.
- the automatic dishwashing compositions according to the invention contain ethylenediamine disuccinic acid (EDDS), preferred automatic dishwashing agents, characterized in that the automatic dishwashing agent, based on its total weight, 3.0 to 35 wt .-%, preferably 4.0 to 30 wt. % and in particular 8.0 to 25 wt .-% ethylenediamine disuccinic acid.
- EDDS ethylenediamine disuccinic acid
- ethylenediamine disuccinic acid encompasses not only the free acids but also their salts, for example their sodium or potassium salts
- EDDS ethylenediamine disuccinic acid
- the weight ratio of the components (hydrogen) carbonate b) and ethylenediamine disuccinic acid c) used in these agents has proven to be essential.
- the Teealisms in the machine dishwashing detergent according to the invention can be improved, wherein weight ratios of the components (hydrogen) carbonate b) and ethylenediamine disuccinic acid c) between 3: 5 and 8: 1, preferably between 1: 1 and 6: 1 and in particular between 1: 1 and 4: 1, have proven to be particularly advantageous.
- Preferred automatic dishwashing detergents are therefore characterized in that, based on their total weight, they contain from 2.0 to 20% by weight, preferably from 2.5 to 15% by weight and in particular from 2.5 to 10% by weight of anionic copolymer, comprising i) one or more polyunsaturated monomers from the group of carboxylic acids ii) one or more polyunsaturated monomers from the group of sulfonic acids iii) optionally contain further ionic or nonionic monomers.
- unsaturated carboxylic acids are acrylic acid, methacrylic acid, ethacrylic acid, ⁇ -chloroacrylic acid, ⁇ -cyanoacrylic acid, crotonic acid, ⁇ -phenyl-acrylic acid, maleic acid, maleic anhydride, fumaric acid, itaconic acid, citraconic acid, methylenemalonic acid, sorbic acid, cinnamic acid or mixtures thereof. It goes without saying that it is also possible to use the unsaturated dicarboxylic acids.
- the sulfonic acid-containing monomers are those of the formula
- R 6 and R 7 are independently selected from -H, -CH 3 , -
- Particularly preferred monomers containing sulfonic acid groups are 1-acrylamido-1-propanesulfonic acid, 2-acrylamido-2-propanesulfonic acid, 2-acrylamido-2-methyl-1-propanesulfonic acid, 2-methacrylamido-2-methyl-1-propanesulfonic acid, 3 Methacrylamido-2-hydroxypropanesulfonic acid, allylsulfonic acid, methallylsulfonic acid, allyloxybenzenesulfonic acid, methallyloxybenzenesulfonic acid, 2-hydroxy-3- (2-propenyloxy) propanesulfonic acid, 2-methyl-2-propene-1-sulfonic acid, styrenesulfonic acid, vinylsulfonic acid, 3-sulfopropyl acrylate, 3-sulfopropyl methacrylate , Sulfomethacrylamide, sulfomethylmethacrylamide and mixtures of said acids or their water-soluble
- the sulfonic acid groups may be wholly or partly in neutralized form, ie that the acidic acid of the sulfonic acid group in some or all sulfonic acid groups may be exchanged for metal ions, preferably alkali metal ions and especially sodium ions.
- metal ions preferably alkali metal ions and especially sodium ions.
- the molar mass of the sulfo copolymers preferably used according to the invention can be varied in order to adapt the properties of the polymers to the desired end use.
- Preferred automatic dishwasher detergents are characterized in that the copolymers have molar masses of from 2000 to 200,000 gmol.sup.- 1 , preferably from 4000 to 25,000 gmol.sup.- 1 and in particular from 5000 to 15,000 gmol.sup.- 1 .
- the polymeric sulfonates in addition to carboxyl-containing monomer and sulfonic acid-containing monomer further comprise at least one nonionic, preferably hydrophobic monomer.
- the use of these hydrophobically modified polymers has made it possible in particular to improve the rinse aid performance of automatic dishwashing detergents according to the invention.
- nonionic monomers are butene, isobutene, pentene, 3-methylbutene, 2-methylbutene, cyclopentene, hexene, hexene-1, 2-methylpentene-1, 3-methylpentene-1, cyclohexene, methylcyclopentene, cycloheptene, methylcyclohexene, 2,4 , 4-trimethylpentene-1, 2,4,4-trimethylpentene-2,3,3-dimethylhexene-1, 2,4-dimethylhexene-1, 2,5-dimethlyhexene-1,3,5-dimethylhexene-1,4 , 4-dimethylhexane-1, ethylcyclohexyne, 1-octene, ⁇ -olefins having 10 or more carbon atoms such as 1-decene, 1-dodecene, 1-hexadecene, 1-octadecene and
- the agents according to the invention preferably further comprise at least one organic cobuilder.
- organic co-builders are polycarboxylates / polycarboxylic acids, dextrins and phosphonates. These classes of substances are described below.
- Useful organic builders are, for example, the polycarboxylic acids which can be used in the form of the free acid and / or their sodium salts, polycarboxylic acids meaning those carboxylic acids which carry more than one acid function.
- these are adipic acid, succinic acid, glutaric acid, malic acid, tartaric acid, maleic acid, fumaric acid, sugar acids, aminocarboxylic acids, nitrilotriacetic acid (NTA), if such use is not objectionable for ecological reasons, and mixtures of these.
- NTA nitrilotriacetic acid
- the free acids also typically have the property of an acidifying component and thus also serve to set a lower and milder pH of detergents or cleaners.
- succinic acid, glutaric acid, adipic acid, gluconic acid and any mixtures of these may be mentioned here.
- Preferred automatic dishwashing agents according to the invention contain less than 1% by weight, preferably less than 0.5% by weight and in particular less than 0.1% by weight.
- Very particularly preferred automatic dishwasher detergents according to the invention are free of methylglycinediacetic acid or salts thereof.
- the complex-forming phosphonates include, in addition to the 1-hydroxyethane-1, 1-diphosphonic acid a number of different compounds such as
- Diethylenetriaminepenta (methylenephosphonic acid) (DTPMP).
