EP0929630B1 - Pastenförmiges wasch- und reinigungsmittel - Google Patents
Pastenförmiges wasch- und reinigungsmittel Download PDFInfo
- Publication number
- EP0929630B1 EP0929630B1 EP97944804A EP97944804A EP0929630B1 EP 0929630 B1 EP0929630 B1 EP 0929630B1 EP 97944804 A EP97944804 A EP 97944804A EP 97944804 A EP97944804 A EP 97944804A EP 0929630 B1 EP0929630 B1 EP 0929630B1
- Authority
- EP
- European Patent Office
- Prior art keywords
- weight
- detergent
- alkyl
- carbon atoms
- general formula
- 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.)
- Expired - Lifetime
Links
- 238000005406 washing Methods 0.000 title description 11
- 239000012459 cleaning agent Substances 0.000 title description 7
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 60
- 239000003599 detergent Substances 0.000 claims abstract description 41
- -1 alkyl benzenesulfonate Chemical compound 0.000 claims abstract description 32
- 125000004432 carbon atom Chemical group C* 0.000 claims abstract description 21
- 150000001298 alcohols Chemical class 0.000 claims abstract description 20
- 125000000217 alkyl group Chemical group 0.000 claims abstract description 17
- 239000003945 anionic surfactant Substances 0.000 claims abstract description 16
- 230000003113 alkalizing effect Effects 0.000 claims abstract description 11
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims abstract description 8
- 229920005646 polycarboxylate Polymers 0.000 claims abstract description 7
- 229910052739 hydrogen Inorganic materials 0.000 claims abstract description 6
- 239000001257 hydrogen Substances 0.000 claims abstract description 6
- 150000005215 alkyl ethers Chemical class 0.000 claims abstract description 5
- 125000003342 alkenyl group Chemical group 0.000 claims abstract 6
- 229940077388 benzenesulfonate Drugs 0.000 claims abstract 2
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims abstract 2
- 239000002736 nonionic surfactant Substances 0.000 claims description 17
- 239000007844 bleaching agent Substances 0.000 claims description 12
- 238000007046 ethoxylation reaction Methods 0.000 claims description 10
- 239000004094 surface-active agent Substances 0.000 claims description 10
- 102000004190 Enzymes Human genes 0.000 claims description 9
- 108090000790 Enzymes Proteins 0.000 claims description 9
- 229940088598 enzyme Drugs 0.000 claims description 9
- 229920000642 polymer Polymers 0.000 claims description 9
- 239000002245 particle Substances 0.000 claims description 7
- 239000000344 soap Substances 0.000 claims description 7
- 239000007790 solid phase Substances 0.000 claims description 7
- 239000004615 ingredient Substances 0.000 claims description 6
- 108091005804 Peptidases Proteins 0.000 claims description 5
- 239000004365 Protease Substances 0.000 claims description 5
- 102000013142 Amylases Human genes 0.000 claims description 4
- 108010065511 Amylases Proteins 0.000 claims description 4
- 235000019418 amylase Nutrition 0.000 claims description 4
- RTZKZFJDLAIYFH-UHFFFAOYSA-N ether Substances CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 claims description 4
- 102000004882 Lipase Human genes 0.000 claims description 3
- 239000004367 Lipase Substances 0.000 claims description 3
- 108090001060 Lipase Proteins 0.000 claims description 3
- 235000019421 lipase Nutrition 0.000 claims description 3
- 239000004382 Amylase Substances 0.000 claims description 2
- 108010059892 Cellulase Proteins 0.000 claims description 2
- 102100037486 Reverse transcriptase/ribonuclease H Human genes 0.000 claims description 2
- 229940106157 cellulase Drugs 0.000 claims description 2
- 230000002401 inhibitory effect Effects 0.000 claims description 2
- 235000019419 proteases Nutrition 0.000 claims description 2
- 239000000470 constituent Substances 0.000 claims 2
- 239000012024 dehydrating agents Substances 0.000 claims 1
- 239000010419 fine particle Substances 0.000 claims 1
- 239000000203 mixture Substances 0.000 description 22
- 239000002253 acid Substances 0.000 description 15
- 150000007513 acids Chemical class 0.000 description 12
- 239000011734 sodium Substances 0.000 description 12
- 239000007788 liquid Substances 0.000 description 11
- 235000011837 pasties Nutrition 0.000 description 10
- 150000003839 salts Chemical class 0.000 description 10
- 229910052708 sodium Inorganic materials 0.000 description 10
- 239000000126 substance Substances 0.000 description 10
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 9
- IMROMDMJAWUWLK-UHFFFAOYSA-N Ethenol Chemical compound OC=C IMROMDMJAWUWLK-UHFFFAOYSA-N 0.000 description 8
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical group OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 8
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 8
- OFOBLEOULBTSOW-UHFFFAOYSA-N Propanedioic acid Natural products OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 0.000 description 8
- 229920001577 copolymer Polymers 0.000 description 8
- 239000012190 activator Substances 0.000 description 7
- 239000003513 alkali Substances 0.000 description 7
- 239000000178 monomer Substances 0.000 description 7
- 239000007787 solid Substances 0.000 description 7
- NIXOWILDQLNWCW-UHFFFAOYSA-N 2-Propenoic acid Natural products OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 6
- 229910052783 alkali metal Inorganic materials 0.000 description 6
- 150000001875 compounds Chemical class 0.000 description 6
- 230000009969 flowable effect Effects 0.000 description 6
- VZCYOOQTPOCHFL-UPHRSURJSA-N maleic acid Chemical compound OC(=O)\C=C/C(O)=O VZCYOOQTPOCHFL-UPHRSURJSA-N 0.000 description 6
- 238000003860 storage Methods 0.000 description 6
- VZCYOOQTPOCHFL-UHFFFAOYSA-N trans-butenedioic acid Natural products OC(=O)C=CC(O)=O VZCYOOQTPOCHFL-UHFFFAOYSA-N 0.000 description 6
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 description 5
- CERQOIWHTDAKMF-UHFFFAOYSA-N Methacrylic acid Chemical compound CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 description 5
- 229910019142 PO4 Inorganic materials 0.000 description 5
- 150000001735 carboxylic acids Chemical class 0.000 description 5
- 239000006260 foam Substances 0.000 description 5
- 239000011976 maleic acid Substances 0.000 description 5
- 238000000034 method Methods 0.000 description 5
- 239000007800 oxidant agent Substances 0.000 description 5
- 235000021317 phosphate Nutrition 0.000 description 5
- 239000002689 soil Substances 0.000 description 5
- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 description 4
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 4
- 230000002378 acidificating effect Effects 0.000 description 4
- 239000004480 active ingredient Substances 0.000 description 4
- 229910052910 alkali metal silicate Inorganic materials 0.000 description 4
- 150000001732 carboxylic acid derivatives Chemical class 0.000 description 4
- 238000004140 cleaning Methods 0.000 description 4
- 235000014113 dietary fatty acids Nutrition 0.000 description 4
- 150000002148 esters Chemical class 0.000 description 4
- 239000000194 fatty acid Substances 0.000 description 4
- 229930195729 fatty acid Natural products 0.000 description 4
- 150000004665 fatty acids Chemical class 0.000 description 4
- 230000005484 gravity Effects 0.000 description 4
- 239000003112 inhibitor Substances 0.000 description 4
- 239000007791 liquid phase Substances 0.000 description 4
- 238000004519 manufacturing process Methods 0.000 description 4
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 description 4
- 239000010452 phosphate Substances 0.000 description 4
- 159000000001 potassium salts Chemical class 0.000 description 4
- BDHFUVZGWQCTTF-UHFFFAOYSA-M sulfonate Chemical compound [O-]S(=O)=O BDHFUVZGWQCTTF-UHFFFAOYSA-M 0.000 description 4
- 229920001897 terpolymer Polymers 0.000 description 4
- HGINCPLSRVDWNT-UHFFFAOYSA-N Acrolein Chemical compound C=CC=O HGINCPLSRVDWNT-UHFFFAOYSA-N 0.000 description 3
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 description 3
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 3
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical group [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 3
- 229920002134 Carboxymethyl cellulose Polymers 0.000 description 3
- 229920001634 Copolyester Polymers 0.000 description 3
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 description 3
- 239000005977 Ethylene Substances 0.000 description 3
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 3
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- 102000035195 Peptidases Human genes 0.000 description 3
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- BGRWYDHXPHLNKA-UHFFFAOYSA-N Tetraacetylethylenediamine Chemical compound CC(=O)N(C(C)=O)CCN(C(C)=O)C(C)=O BGRWYDHXPHLNKA-UHFFFAOYSA-N 0.000 description 3
- 150000008051 alkyl sulfates Chemical class 0.000 description 3
- 150000001720 carbohydrates Chemical class 0.000 description 3
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 3
- 239000001768 carboxy methyl cellulose Substances 0.000 description 3
- 235000010948 carboxy methyl cellulose Nutrition 0.000 description 3
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 description 3
- VTIIJXUACCWYHX-UHFFFAOYSA-L disodium;carboxylatooxy carbonate Chemical compound [Na+].[Na+].[O-]C(=O)OOC([O-])=O VTIIJXUACCWYHX-UHFFFAOYSA-L 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 150000002170 ethers Chemical class 0.000 description 3
- 150000002191 fatty alcohols Chemical class 0.000 description 3
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 description 3
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 3
- 230000003287 optical effect Effects 0.000 description 3
- 239000003960 organic solvent Substances 0.000 description 3
- 229920001296 polysiloxane Polymers 0.000 description 3
- 230000008569 process Effects 0.000 description 3
- 150000004760 silicates Chemical class 0.000 description 3
- 229940045872 sodium percarbonate Drugs 0.000 description 3
- 229910052723 transition metal Inorganic materials 0.000 description 3
- 239000010457 zeolite Substances 0.000 description 3
- XSVSPKKXQGNHMD-UHFFFAOYSA-N 5-bromo-3-methyl-1,2-thiazole Chemical compound CC=1C=C(Br)SN=1 XSVSPKKXQGNHMD-UHFFFAOYSA-N 0.000 description 2