- Hydroxyalkane or aminoalkane phosphonates are particularly preferred in this application.
- 1-hydroxyethane-1,1-diphosphonate HEDP
- HEDP 1-hydroxyethane-1,1-diphosphonate
- Preferred aminoalkanephosphonates are ethylenediaminetetramethylenephosphonate (EDTMP), diethylenetriaminepentamethylenephosphonate (DTPMP) and their higher homologs. They are preferably in the form of neutral sodium salts, eg. B.
- the builder used here is preferably HEDP from the class of phosphonates.
- the aminoalkanephosphonates also have a pronounced heavy metal binding capacity. Accordingly, in particular if the agents also contain bleach, it may be preferable to use aminoalkanephosphonates, in particular DTPMP, or to use mixtures of the phosphonates mentioned.
- An automatic dishwashing agent preferred in the context of this application contains one or more phosphonate (s) from the group a) aminotrimethylenephosphonic acid (ATMP) and / or salts thereof; b) ethylenediaminetetra (methylenephosphonic acid) (EDTMP) and / or salts thereof; c) diethylenetriamine penta (methylenephosphonic acid) (DTPMP) and / or salts thereof; d) 1-hydroxyethane-1, 1-diphosphonic acid (HEDP) and / or salts thereof; e) 2-phosphonobutane-1,2,4-tricarboxylic acid (PBTC) and / or salts thereof; f) hexamethylenediaminetetra (methylenephosphonic acid) (HDTMP) and / or salts thereof; g) nitrilotri (methylenephosphonic acid) (NTMP) and / or salts thereof.
- ATMP aminotrimethylenephosphonic acid
- ETMP ethylenedi
- automatic dishwasher detergents which contain, as phosphonates, 1-hydroxyethane-1,1-diphosphonic acid (HEDP) or diethylene triamine penta (methylenephosphonic acid) (DTPMP).
- HEDP 1-hydroxyethane-1,1-diphosphonic acid
- DTPMP diethylene triamine penta
- the automatic dishwashing compositions of the invention may contain two or more different phosphonates.
- the proportion by weight of the phosphonates in the total weight of automatic dishwashing detergents according to the invention is preferably from 1 to 8% by weight, preferably from 1.2 to 6% by weight and in particular from 1.5 to 4% by weight.
- preferred automatic dishwasher detergents according to the invention contain alkali metal hydroxide (s).
- the alkali metal hydroxides are preferably used in the cleaning agents in amounts below 12% by weight, preferably between 2 and 10% by weight and in particular between 3 and 8% by weight, in each case based on the total weight of the cleaning agent.
- Preferred automatic dishwasher detergents according to the invention comprise less than 2% by weight, preferably less than 1% by weight and in particular less than 0.5% by weight, of silicate. Very particularly preferred automatic dishwasher detergents according to the invention are silicate-free.
- dishwashing agents according to the invention may contain enzyme (s). These include in particular proteases, amylases, lipases, hemicellulases, cellulases, perhydrolases or oxidoreductases, and preferably mixtures thereof. These enzymes are basically of natural origin; Starting from the natural molecules, improved variants are available for use in detergents or cleaners, which are preferably used accordingly. Washing or cleaning composition preferably contain enzymes in total amounts of 1 x 10 "-6 to 5 wt .-% based on active protein. The protein concentration can be determined using known methods, for example the BCA method and the biuret method.
- subtilisin type those of the subtilisin type are preferable.
- these are the subtilisins BPN 'and Carlsberg and their further developed forms, the protease PB92, the subtilisins 147 and 309, the alkaline protease from Bacillus lentus, subtilisin DY and the enzymes thermitase which can no longer be assigned to the subtilisins in the narrower sense, Proteinase K and the proteases TW3 and TW7.
- amylases which can be used according to the invention are the ⁇ -amylases from Bacillus licheniformis, from ⁇ . amyloliquefaciens, from ⁇ . stearothermophilus, from Aspergillus niger and A. oryzae, as well as improved for use in detergents and cleaners further developments of the aforementioned amylases. Furthermore, for this purpose, the ⁇ -amylase from Bacillus sp. A 7-7 (DSM 12368) and cyclodextrin glucanotransferase (CGTase) from ⁇ . agaradherens (DSM 9948).
- lipases or cutinases are also usable according to the invention, in particular because of their triglyceride-splitting activities, but also in order to generate in situ peracids from suitable precursors.
- lipases or cutinases include, for example, the lipases originally obtainable from Humicola lanuginosa (Thermomyces lanuginosus) or further developed, in particular those with the amino acid exchange D96L.
- Oxidoreductases for example oxidases, oxygenases, catalases, peroxidases, such as halo, chloro, bromo, lignin, glucose or manganese peroxidases, dioxygenases or laccases (phenol oxidases, polyphenol oxidases) can be used according to the invention to increase the bleaching effect.
- a protein and / or enzyme may be particularly protected during storage against damage such as inactivation, denaturation or degradation, such as by physical influences, oxidation or proteolytic cleavage.
- damage such as inactivation, denaturation or degradation, such as by physical influences, oxidation or proteolytic cleavage.
- inhibition of proteolysis is particularly preferred, especially if the agents also contain proteases.
- Detergents may contain stabilizers for this purpose; the provision of such means constitutes a preferred embodiment of the present invention.
- Washing or cleaning-active proteases and amylases are generally not provided in the form of the pure protein but rather in the form of stabilized, storable and transportable preparations.
- Such prefabricated preparations include, for example, the solid preparations obtained by granulation, extrusion or lyophilization or, especially in the case of liquid or gel-form detergents, solutions of the enzymes, advantageously as concentrated as possible, low in water and / or added with stabilizers or further auxiliaries.
- the enzymes may be encapsulated for both the solid and liquid dosage forms, for example by spray-drying or extruding the enzyme solution together with a preferably natural polymer or in the form of capsules, for example those in which the enzymes are entrapped as in a solidified gel or in those of the core-shell type in which an enzyme-containing core is coated with a water, air and / or chemical impermeable protective layer.