- BVKZGUZCCUSVTD-UHFFFAOYSA-M Bicarbonate Chemical compound OC([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-M 0.000 description 2
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 description 2
- RGHNJXZEOKUKBD-SQOUGZDYSA-N D-gluconic acid Chemical compound OC[C@@H](O)[C@@H](O)[C@H](O)[C@@H](O)C(O)=O RGHNJXZEOKUKBD-SQOUGZDYSA-N 0.000 description 2
- AEMRFAOFKBGASW-UHFFFAOYSA-N Glycolic acid Chemical compound OCC(O)=O AEMRFAOFKBGASW-UHFFFAOYSA-N 0.000 description 2
- KFSLWBXXFJQRDL-UHFFFAOYSA-N Peracetic acid Chemical compound CC(=O)OO KFSLWBXXFJQRDL-UHFFFAOYSA-N 0.000 description 2
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical class OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 2
- 229920003171 Poly (ethylene oxide) Polymers 0.000 description 2
- 239000002202 Polyethylene glycol Substances 0.000 description 2
- 239000004115 Sodium Silicate Substances 0.000 description 2
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 description 2
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 description 2
- KKEYFWRCBNTPAC-UHFFFAOYSA-N Terephthalic acid Chemical group OC(=O)C1=CC=C(C(O)=O)C=C1 KKEYFWRCBNTPAC-UHFFFAOYSA-N 0.000 description 2
- 230000009471 action Effects 0.000 description 2
- 238000007792 addition Methods 0.000 description 2
- 125000002947 alkylene group Chemical group 0.000 description 2
- 229910000323 aluminium silicate Inorganic materials 0.000 description 2
- 229940025131 amylases Drugs 0.000 description 2
- 125000003118 aryl group Chemical group 0.000 description 2
- 239000004305 biphenyl Substances 0.000 description 2
- 235000010290 biphenyl Nutrition 0.000 description 2
- 238000004061 bleaching Methods 0.000 description 2
- OSGAYBCDTDRGGQ-UHFFFAOYSA-L calcium sulfate Chemical compound [Ca+2].[O-]S([O-])(=O)=O OSGAYBCDTDRGGQ-UHFFFAOYSA-L 0.000 description 2
- 150000007942 carboxylates Chemical class 0.000 description 2
- 239000008112 carboxymethyl-cellulose Substances 0.000 description 2
- 239000003054 catalyst Substances 0.000 description 2
- 229920003086 cellulose ether Polymers 0.000 description 2
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 2
- 239000003205 fragrance Substances 0.000 description 2
- 150000004676 glycans Chemical class 0.000 description 2
- 229920001519 homopolymer Polymers 0.000 description 2
- 239000003752 hydrotrope Substances 0.000 description 2
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- 238000006386 neutralization reaction Methods 0.000 description 2
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- 229910052760 oxygen Inorganic materials 0.000 description 2
- 239000012188 paraffin wax Substances 0.000 description 2
- 150000002978 peroxides Chemical class 0.000 description 2
- ZUOUZKKEUPVFJK-UHFFFAOYSA-N phenylbenzene Natural products C1=CC=CC=C1C1=CC=CC=C1 ZUOUZKKEUPVFJK-UHFFFAOYSA-N 0.000 description 2
- 229920000728 polyester Polymers 0.000 description 2
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- 238000005204 segregation Methods 0.000 description 2
- 239000000377 silicon dioxide Substances 0.000 description 2
- NTHWMYGWWRZVTN-UHFFFAOYSA-N sodium silicate Chemical compound [Na+].[Na+].[O-][Si]([O-])=O NTHWMYGWWRZVTN-UHFFFAOYSA-N 0.000 description 2
- 229910052911 sodium silicate Inorganic materials 0.000 description 2
- 235000019832 sodium triphosphate Nutrition 0.000 description 2
- AKEJUJNQAAGONA-UHFFFAOYSA-N sulfur trioxide Chemical compound O=S(=O)=O AKEJUJNQAAGONA-UHFFFAOYSA-N 0.000 description 2
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- 150000003624 transition metals Chemical class 0.000 description 2
- DCCWEYXHEXDZQW-BYPYZUCNSA-N (2s)-2-[bis(carboxymethyl)amino]butanedioic acid Chemical compound OC(=O)C[C@@H](C(O)=O)N(CC(O)=O)CC(O)=O DCCWEYXHEXDZQW-BYPYZUCNSA-N 0.000 description 1
- KEQGZUUPPQEDPF-UHFFFAOYSA-N 1,3-dichloro-5,5-dimethylimidazolidine-2,4-dione Chemical compound CC1(C)N(Cl)C(=O)N(Cl)C1=O KEQGZUUPPQEDPF-UHFFFAOYSA-N 0.000 description 1
- XUJLWPFSUCHPQL-UHFFFAOYSA-N 11-methyldodecan-1-ol Chemical compound CC(C)CCCCCCCCCCO XUJLWPFSUCHPQL-UHFFFAOYSA-N 0.000 description 1
- LCPVQAHEFVXVKT-UHFFFAOYSA-N 2-(2,4-difluorophenoxy)pyridin-3-amine Chemical compound NC1=CC=CN=C1OC1=CC=C(F)C=C1F LCPVQAHEFVXVKT-UHFFFAOYSA-N 0.000 description 1
- NSMMFSKPGXCMOE-UHFFFAOYSA-N 2-[2-(2-sulfophenyl)ethenyl]benzenesulfonic acid Chemical compound OS(=O)(=O)C1=CC=CC=C1C=CC1=CC=CC=C1S(O)(=O)=O NSMMFSKPGXCMOE-UHFFFAOYSA-N 0.000 description 1
- XEEYSDHEOQHCDA-UHFFFAOYSA-N 2-methylprop-2-ene-1-sulfonic acid Chemical compound CC(=C)CS(O)(=O)=O XEEYSDHEOQHCDA-UHFFFAOYSA-N 0.000 description 1
- REJHVSOVQBJEBF-OWOJBTEDSA-N 5-azaniumyl-2-[(e)-2-(4-azaniumyl-2-sulfonatophenyl)ethenyl]benzenesulfonate Chemical class OS(=O)(=O)C1=CC(N)=CC=C1\C=C\C1=CC=C(N)C=C1S(O)(=O)=O REJHVSOVQBJEBF-OWOJBTEDSA-N 0.000 description 1
- SFHBJXIEBWOOFA-UHFFFAOYSA-N 5-methyl-3,6-dioxabicyclo[6.2.2]dodeca-1(10),8,11-triene-2,7-dione Chemical compound O=C1OC(C)COC(=O)C2=CC=C1C=C2 SFHBJXIEBWOOFA-UHFFFAOYSA-N 0.000 description 1
- 229910018072 Al 2 O 3 Inorganic materials 0.000 description 1
- UXVMQQNJUSDDNG-UHFFFAOYSA-L Calcium chloride Chemical compound [Cl-].[Cl-].[Ca+2] UXVMQQNJUSDDNG-UHFFFAOYSA-L 0.000 description 1