- a preferably natural polymer or in the form of capsules for example those in which the enzymes are entrapped as in a solidified gel or in those of the core-shell type in which an enzyme-containing core is coated with a water, air and / or chemical impermeable protective layer.
- further active ingredients for example stabilizers, emulsifiers, pigments, bleaches or dyes, may additionally be applied.
- Such capsules are applied by methods known per se, for example by shaking or rolling granulation or in fluid-bed processes.
- such granules for example by applying polymeric film-forming agent, low in dust and storage stable due to the coating.
- a preferred machine dishwashing detergent according to the invention is characterized in that the dishwashing detergent, based on its total weight, enzyme preparation in amounts of 0.1 to 12 wt .-%, preferably from 0.2 to 10 wt .-% and in particular from 0.5 to 8 wt .-% contains.
- the enzyme protein forms only a fraction of the total weight of conventional enzyme preparations.
- Protease and amylase preparations preferably used according to the invention contain between 0.1 and 40% by weight, preferably between 0.2 and 30% by weight, particularly preferably between 0.4 and 20% by weight and in particular between 0, 8 and 10 wt .-% of the enzyme protein.
- compositions according to the invention may contain further washing or cleaning-active substances, preferably from the group of surfactants, enzymes, organic solvents, glass corrosion inhibitors, corrosion inhibitors, fragrances and perfume carriers. These preferred ingredients will be described in more detail below.
- nonionic surfactants known to the person skilled in the art can be used as nonionic surfactants.
- Suitable nonionic surfactants are, for example, alkyl glycosides of the general formula RO (G) x in which R is a primary straight-chain or methyl-branched, in particular 2-methyl-branched aliphatic radical having 8 to 22, preferably 12 to 18 carbon atoms and G is the symbol which is a glycose unit having 5 or 6 C atoms, preferably glucose.
- the degree of oligomerization x which indicates the distribution of monoglycosides and oligoglycosides, is any number between 1 and 10; preferably x is 1, 2 to 1, 4.
- Nonionic surfactants of the amine oxide type for example N-cocoalkyl-N, N-dimethylamine oxide and N-tallowalkyl-N, N-dihydroxyethylamine oxide, and the fatty acid alkanolamides may also be suitable.
- the amount of these nonionic surfactants is preferably not more than that of the ethoxylated fatty alcohols, especially not more than half thereof.
- nonionic surfactants used either as the sole nonionic surfactant or in combination with other nonionic surfactants are alkoxylated, preferably ethoxylated or ethoxylated and propoxylated fatty acid alkyl esters, preferably having from 1 to 4 carbon atoms in the alkyl chain.
- washing or cleaning agents in particular automatic dishwashing detergents, contain nonionic surfactants from the group of the alkoxylated alcohols.
- the nonionic surfactants used are preferably alkoxylated, advantageously ethoxylated, in particular primary, alcohols having preferably 8 to 18 carbon atoms and on average 1 to 12 moles of ethylene oxide (EO) per mole of alcohol, in which the alcohol radical can be linear or preferably methyl-branched in the 2-position or linear and methyl-branched radicals in the mixture can contain, as they are usually present in Oxoalkoholresten.
- EO ethylene oxide
- alcohol ethoxylates with linear radicals of alcohols of natural origin having 12 to 18 carbon atoms, for example of coconut, palm, tallow or oleyl alcohol, and on average 2 to 8 moles of EO per mole of alcohol are preferred.
- the preferred ethoxylated alcohols include, for example, C- 2 - 14 -alcohols with 3 EO or 4 EO, C 9 .n-alcohol with 7 EO, Ci 3 _i 5 -alcohols with 3 EO, 5 EO, 7 EO or 8 EO, Ci 2 -i 8 -alcohols with 3 EO, 5 EO or 7 EO and mixtures of these, such as mixtures of C
- the degrees of ethoxylation indicated represent statistical averages that may correspond to a particular product of an integer or a fractional number.
- Preferred alcohol ethoxylates have a narrow homolog distribution (narrow rank ethoxylates, NRE).
- NRE narrow rank ethoxylates
- fatty alcohols with more than 12 EO can also be used. Examples of these are tallow fatty alcohol with 14 EO, 25 EO, 30 EO or 40 EO.
- ethoxylated nonionic surfactant selected from C 6 - 2 o-monohydroxy alkanols or C 6 - 2 o-alkyl phenols or C 16-2 o-fatty alcohols and more than 12 mol, preferably more than 15 mol and in particular more than 20 mol Ethylene oxide per mole of alcohol were used.
- a particularly preferred nonionic surfactant is selected from a straight chain fatty alcohol having 16 to 20 carbon atoms (C 16-2 alcohol), preferably a C 18 alcohol obtained and at least 12 mole, preferably at least 15 mol and in particular at least 20 moles of ethylene oxide.
- C 16-2 alcohol straight chain fatty alcohol having 16 to 20 carbon atoms
- C 18 alcohol preferably a C 18 alcohol obtained and at least 12 mole, preferably at least 15 mol and in particular at least 20 moles of ethylene oxide.
- the so-called “narrow ranks ethoxylates" are particularly preferred.
- Nonionic surfactants which have a melting point above room temperature.
- Nonionic surfactants from the group of alkoxylated alcohols are also used with particular preference.
- the nonionic surfactant solid at room temperature preferably has propylene oxide units in the molecule.
- such PO units make up to 25 wt .-%, more preferably up to 20 wt .-% and in particular up to 15 wt .-% of the total molecular weight of the nonionic surfactant from.
- Particularly preferred nonionic surfactants are ethoxylated monohydroxyalkanols or alkylphenols which additionally have polyoxyethylene-polyoxypropylene block copolymer units.
- the alcohol or alkylphenol content of such nonionic surfactant molecules preferably makes up more than 30% by weight, more preferably more than 50%
- Preferred agents are characterized in that they contain ethoxylated and propoxylated nonionic surfactants in which the propylene oxide units in the molecule up to 25 wt .-%, preferably up to 20 wt .-% and in particular up to 15 wt .-% of the total molecular weight of the nonionic Make up surfactants.
- surfactants come from the groups of alkoxylated nonionic surfactants, in particular the ethoxylated primary alcohols and mixtures of these surfactants with structurally more complicated surfactants such as polyoxypropylene / polyoxyethylene / polyoxypropylene ((PO / EO / PO) surfactants).
- Such (PO / EO / PO) nonionic surfactants are also distinguished by good visual control.
- More particularly preferred nonionic surfactants having melting points above room temperature contain from 40 to 70% of a polyoxypropylene / polyoxyethylene / polyoxypropylene block polymer blend containing 75% by weight of a reverse block copolymer of polyoxyethylene and polyoxypropylene with 17 moles of ethylene oxide and 44 moles of propylene oxide and 25% by weight. % of a block copolymer of polyoxyethylene and polyoxypropylene initiated with trimethylolpropane and containing 24 moles of ethylene oxide and 99 moles of propylene oxide per mole of trimethylolpropane.
- nonionic surfactants have been low foaming nonionic surfactants which have alternating ethylene oxide and alkylene oxide units.
- surfactants with EO-AO-EO-AO blocks are preferred, wherein in each case one to ten EO or AO groups are bonded to each other before a block of the other groups follows.
- R 1 is a straight-chain or branched, saturated or mono- or polyunsaturated C 6 - 24 represents alkyl or alkenyl; each group R 2 or R 3 is independently selected from -CH 3 , -CH 2 CH 3 , -CH 2 CH 2 -CH 3 , CH (CH 3 ) 2 and the indices w, x, y, z independently stand for integers from 1 to 6.
- the preferred nonionic surfactants of the above formula can be prepared by known methods from the corresponding alcohols R 1 -OH and ethylene or alkylene oxide.
- the radical R 1 in the above formula may vary depending on the origin of the alcohol. If native sources are used, the radical R 1 has an even number of carbon atoms and is usually unbranched, the linear radicals being selected from alcohols of natural origin having 12 to 18 C atoms, for example from coconut, palm, tallow or Oleyl alcohol, are preferred.
- Alcohols which are accessible from synthetic sources are, for example, the Guerbet alcohols or methyl-branched or linear and methyl-branched radicals in the 2-position, as they are usually present in oxo alcohol radicals.
- nonionic surfactants in which R 1 in the above formula is an alkyl radical having 6 to 24, preferably 8 to 20, particularly preferably 9 to 15 and in particular 9 to 11 Carbon atoms.
- R 1 in the above formula is an alkyl radical having 6 to 24, preferably 8 to 20, particularly preferably 9 to 15 and in particular 9 to 11 Carbon atoms.
- alkylene oxide unit which is contained in the preferred nonionic surfactants in alternation with the ethylene oxide unit, in particular butylene oxide is considered in addition to propylene oxide.
- R 2 or R 3 are independently selected from -CH 2 CH 2 -CH 3 or - CH (CH 3 ) 2 are suitable.
- RR 22 b for example RR 33
- RR 33 is suitable for the purposes of determining R - - CHCH 33 , w and n x x uunna abbhphinnggiigg vvoorn each other for values of 3 or 4 and y and z, independently of one another, represent values of 1 or 2 ,
- Nonionic surfactants are summary particularly preferred which have a C. 9-i 5 alkyl radical having 1 to 4 ethylene oxide units, followed by 1 to 4 propylene oxide units, followed by 1 to 4 ethylene oxide units, followed by 1 to 4 propylene oxide units. These surfactants have the required low viscosity in aqueous solution and can be used according to the invention with particular preference.
- R 1 -CH (OH) CH 2 O- (AO) w - (A'O) x - (A "O) y - (A '" O) z -R 2 Surfactants of the general formula R 1 -CH (OH) CH 2 O- (AO) w - (A'O) x - (A "O) y - (A '" O) z -R 2 , in which R 1 and R 2 independently of one another represent a straight-chain or branched, saturated or mono- or polyunsaturated C 2 .
- A, A ', A "and A'” independently represent a radical from the group -CH 2 CH 2 , -CH 2 CH 2 -CH 2 , -CH 2 -CH (CH 3 ), -CH 2 -CH 2 -CH 2 -CH 2 , -CH 2 - CH (CHs) -CH 2 -, -CH 2 -CH (CH 2 -CH 3 ); and w, x, y and z are values between 0.5 and 90, where x, y and / or z can also be 0 are preferred according to the invention.
- end-capped poly (oxyalkylated) nonionic surfactants which, in accordance with the formula R 1 O [CH 2 CH 2 O] x CH 2 CH (OH) R 2 , in addition to a radical R 1 , which is linear or branched, saturated or unsaturated, aliphatic or aromatic hydrocarbon radicals having from 2 to 30 carbon atoms, preferably having from 4 to 22 carbon atoms, furthermore having a linear or branched, saturated or unsaturated, aliphatic or aromatic hydrocarbon radical R 2 having from 1 to 30 carbon atoms, where x is from 1 to 30 carbon atoms 90, preferably for values between 30 and 80 and in particular for values between 30 and 60.
- surfactants of the formula R 1 O [CH 2 CH (CH 3 ) O] x [CH 2 CH 2 O] y CH 2 CH (OH) R 2 , in which R 1 is a linear or branched aliphatic hydrocarbon radical with 4 R 2 is a linear or branched hydrocarbon radical having 2 to 26 carbon atoms or mixtures thereof and x is values between 0.5 and 1, 5 and y is a value of at least 15.
- nonionic surfactants having a free hydroxyl group on one of the two terminal alkyl radicals By using the above-described nonionic surfactants having a free hydroxyl group on one of the two terminal alkyl radicals, the formation of deposits in machine dishwashing can be markedly improved compared to conventional polyalkoxylated fatty alcohols without a free hydroxyl group.