- 102000005701 Calcium-Binding Proteins Human genes 0.000 description 1
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- KRKNYBCHXYNGOX-UHFFFAOYSA-K Citrate Chemical compound [O-]C(=O)CC(O)(CC([O-])=O)C([O-])=O KRKNYBCHXYNGOX-UHFFFAOYSA-K 0.000 description 1
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- RGHNJXZEOKUKBD-UHFFFAOYSA-N D-gluconic acid Natural products OCC(O)C(O)C(O)C(O)C(O)=O RGHNJXZEOKUKBD-UHFFFAOYSA-N 0.000 description 1
- SNRUBQQJIBEYMU-UHFFFAOYSA-N Dodecane Natural products CCCCCCCCCCCC SNRUBQQJIBEYMU-UHFFFAOYSA-N 0.000 description 1
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- DBVJJBKOTRCVKF-UHFFFAOYSA-N Etidronic acid Chemical compound OP(=O)(O)C(O)(C)P(O)(O)=O DBVJJBKOTRCVKF-UHFFFAOYSA-N 0.000 description 1
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- QPCDCPDFJACHGM-UHFFFAOYSA-N N,N-bis{2-[bis(carboxymethyl)amino]ethyl}glycine Chemical compound OC(=O)CN(CC(O)=O)CCN(CC(=O)O)CCN(CC(O)=O)CC(O)=O QPCDCPDFJACHGM-UHFFFAOYSA-N 0.000 description 1
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- UAOKXEHOENRFMP-ZJIFWQFVSA-N [(2r,3r,4s,5r)-2,3,4,5-tetraacetyloxy-6-oxohexyl] acetate Chemical compound CC(=O)OC[C@@H](OC(C)=O)[C@@H](OC(C)=O)[C@H](OC(C)=O)[C@@H](OC(C)=O)C=O UAOKXEHOENRFMP-ZJIFWQFVSA-N 0.000 description 1
- 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 1
- 238000010521 absorption reaction Methods 0.000 description 1
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- DPXJVFZANSGRMM-UHFFFAOYSA-N acetic acid;2,3,4,5,6-pentahydroxyhexanal;sodium Chemical compound [Na].CC(O)=O.OCC(O)C(O)C(O)C(O)C=O DPXJVFZANSGRMM-UHFFFAOYSA-N 0.000 description 1
- 230000003213 activating effect Effects 0.000 description 1
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- 125000003158 alcohol group Chemical group 0.000 description 1
- 150000001335 aliphatic alkanes Chemical class 0.000 description 1
- 229910000318 alkali metal phosphate Inorganic materials 0.000 description 1
- 238000005904 alkaline hydrolysis reaction Methods 0.000 description 1
- 150000001336 alkenes Chemical class 0.000 description 1
- 150000004996 alkyl benzenes Chemical class 0.000 description 1
- 125000005263 alkylenediamine group Chemical group 0.000 description 1
- 108090000637 alpha-Amylases Proteins 0.000 description 1
- 229910000147 aluminium phosphate Inorganic materials 0.000 description 1
- 150000003863 ammonium salts Chemical class 0.000 description 1
- 229940040526 anhydrous sodium acetate Drugs 0.000 description 1
- 125000004429 atom Chemical group 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 239000002585 base Substances 0.000 description 1
- 150000001555 benzenes Chemical class 0.000 description 1
- 125000006267 biphenyl group Chemical group 0.000 description 1
- 238000009835 boiling Methods 0.000 description 1
- JHIWVOJDXOSYLW-UHFFFAOYSA-N butyl 2,2-difluorocyclopropane-1-carboxylate Chemical compound CCCCOC(=O)C1CC1(F)F JHIWVOJDXOSYLW-UHFFFAOYSA-N 0.000 description 1
- 125000000484 butyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 239000001110 calcium chloride Substances 0.000 description 1
- 229910001628 calcium chloride Inorganic materials 0.000 description 1
- 235000011148 calcium chloride Nutrition 0.000 description 1
- 235000011132 calcium sulphate Nutrition 0.000 description 1
- BVKZGUZCCUSVTD-UHFFFAOYSA-N carbonic acid Chemical class OC(O)=O BVKZGUZCCUSVTD-UHFFFAOYSA-N 0.000 description 1
- 150000001244 carboxylic acid anhydrides Chemical class 0.000 description 1
- 150000001733 carboxylic acid esters Chemical class 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- XTHPWXDJESJLNJ-UHFFFAOYSA-N chlorosulfonic acid Substances OS(Cl)(=O)=O XTHPWXDJESJLNJ-UHFFFAOYSA-N 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 239000003086 colorant Substances 0.000 description 1
- 229910052802 copper Inorganic materials 0.000 description 1
- 238000002425 crystallisation Methods 0.000 description 1
- 230000008025 crystallization Effects 0.000 description 1
- 108010005400 cutinase Proteins 0.000 description 1
- 150000007973 cyanuric acids Chemical class 0.000 description 1
- 125000002993 cycloalkylene group Chemical group 0.000 description 1
- 125000001142 dicarboxylic acid group Chemical group 0.000 description 1
- 150000001991 dicarboxylic acids Chemical class 0.000 description 1
- HNPSIPDUKPIQMN-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Al]O[Al]=O HNPSIPDUKPIQMN-UHFFFAOYSA-N 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- JHUXOSATQXGREM-UHFFFAOYSA-N dodecanediperoxoic acid Chemical compound OOC(=O)CCCCCCCCCCC(=O)OO JHUXOSATQXGREM-UHFFFAOYSA-N 0.000 description 1
- 125000003438 dodecyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- NFDRPXJGHKJRLJ-UHFFFAOYSA-N edtmp Chemical compound OP(O)(=O)CN(CP(O)(O)=O)CCN(CP(O)(O)=O)CP(O)(O)=O NFDRPXJGHKJRLJ-UHFFFAOYSA-N 0.000 description 1
- 239000000835 fiber Substances 0.000 description 1
- 239000000174 gluconic acid Substances 0.000 description 1
- 235000012208 gluconic acid Nutrition 0.000 description 1
- PEDCQBHIVMGVHV-UHFFFAOYSA-N glycerol group Chemical group OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 description 1
- 125000003827 glycol group Chemical group 0.000 description 1
- 125000001046 glycoluril group Chemical group [H]C12N(*)C(=O)N(*)C1([H])N(*)C(=O)N2* 0.000 description 1
- 238000000227 grinding Methods 0.000 description 1
- 108010002430 hemicellulase Proteins 0.000 description 1
- 150000001469 hydantoins Chemical class 0.000 description 1
- 230000036571 hydration Effects 0.000 description 1
- 238000006703 hydration reaction Methods 0.000 description 1
- 229940042795 hydrazides for tuberculosis treatment Drugs 0.000 description 1
- 229930195733 hydrocarbon Natural products 0.000 description 1
- 150000002430 hydrocarbons Chemical class 0.000 description 1
- 150000002431 hydrogen Chemical class 0.000 description 1
- 230000003165 hydrotropic effect Effects 0.000 description 1
- 229920013821 hydroxy alkyl cellulose Polymers 0.000 description 1
- 239000001863 hydroxypropyl cellulose Substances 0.000 description 1
- 235000010977 hydroxypropyl cellulose Nutrition 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- 235000014666 liquid concentrate Nutrition 0.000 description 1
- 239000012669 liquid formulation Substances 0.000 description 1
- HCWCAKKEBCNQJP-UHFFFAOYSA-N magnesium orthosilicate Chemical compound [Mg+2].[Mg+2].[O-][Si]([O-])([O-])[O-] HCWCAKKEBCNQJP-UHFFFAOYSA-N 0.000 description 1
- 239000000391 magnesium silicate Substances 0.000 description 1
- 229910052919 magnesium silicate Inorganic materials 0.000 description 1
- 235000019792 magnesium silicate Nutrition 0.000 description 1
- FPYJFEHAWHCUMM-UHFFFAOYSA-N maleic anhydride Chemical compound O=C1OC(=O)C=C1 FPYJFEHAWHCUMM-UHFFFAOYSA-N 0.000 description 1
- 229910052748 manganese Inorganic materials 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 230000008018 melting Effects 0.000 description 1
- 238000002844 melting Methods 0.000 description 1
- 229910044991 metal oxide Inorganic materials 0.000 description 1
- 150000004706 metal oxides Chemical class 0.000 description 1
- XJRBAMWJDBPFIM-UHFFFAOYSA-N methyl vinyl ether Chemical class COC=C XJRBAMWJDBPFIM-UHFFFAOYSA-N 0.000 description 1
- 125000000250 methylamino group Chemical group [H]N(*)C([H])([H])[H] 0.000 description 1
- 229910052750 molybdenum Inorganic materials 0.000 description 1
- 150000002763 monocarboxylic acids Chemical class 0.000 description 1
- 125000004573 morpholin-4-yl group Chemical group N1(CCOCC1)* 0.000 description 1
- 125000001421 myristyl 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])[H] 0.000 description 1
- MGFYIUFZLHCRTH-UHFFFAOYSA-N nitrilotriacetic acid Chemical compound OC(=O)CN(CC(O)=O)CC(O)=O MGFYIUFZLHCRTH-UHFFFAOYSA-N 0.000 description 1
- SXLLDUPXUVRMEE-UHFFFAOYSA-N nonanediperoxoic acid Chemical compound OOC(=O)CCCCCCCC(=O)OO SXLLDUPXUVRMEE-UHFFFAOYSA-N 0.000 description 1
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 description 1
- 229920001542 oligosaccharide Polymers 0.000 description 1
- 230000004792 oxidative damage Effects 0.000 description 1
- 230000001590 oxidative effect Effects 0.000 description 1
- 125000006353 oxyethylene group Chemical group 0.000 description 1
- 239000001301 oxygen 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
- 235000019809 paraffin wax Nutrition 0.000 description 1
- 229960003330 pentetic acid Drugs 0.000 description 1
- 150000004965 peroxy acids Chemical class 0.000 description 1
- JRKICGRDRMAZLK-UHFFFAOYSA-L persulfate group Chemical group S(=O)(=O)([O-])OOS(=O)(=O)[O-] JRKICGRDRMAZLK-UHFFFAOYSA-L 0.000 description 1
- 235000019271 petrolatum Nutrition 0.000 description 1
- 239000012071 phase Substances 0.000 description 1
- 238000005191 phase separation Methods 0.000 description 1
- PATMLLNMTPIUSY-UHFFFAOYSA-N phenoxysulfonyl 7-methyloctanoate Chemical compound CC(C)CCCCCC(=O)OS(=O)(=O)OC1=CC=CC=C1 PATMLLNMTPIUSY-UHFFFAOYSA-N 0.000 description 1
- 150000003013 phosphoric acid derivatives Chemical class 0.000 description 1
- 229910052615 phyllosilicate Inorganic materials 0.000 description 1
- 229920000058 polyacrylate Polymers 0.000 description 1
- 229920001515 polyalkylene glycol Polymers 0.000 description 1
- 229920002647 polyamide Polymers 0.000 description 1
- 229920000139 polyethylene terephthalate Polymers 0.000 description 1
- 239000005020 polyethylene terephthalate Substances 0.000 description 1
- 229920000151 polyglycol Polymers 0.000 description 1
- 239000010695 polyglycol Substances 0.000 description 1
- 238000006116 polymerization reaction Methods 0.000 description 1
- 229920000193 polymethacrylate Polymers 0.000 description 1
- 229920006324 polyoxymethylene Polymers 0.000 description 1
- 229920002451 polyvinyl alcohol Polymers 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
- 125000001436 propyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- QQONPFPTGQHPMA-UHFFFAOYSA-N propylene Natural products CC=C QQONPFPTGQHPMA-UHFFFAOYSA-N 0.000 description 1
- 125000004805 propylene group Chemical group [H]C([H])([H])C([H])([*:1])C([H])([H])[*:2] 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 239000011347 resin Substances 0.000 description 1
- 229920005989 resin Polymers 0.000 description 1