- nonionic surfactants are the end-capped poly (oxyalkylated) nonionic surfactants of the formula R 1 O [CH 2 CH (R 3 P] x [CH 2 J k CH (OH) [CH 2 ] J OR 2 in which R 1 and R 2 are linear or branched, saturated or unsaturated, aliphatic or aromatic hydrocarbon radicals having 1 to 30 carbon atoms, R 3 is H or a methyl, ethyl, n-propyl, iso-propyl, n-butyl, 2-butyl - or 2-methyl-2-butyl radical, x are values between 1 and 30, k and j are values between 1 and 12, preferably between 1 and 5.
- each R 3 in the R 1 O [CH 2 CH (R 3 P] x [CH 2 Ik CH (OH) [CH 2 ] J OR 2 above may be different.
- R 1 and R 2 are preferably linear or branched, saturated or unsaturated, aliphatic or aromatic hydrocarbon radicals having 6 to 22 carbon atoms, with radicals having 8 to 18 carbon atoms being particularly preferred, for the radical R 3 are H, -CH 3 or -CH 2 CH 3 in particular ders preferred.
- Particularly preferred values for x are in the range from 1 to 20, in particular from 6 to 15.
- each R 3 in the above formula may be different if x> 2.
- the alkylene oxide unit in the square bracket can be varied.
- the value 3 for x has been selected here by way of example and may well be greater, with the variation width increasing with increasing x values and including, for example, a large number (EO) groups combined with a small number (PO) groups, or vice versa ,
- R 1 , R 2 and R 3 are as defined above and x is from 1 to 30, preferably from 1 to 20 and in particular from 6 to 18.
- Particularly preferred are surfactants in which the radicals R 1 and R 2 has 9 to 14 C atoms, R 3 is H and x assumes values of 6 to 15.
- the stated C chain lengths and degrees of ethoxylation or degrees of alkoxylation of the abovementioned nonionic surfactants represent statistical mean values which, for a specific product, may be an integer or a fractional number. Due to the manufacturing process, commercial products of the formulas mentioned are usually not made of an individual representative, but of mixtures, which may result in mean values for the C chain lengths as well as for the degrees of ethoxylation or degrees of alkoxylation and subsequently broken numbers.
- surfactants of the general formula R 1 O (AlkO) x M (OAlk) y OR 2 , in which
- R 1 and R 2 independently of one another represent a branched or unbranched, saturated or unsaturated, optionally hydroxylated alkyl radical having 4 to 22 carbon atoms;
- Alk is a branched or unbranched alkyl radical having 2 to 4 carbon atoms
- M is an alkyl radical from the group CH 2 , CHR 3 , CR 3 R 4 , CH 2 CHR 3 and CHR 3 CHR 4 , where R 3 and R 4 independently of one another represent a branched or unbranched, saturated or unsaturated alkyl radical having 1 to 18 carbon atoms;
- the proportion by weight of this specific nonionic surfactant in the total weight of the inventive automatic dishwashing agent in a preferred embodiment is between 0.05 and 10
- Wt .-% preferably between 0.1 and 8 wt .-%, preferably between 0.5 and 5 wt .-% and in particular between 1 and 3 wt .-%.
- the group of nonionic surfactants of the general formula R 1 O (AlkO) x M (OAlk) y OR 2 comprises a number of particularly preferred compounds.
- automatic dishwashing agents contain as nonionic surfactant A a surfactant of the general formula R 1 -CH (OH) CH 2 -O (CH 2 CH 2 O) x CH 2 CHR (OCH 2 CH 2 ) y O-CH 2 CH (OH) -R 2 is used in the
- R, R 1 and R 2 independently represent an alkyl radical or alkenyl radical having 6 to 22 carbon atoms
- R 1 -CH (OH) CH 2 -O (CH 2 CH 2 O) x CH 2 CHR (OCH 2 CH 2 ) y O-CH 2 CH (OH) -R 2 in which R is a linear, saturated alkyl radical having 8 to 16 carbon atoms, preferably 10 to 14 carbon atoms, and n and m independently of one another have values of 20 to 30.
- Appropriate connections can For example, by reacting alkyldiols HO-CHR-CH 2 -OH with ethylene oxide are obtained, followed by a reaction with an Alkylepoxid to close the free OH functions to form a dihydroxy ether.
- machine dishwashing detergents contain nonionic surfactant of the general formula R 1 -O (CH 2 CH 2 O) x CR 3 R 4 (OCH 2 CH 2) y O in which
- R 1 and R 2 independently represent an alkyl radical or alkenyl radical having 4 to 22 carbon atoms;
- R 3 and R 4 independently of one another are H or an alkyl radical or alkenyl radical having 1 to 18 carbon atoms and
- - x and y independently represent values between 1 and 40;
- R 1 are preferably - O (CH 2 CH 2 O) x CR 3 R 4 (OCH 2 CH 2) y OR 2, are in which R 3 and R 4 is H, and the subscripts x and y are independently from each other assume values from 1 to 40, preferably from 1 to 15.
- radicals R 1 and R 2 independently of one another represent saturated alkyl radicals having 4 to 14 carbon atoms and the indices x and y independently of one another Assume values of 1 to 15 and especially of 1 to 12.
- nonionic surfactants can be used not only as individual substances, but also as surfactant mixtures of two, three, four or more surfactants.
- Mixtures of surfactants are not mixtures of nonionic surfactants which fall in their entirety under one of the abovementioned general formulas, but rather mixtures which contain two, three, four or more nonionic surfactants which can be described by different general formulas ,
- the proportion by weight of the nonionic surfactants in the total weight of the inventive automatic dishwashing agent in a preferred embodiment is between 0.1 and 15 Wt .-%, preferably between 0.2 and 10 wt .-%, preferably between 0.5 and 8 wt .-% and in particular between 1, 0 and 6 wt .-%.
- a particularly preferred automatic dishwashing detergent according to the invention comprises a) 5 to 40% by weight of citrate b) 0.1 to 8% by weight of amylase and / or protease enzyme preparation c) 4.0 to 30% by weight of ethylenediamine disuccinic acid d) ( Hydrogen) carbonate e) from 2.0 to 20% by weight of anionic copolymer comprising i) mono- or polyunsaturated monomers from the group of carboxylic acids ii) mono- or polyunsaturated monomers from the group of sulfonic acids iii) optionally further ionic or nonionic monomers f) 0.2 to 10 wt .-% of nonionic surfactant, wherein the weight ratio of components b) and c) is between 1: 1 and 6: 1.
- Weight ratios (hydrogen) carbonate b) and EDDS c) between 3: 5 and 8: 1 2 ) Weight ratios (hydrogen) carbonate b) and EDDS c) between 1: 1 and 6: 1
- organic solvents are derived, for example, from the groups of the monoalcohols, diols, triols or polyols, the ethers, esters and / or amides. Particular preference is given to organic solvents which are water-soluble, "water-soluble" solvents in the context of the present application being solvents which are completely miscible with water at room temperature, that is to say without a miscibility gap.
- Organic solvents which can be used in the compositions according to the invention preferably originate from the group of monohydric or polyhydric alcohols, alkanolamines or glycol ethers, provided they are miscible with water in the given concentration range.
- the solvents are preferably selected from ethanol, n- or i-propanol, butanols, glycol, propane- or butanediol, glycerol, diglycol, propyl- or butyldiglycol, hexylene glycol, ethylene glycol methyl ether, ethylene glycol ethyl ether, ethylene glycol propyl ether, etheylene glycol mono-n-butyl ether, diethylene glycol methyl ether, di ethylene glycol ethyl ether, propylene glycol methyl, ethyl or propyl ether, dipropylene glycol methyl or ethyl ether, methoxy, ethoxy or butoxy trig
- organic amines in particular the primary and the secondary alkyl amines, the
- Alkyleneamines and mixtures of these organic amines are preferred.
- the group of preferred primary alkylamines include monomethylamine, monoethylamine, monopropylamine, monobutylamine, Monopentylamine and cyclohexylamine.
- the group of preferred secondary alkylamines includes in particular dimethylamine.
- Preferred alkanolamines are in particular the primary, secondary and tertiary alkanolamines and mixtures thereof.
- Particularly preferred primary alkanolamines are monoethanolamine (2-aminoethanol, MEA), monoisopropanolamine, diethylethanolamine (2- (diethylamino) ethanol).
- Particularly preferred secondary alkanolamines are diethanolamine (2,2'-lminodiethanol, DEA, bis (2-hydroxyethyl) amine), N-methyl-diethanolamine, N-ethyl-diethanolamine. Diisopropanolamine and morpholine.
- Particularly preferred tertiary alkanolamines are triethanolamine and triisopropanolamine.
- Machine dishwashing detergent characterized in that it, based on its total weight, organic amine and / or alkanolamine, preferably ethanolamine, in amounts of 0.1 to 15% by weight, preferably 0.2 to 10 wt .-%, particularly preferably 0.5 to 8 wt .-% and in particular from 1, 0 to 6 wt .-%, are particularly preferred according to the invention.
- the automatic dishwasher detergents according to the invention can be present in the ready-to-use form known to the person skilled in the art, that is to say, for example, in solid or liquid form but also as a combination of solid and liquid supply forms.
- Powder, granules, extrudates or compactates, in particular tablets, are particularly suitable as firm supply forms.
- the liquid supply forms based on water and / or organic solvents may be thickened, in the form of gels.
- Inventive agents can be formulated as single-phase or multi-phase products.
- automatic dishwashing detergents with one, two, three or four phases are preferred.
- Machine dishwashing detergents characterized in that they are in the form of a prefabricated dosing unit with two or more phases, are particularly preferred.
- the individual phases of multiphase agents may have the same or different states of matter.
- Machine dishwashing detergents which have at least two different solid phases and / or at least two liquid phases and / or at least one solid and at least one liquid phase are preferred.
- Particularly preferred are in particular two- or multi-phase tablets, for example two-layer tablets, in particular two-layer tablets with a trough and a mold body located in the trough.
- Automatic dishwasher detergents according to the invention are preferably prefabricated to form metering units. These metering units preferably comprise the necessary for a cleaning cycle amount of washing or cleaning-active substances.
- Preferred metering units have a weight between 12 and 30 g, preferably between 14 and 26 g and in particular between 15 and 22 g.
- the volume of the aforementioned metering units and their spatial form are selected with particular preference so that a metering of the prefabricated units is ensured via the metering chamber of a dishwasher.
- the volume of the dosing unit is therefore preferably between 10 and 35 ml, preferably between 12 and 30 ml and in particular between 15 and 25 ml.
- the automatic dishwasher detergents according to the invention in particular the prefabricated metering units, have a water-soluble coating, with particular preference.
- disintegration aids so-called tablet disintegrants
- disintegration aids in amounts of from 0.5 to 10% by weight, preferably from 3 to 7% by weight and in particular from 4 to 6% by weight, based in each case on the total weight of the disintegration aid-containing agent.
- Preferred disintegrating agents are cellulosic disintegrating agents, so that preferred washing or cleaning agents comprise such cellulose-based disintegrants in amounts of from 0.5 to 10% by weight, preferably from 3 to 7% by weight and in particular from 4 to 6% by weight. % contain.
- the cellulose used as a disintegration aid is preferably not used in finely divided form, but converted into a coarser form, for example granulated or compacted, before it is added to the premixes to be tabletted.
- the particle sizes of such Disintegrating agents are usually above 200 microns, preferably at least 90 wt .-% between 300 and 1600 microns and in particular at least 90 wt .-% between 400 and 1200 microns.
- Preferred disintegration aids preferably a disintegration aid based on cellulose, preferably in granular, cogranulated or compacted form, are present in the disintegrating agent-containing agents in amounts of from 0.5 to 10% by weight, preferably from 3 to 7% by weight and in particular from 4 to 6 wt .-%, each based on the total weight of the disintegrating agent-containing agent.