- 230000002441 reversible effect Effects 0.000 description 1
- 238000007127 saponification reaction Methods 0.000 description 1
- 150000004671 saturated fatty acids Chemical class 0.000 description 1
- 235000003441 saturated fatty acids Nutrition 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 239000003352 sequestering agent Substances 0.000 description 1
- 235000019812 sodium carboxymethyl cellulose Nutrition 0.000 description 1
- 229920001027 sodium carboxymethylcellulose Polymers 0.000 description 1
- 235000011121 sodium hydroxide Nutrition 0.000 description 1
- 235000019795 sodium metasilicate Nutrition 0.000 description 1
- QSKQNALVHFTOQX-UHFFFAOYSA-M sodium nonanoyloxybenzenesulfonate Chemical compound [Na+].CCCCCCCCC(=O)OC1=CC=CC=C1S([O-])(=O)=O QSKQNALVHFTOQX-UHFFFAOYSA-M 0.000 description 1
- 239000012418 sodium perborate tetrahydrate Substances 0.000 description 1
- CHQMHPLRPQMAMX-UHFFFAOYSA-L sodium persulfate Substances [Na+].[Na+].[O-]S(=O)(=O)OOS([O-])(=O)=O CHQMHPLRPQMAMX-UHFFFAOYSA-L 0.000 description 1
- 159000000000 sodium salts Chemical class 0.000 description 1
- SZHIIIPPJJXYRY-UHFFFAOYSA-M sodium;2-methylprop-2-ene-1-sulfonate Chemical compound [Na+].CC(=C)CS([O-])(=O)=O SZHIIIPPJJXYRY-UHFFFAOYSA-M 0.000 description 1
- QUCDWLYKDRVKMI-UHFFFAOYSA-M sodium;3,4-dimethylbenzenesulfonate Chemical compound [Na+].CC1=CC=C(S([O-])(=O)=O)C=C1C QUCDWLYKDRVKMI-UHFFFAOYSA-M 0.000 description 1
- IBDSNZLUHYKHQP-UHFFFAOYSA-N sodium;3-oxidodioxaborirane;tetrahydrate Chemical compound O.O.O.O.[Na+].[O-]B1OO1 IBDSNZLUHYKHQP-UHFFFAOYSA-N 0.000 description 1
- CVYDEWKUJFCYJO-UHFFFAOYSA-M sodium;docosanoate Chemical compound [Na+].CCCCCCCCCCCCCCCCCCCCCC([O-])=O CVYDEWKUJFCYJO-UHFFFAOYSA-M 0.000 description 1
- 238000007711 solidification Methods 0.000 description 1
- 230000008023 solidification Effects 0.000 description 1
- 239000002195 soluble material Substances 0.000 description 1
- 239000005720 sucrose Substances 0.000 description 1
- 230000001180 sulfating effect Effects 0.000 description 1
- 230000019635 sulfation Effects 0.000 description 1
- 238000005670 sulfation reaction Methods 0.000 description 1
- 238000006277 sulfonation reaction Methods 0.000 description 1
- 229920002994 synthetic fiber Polymers 0.000 description 1
- 238000009988 textile finishing Methods 0.000 description 1
- 229910052719 titanium Inorganic materials 0.000 description 1
- URAYPUMNDPQOKB-UHFFFAOYSA-N triacetin Chemical compound CC(=O)OCC(OC(C)=O)COC(C)=O URAYPUMNDPQOKB-UHFFFAOYSA-N 0.000 description 1
- 150000003852 triazoles Chemical class 0.000 description 1
- 229910052720 vanadium Inorganic materials 0.000 description 1
- 229920001567 vinyl ester resin Polymers 0.000 description 1
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 description 1
- 238000004065 wastewater treatment Methods 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
- C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
- C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
- C11D3/16—Organic compounds
- C11D3/20—Organic compounds containing oxygen
- C11D3/2068—Ethers
-
- C—CHEMISTRY; METALLURGY
- C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
- C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
- C11D1/00—Detergent compositions based essentially on surface-active compounds; Use of these compounds as a detergent
- C11D1/66—Non-ionic compounds
- C11D1/825—Mixtures of compounds all of which are non-ionic
-
- 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
- C11D17/0004—Non aqueous liquid compositions comprising insoluble particles
-
- 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
- C11D17/0008—Detergent materials or soaps characterised by their shape or physical properties aqueous liquid non soap compositions
- C11D17/003—Colloidal solutions, e.g. gels; Thixotropic solutions or pastes
-
- C—CHEMISTRY; METALLURGY
- C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
- C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
- C11D1/00—Detergent compositions based essentially on surface-active compounds; Use of these compounds as a detergent
- C11D1/66—Non-ionic compounds
- C11D1/72—Ethers of polyoxyalkylene glycols
Definitions
- the present invention relates to pasty detergents and cleaning agents and a Process for their production.
- Detergents used in the household are tailored to the needs there; so they are usually powdery or sufficiently liquid to be themselves pour and dispense easily. Because such liquid detergents should be stable in storage within relatively wide temperature ranges are common Additions of organic solvents and / or hydrotropes added, however itself make no contribution to the washing or cleaning result are undesirable for this reason.
- a way to circumvent any Dosing problems with insufficiently liquid agents are in the European Patent application EP 253 151 A2 proposed. From this document, liquid, some highly viscous detergents based on non-ionic and anionic surfactants known which contain polyethylene glycol as hydrotrope and which the user does not must be dosed in liquid form, but portioned into bags water-soluble material, for example polyvinyl alcohol.
- the paste-like detergent described in European patent EP 295 525 B1 consists of a liquid phase in the temperature range below 10 ° C nonionic surfactant is formed, and a solid phase dispersed therein Grain size, which consists of washing alkalis, sequestrants and optionally Anionic surfactants is formed.
- the pour point solidification point
- This Detergent paste is intended for commercial laundries and is so flowable that it can be conveyed via a suction line using a conventional feed pump.
- Another pasty Detergent which is a nonionic surfactant 40 to 70 wt .-% liquid at room temperature ethoxylated fatty alcohol with 10 to 20 carbon atoms and an average degree of ethoxylation from 1 to 8 and 20 to 50% by weight of ethoxylated and liquid at room temperature propoxylated fatty alcohol with 10 to 20 carbon atoms and a medium Degree of ethoxylation from 2 to 8 and an average degree of propoxylation from 1 to 6 and 1 to 10 Wt .-% soap, is described in international patent application WO 95/09229.
- This pasty detergent is so structurally viscous that it is Room temperature is not flowable under the influence of gravity, but one under shear has significantly lower viscosity and is then flowable under the influence of gravity.
- the dosage of this pasty detergent or cleaning agent is preferably carried out in that the agent for lowering the viscosity is subjected to shear and that then flowable agents can be metered by means of feed pumps.
- the present invention was therefore based on the object of a pasty detergent for to provide use in commercial laundries with good storage stability has a good washing performance, although it is based on the synthetic materials normally required for this Anionic surfactants of the alkylbenzenesulfonate type are dispensed with.
- the present invention relates to a pasty detergent for use in commercial laundries, containing nonionic surfactant, organic and / or inorganic builders, alkalizing agents and optionally bleaching agent, enzyme, graying-inhibiting polymer and / or other conventional ingredients, which is characterized in that it is free from synthetic anionic surfactant of the alkylbenzenesulfonate type and 5% by weight to 30% by weight, in particular 10% by weight to 25% by weight, of an ethoxylated alcohol of the general formula I, R 1 - (OC 2 H 4 ) m -OH in which R 1 denotes an alkyl or alkenyl radical with 8 to 14 carbon atoms and the average degree of ethoxylation m can assume values from 1 to 8, 1% by weight to 20% by weight, in particular 5% by weight to 15 % By weight of an ethoxylated alcohol of the general formula II, R 2 - (OC 2 H 4 ) n -OH in which R 2 denotes an alky
- the liquid phase of the paste-like composition according to the invention is essentially formed by the nonionic surfactants of the formulas I and II, which have different carbon chain lengths and different degrees of ethoxylation, and the alcohols or ethers of the formula III.
- the viscosity of the agent according to the invention can be adjusted by combining ethoxylated alcohols with the formulas I and II.
- the radicals R 1 and R 2 can be linear or branched, for example methyl-branched in the 2-position, linear radicals having primary etherified alcohol functions being preferred.
- the nonionic surfactant according to formula I preferably has a carbon chain length of 8 to 14, in particular 12 to 14, carbon atoms and an average degree of alkoxylation m of 1 to 8.
- the nonionic surfactant according to formula II has a broader carbon chain length distribution towards longer chains with 12 to 22, in particular 12 to 18, carbon atoms and a higher average degree of alkoxylation n of 3 to 14.
- the ethoxylated alcohols of the formula I and the ethoxylated alcohols of the formula II are preferably in weight ratios of 2: 1 to 1: 1.8.
- the agent according to the invention can contain further nonionic surfactants commonly used in washing and cleaning agents, such as, for example, alkyl polyglycosides and / or fatty acid polyhydroxyamides.
- the surfactant component is preferably free from propoxylated alcohols, since poorer biodegradability is expected from these.
- the above applies essentially to the radicals R 3 for the radicals R 1 and R 2 .
- R 4 is preferably a methyl, ethyl, propyl or butyl group, with hydrogen and the methyl group being particularly preferred.
- the agents contain up to 10% by weight, preferably 2% by weight to 6% by weight, of substances according to general formula III.
- the agent can contain up to 5% by weight, in particular 0.5% by weight to 3% by weight, of natural or synthetic anionic surfactants as further surfactants.
- Suitable synthetic anionic surfactants which can preferably be incorporated into the agent according to the invention in solid, finely divided, largely anhydrous form, include, in particular, those of the sulfonate or sulfate type, which are normally present as alkali metal salts, preferably as sodium salts.
- the surfactants of the sulfonate type mentioned can also be used in the form of their free acids.
- Suitable anionic surfactants of the sulfonate type are linear alkanesulfonates with 11 to 15 carbon atoms, as can be obtained by sulfochlorination or sulfoxidation of alkanes and subsequent saponification or neutralization, salts of sulfofatty acids and their esters, which are sulfonated in particular in the ⁇ -position derived saturated C 12 to C 18 fatty acids and lower alcohols, such as methanol, ethanol and propanol, and olefin sulfonates, as are formed, for example, by sulfonation of terminal C 12 to C 18 olefins and subsequent alkaline hydrolysis.
- Suitable surfactants of the sulfate type are, in particular, the primary alkyl sulfates with preferably linear alkyl radicals having 10 to 20 carbon atoms, which have an alkali, ammonium or alkyl or hydroxyalkyl-substituted ammonium ion as countercation.
- the derivatives of linear alcohols with in particular 12 to 18 carbon atoms and their branched-chain analogs, the so-called oxo alcohols are particularly suitable. Accordingly, the sulfation products of primary fatty alcohols with linear dodecyl, tetradecyl or octadecyl radicals and mixtures thereof are particularly useful.