- gas-evolving effervescent systems can furthermore be used as tablet disintegration auxiliaries.
- preferred effervescent systems consist of at least two constituents which react with one another to form gas, for example from alkali metal carbonate and / or bicarbonate and an acidifying agent which is suitable for liberating carbon dioxide from the alkali metal salts in aqueous solution.
- An acidifying agent which releases carbon dioxide from the alkali salts in aqueous solution is, for example, citric acid.
- the automatic dishwashing compositions according to the invention are in liquid form.
- Preferred liquid dosage forms are based on an aqueous matrix which optionally has proportions of organic solvents.
- a particularly preferred liquid automatic dishwashing detergent according to the invention comprises a) 5 to 40% by weight of citrate b) 0.1 to 8% by weight of amylase and / or protease enzyme preparation c) 4.0 to 30% by weight of ethylenediamine disuccinic acid d) (Hydrogen) carbonate e) 2.0 to 20% by weight of anionic copolymer comprising i) mono- or polyunsaturated monomers from the group of carboxylic acids ii) mono- or polyunsaturated monomers from the group of sulfonic acids iii) optionally further ionic or nonionic Monomers f) 0.2 to 10% by weight of nonionic surfactant g) 20 to 70% by weight of water, the weight ratio of components b) and c) being between 1: 1 and 6: 1.
- these agents preferably contain from 20 to 80% by weight, preferably from 30 to 70% by weight and in particular from 40 to 60% by weight, of water.
- the metering units of these liquid supply forms preferably comprise the amount of washing or cleaning-active substances necessary for a cleaning cycle.
- preferred Liquid metering units have a weight between 25 and 60 g, preferably between 30 and 55 g and in particular between 55 and 50 g.
- Another object of the present application is a method for cleaning dishes in a dishwasher, using a machine dishwashing agent according to the invention, wherein the automatic dishwashing detergent preferably metered during the passage of a dishwasher, before the main wash cycle or during the main wash cycle in the interior of a dishwasher become.
- the metering or the entry of the agent according to the invention into the interior of the dishwasher can be done manually, but preferably the agent is metered into the interior of the dishwasher by means of the metering chamber of the dishwasher.
- no additional water softener and no additional rinse aid is dosed into the interior of the dishwasher.
- a kit for a dishwasher comprising a) a machine dishwashing detergent according to the invention; (b) instructions instructing the consumer to use the automatic dishwashing detergent without the addition of a rinse aid and / or a softening salt are another subject of this application.
- the dishwasher detergents according to the invention exhibit their advantageous cleaning and drying properties, in particular also in low-temperature cleaning processes.
- Preferred dishwashing method using the inventive agent are therefore characterized in that the dishwashing process are carried out at a liquor temperature below 6O 0 C, preferably below 5O 0 C.
- agents according to the invention are distinguished from conventional automatic dishwasher detergents by improved tea cleaning.
- Another object of the present application is therefore the use of a machine dishwashing detergent according to the invention for improving the dough cleaning in automatic dishwashing. Examples
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Abstract
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EP3114219A1 (fr) | 2014-03-05 | 2017-01-11 | Novozymes A/S | Compositions et procédés destinés à améliorer les propriétés de matériaux textiles non-cellulosiques par l'utilisation d'endo-xyloglucane transférase |
CN106062271A (zh) | 2014-03-05 | 2016-10-26 | 诺维信公司 | 用于改进具有木葡聚糖内糖基转移酶的纤维素纺织材料的性质的组合物和方法 |
US20170015950A1 (en) | 2014-04-01 | 2017-01-19 | Novozymes A/S | Polypeptides having alpha amylase activity |
US20170121695A1 (en) | 2014-06-12 | 2017-05-04 | Novozymes A/S | Alpha-amylase variants and polynucleotides encoding same |
EP3739029A1 (fr) | 2014-07-04 | 2020-11-18 | Novozymes A/S | Variants de subtilase et polynucléotides codant pour ceux-ci |
WO2016001449A1 (fr) | 2014-07-04 | 2016-01-07 | Novozymes A/S | Variants de subtilase et polynucléotides codant pour ceux-ci |
US10287562B2 (en) | 2014-11-20 | 2019-05-14 | Novoszymes A/S | Alicyclobacillus variants and polynucleotides encoding same |
US10683491B2 (en) | 2014-12-04 | 2020-06-16 | Novozymes A/S | Subtilase variants and polynucleotides encoding same |
WO2016096714A1 (fr) | 2014-12-15 | 2016-06-23 | Henkel Ag & Co. Kgaa | Composition de détergent comprenant des variants de subtilase |
GB201507289D0 (en) | 2015-04-29 | 2015-06-10 | Reckitt Benckiser Brands Ltd | Method of cleaning tableware |
EP3310912B1 (fr) | 2015-06-18 | 2021-01-27 | Novozymes A/S | Variants de subtilase et polynucléotides codant pour ceux-ci |
EP3106508B1 (fr) | 2015-06-18 | 2019-11-20 | Henkel AG & Co. KGaA | Composition détergente comprenant des variantes de subtilase |
CN108291215A (zh) | 2015-10-14 | 2018-07-17 | 诺维信公司 | 具有蛋白酶活性的多肽以及编码它们的多核苷酸 |
EP3362556B1 (fr) | 2015-10-14 | 2024-07-10 | Novozymes A/S | Variants polypeptidiques |
WO2017102868A1 (fr) * | 2015-12-18 | 2017-06-22 | Henkel Ag & Co. Kgaa | Composition détergente liquide comprenant cinq éléments |
ES2575999B1 (es) * | 2016-03-10 | 2017-04-19 | Elisa SORO LEFREBRE | Detergente sólido multifuncional para lavavajillas |
WO2017207762A1 (fr) | 2016-06-03 | 2017-12-07 | Novozymes A/S | Variants de subtilase et polynucléotides codant pour ceux-ci |
CN109642222A (zh) | 2016-07-13 | 2019-04-16 | 诺维信公司 | 食物芽孢杆菌dna酶变体 |
EP3622049B1 (fr) | 2017-05-12 | 2023-08-16 | Unilever Global IP Limited | Composition de détergent de lave-vaisselle automatique sans phosphate |
EP3701017A1 (fr) | 2017-10-27 | 2020-09-02 | Novozymes A/S | Variants de dnase |
CN111386340B (zh) | 2017-10-27 | 2024-05-24 | 宝洁公司 | 包含多肽变体的洗涤剂组合物 |
WO2019201793A1 (fr) | 2018-04-17 | 2019-10-24 | Novozymes A/S | Polypeptides ayant une activité de liaison des hydrates de carbone dans des compositions détergentes et leur utilisation pour réduire les plis de textiles ou de tissus |
BR112021018731A2 (pt) | 2019-03-21 | 2021-12-21 | Novozymes As | Variantes de alfa-amilase e polinucleotídeos codificando as mesmas |
WO2020207944A1 (fr) | 2019-04-10 | 2020-10-15 | Novozymes A/S | Variants polypeptidiques |
US20220325204A1 (en) | 2019-08-27 | 2022-10-13 | Novozymes A/S | Detergent composition |
US20220315866A1 (en) | 2019-09-19 | 2022-10-06 | Novozymes A/S | Detergent Composition |
WO2021064068A1 (fr) | 2019-10-03 | 2021-04-08 | Novozymes A/S | Polypeptides comprenant au moins deux domaines de liaison aux hydrates de carbone |
EP3892708A1 (fr) | 2020-04-06 | 2021-10-13 | Henkel AG & Co. KGaA | Compositions de nettoyage comprenant des variantes de dispersine |
WO2022074037A2 (fr) | 2020-10-07 | 2022-04-14 | Novozymes A/S | Variants d'alpha-amylase |
WO2022171780A2 (fr) | 2021-02-12 | 2022-08-18 | Novozymes A/S | Variants d'alpha-amylase |
EP4359518A1 (fr) | 2021-06-23 | 2024-05-01 | Novozymes A/S | Polypeptides d'alpha-amylase |
WO2024131880A2 (fr) | 2022-12-23 | 2024-06-27 | Novozymes A/S | Composition détergente comprenant une catalase et une amylase |
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US4704233A (en) * | 1986-11-10 | 1987-11-03 | The Procter & Gamble Company | Detergent compositions containing ethylenediamine-N,N'-disuccinic acid |
DE4232170C2 (de) | 1992-09-25 | 1999-09-16 | Henkel Kgaa | Schwachalkalische Geschirreinigungsmittel |
DE4315048A1 (de) | 1993-04-01 | 1994-10-06 | Henkel Kgaa | Verfahren zur Herstellung stabiler, bifunktioneller, phosphat-, metasilikat- und polymerfreier niederalkalischer Reinigungsmitteltabletten für das maschinelle Geschirrspülen |
WO1996006908A1 (fr) * | 1994-08-26 | 1996-03-07 | The Procter & Gamble Company | Ethylenediamine disuccinate utilise comme detergent |
US5968881A (en) * | 1995-02-02 | 1999-10-19 | The Procter & Gamble Company | Phosphate built automatic dishwashing compositions comprising catalysts |
ES2160355T3 (es) | 1996-06-21 | 2001-11-01 | Reckitt Benckiser Nv | Agente de lavado de baja alcalinidad, para lavavajillas, que contiene acido metilglicindiacetico. |
DE10159499A1 (de) * | 2001-12-04 | 2003-10-02 | Henkel Kgaa | Wasch- und/oder Reinigungsartikel |
DE10163603B4 (de) * | 2001-12-21 | 2006-05-04 | Henkel Kgaa | Verfahren zur Herstellung builderhaltiger Tensidgranulate |
DE10340683A1 (de) * | 2003-09-04 | 2005-04-07 | Henkel Kgaa | Wasch- oder Reinigungsmittel |
WO2005051770A1 (fr) * | 2003-10-31 | 2005-06-09 | Henkel Kommanditgesellschaft Auf Aktien | Procedes d'emballage |
DE102004005344A1 (de) * | 2004-02-04 | 2005-09-01 | Henkel Kgaa | Maschinelles Geschirrspülmittel #### |
DE102004044411A1 (de) | 2004-09-14 | 2006-03-30 | Basf Ag | Reinigungsformulierungen für die maschinelle Geschirrreinigung enthaltend hydrophob modifizierte Polycarboxylate |
JP2006265463A (ja) * | 2005-03-25 | 2006-10-05 | Adeka Corp | 自動食器洗浄機用洗浄剤組成物 |
DE102005041709A1 (de) * | 2005-09-02 | 2007-03-08 | Henkel Kgaa | Reinigungsmittel |
CA2660193A1 (fr) * | 2006-08-10 | 2008-02-14 | Basf Se | Formulation de nettoyage pour des lave-vaisselle |
-
2008
- 2008-12-19 DE DE102008063801A patent/DE102008063801A1/de not_active Withdrawn
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2009
- 2009-12-14 EP EP09795392.1A patent/EP2367920B1/fr active Active
- 2009-12-14 PL PL09795392T patent/PL2367920T3/pl unknown
- 2009-12-14 ES ES09795392.1T patent/ES2558435T3/es active Active
- 2009-12-14 WO PCT/EP2009/067038 patent/WO2010069905A1/fr active Application Filing
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Non-Patent Citations (1)
Title |
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See references of WO2010069905A1 * |
Also Published As
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US20110240063A1 (en) | 2011-10-06 |
WO2010069905A1 (fr) | 2010-06-24 |
PL2367920T3 (pl) | 2016-06-30 |
EP2367920B1 (fr) | 2015-12-09 |
DE102008063801A1 (de) | 2010-06-24 |
US8268768B2 (en) | 2012-09-18 |
ES2558435T3 (es) | 2016-02-04 |
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