- alkyl sulfates contain a tallow alkyl radical, that is to say mixtures with essentially hexadecyl and octadecyl radicals.
- the alkyl sulfates can be prepared in a known manner by reaction of the corresponding alcohol component with a customary sulfating reagent, in particular sulfur trioxide or chlorosulfonic acid, and subsequent neutralization with alkali, ammonium or alkyl or hydroxyalkyl-substituted ammonium bases.
- a customary sulfating reagent in particular sulfur trioxide or chlorosulfonic acid
- the sulfated alkoxylation products of such alcohols so-called ether sulfates, can be contained in the compositions.
- Such ether sulfates preferably contain 2 to 30, in particular 4 to 10, ethylene glycol groups per molecule.
- Synthetic anionic surfactants of the alkylbenzenesulfonate type are completely absent in the agents according to the invention.
- the agent is completely free from synthetic anionic surfactants.
- the naturally occurring anionic surfactants include, in particular, the soaps, which can be present in the agents according to the invention preferably in amounts of up to 5% by weight, in particular from 0.5% by weight to 2% by weight.
- Suitable soaps are in particular the alkali metal salts of the saturated and / or unsaturated C 12-18 fatty acids, for example coconut, palm kernel or tallow fatty acid.
- salts of a carboxylic acid mixture of, in each case based on the total carboxylic acid mixture, from 2% by weight to 8% by weight of C 14- , up to 1% by weight of C 15- , 18% by weight to 24 is particularly preferred %
- C 16 - up to 3% by weight C 17 -, 20% by weight to 42% by weight C 18 - and 30% by weight to 44% by weight C 20-22 - Carboxylic acid.
- the solid phase of the agent according to the invention is essentially from the Alkalizing agents and builder substances are formed, optionally further particulate auxiliaries may be present.
- the solid phase should be in the liquid Be dispersed as homogeneously as possible.
- the contained as a solid phase Components of the paste-like agent should be finely divided and an average grain size have in the range of 5 microns to 200 microns, with at most 10% of the particles Have grain size of more than 200 microns.
- the average grain size is preferably that of the solid phase Particles 10 microns to 80 microns and especially 10 microns to 60 microns, the maximum Grain size is less than 300 microns, especially less than 250 microns. Are preferred 90 wt .-% of the solid powdery components smaller than 200 microns, in particular smaller than 140 ⁇ m.
- the average grain size can be determined by known methods (for example using laser diffraction or a Coulter Counter).
- the alkalizing agents contained as a further component are often also referred to as washing alkalis. They are mainly assigned to the fixed phase. Under the conditions of use of agents according to the invention, they ensure a pH in the alkaline range which is normally in the range from 9 to 13, in particular from 10 to 12 (in each case measured in a 1% strength by weight solution of the agent in ion-exchanged water).
- the preferred alkalizing agent is amorphous alkali silicate, in particular sodium metasilicate of the composition Na 2 O: SiO 2 from 1: 0.8 to 1: 1.3, preferably 1: 1, which is used in anhydrous form.
- anhydrous alkali carbonate or alkali hydrogen carbonate are also suitable, which, however, requires larger proportions of the liquid phase due to absorption processes and is therefore less preferred.
- the proportion of alkalizing agents in the agents is 20% by weight to 80% by weight, preferably 30% by weight to 70% by weight and in particular 40% by weight to 60% by weight.
- the alkalizing agent component of the agent according to the invention can consist solely of silicate.
- Alkali carbonate or alkali hydrogen carbonate is preferably present at most up to 20% by weight, in particular below 10% by weight.
- polymeric alkali metal phosphates such as sodium tripolyphosphate
- Their proportion is preferably up to 70% by weight, in particular 15% by weight to 25% by weight, based on the total composition, the proportion of the other solids, for example the alkali silicate and / or optionally contained aluminosilicate, accordingly can be reduced.
- Suitable organic builder substances are, in particular, monomeric polycarboxylic acids or hydroxycarboxylic acids such as citric acid or gluconic acid or their salts and, in addition, those from the class of the aminopolycarboxylic acids and polyphosphonic acids.
- the aminopolycarboxylic acids include nitrilotriacetic acid, ethylenediaminetetraacetic acid, diethylenetriaminepentaacetic acid and their higher homologues, preference being given to using N, N-bis (carboxymethyl) aspartic acid.
- Suitable polyphosphonic acids are 1-hydroxyethane-1,1-diphosphonic acid, amino-tri (methylenephosphonic acid), ethylenediaminetetra (methylenephosphonic acid) and their higher homologs, such as, for example, diethylene tetramine tetra (methylenephosphonic acid).
- the abovementioned acids are usually used in the form of their alkali metal salts, in particular the sodium or potassium salts.
- the builders which can also be used include homopolymeric and / or copolymeric carboxylic acids or their alkali metal salts, the sodium or potassium salts also being particularly preferred here.
- Polymer carboxylates or polymer carboxylic acids with a relative molecular weight of at least 350 in the form of their water-soluble salts, in particular in the form of the sodium and / or potassium salts, have proven to be particularly suitable, such as oxidized polysaccharides according to international patent application WO 93/08251, polyacrylates , Polymethacrylates, polymaleates and in particular copolymers of acrylic acid with maleic acid or maleic anhydride, preferably those of 50 to 70% acrylic acid and 50 to 10% maleic acid, as are characterized, for example, in European patent EP 022 551.
- the relative molecular weight of the homopolymers is generally between 1000 and 100000, that of the copolymers between 2000 and 200000, preferably 50,000 to 120,000, based on free acid.
- a particularly preferred acrylic acid-maleic acid copolymer has a relative molecular weight of 50,000 to 100,000.
- Suitable, albeit less preferred, compounds of this class are copolymers of acrylic acid or methacrylic acid with vinyl ethers, such as vinyl methyl ethers, vinyl esters, ethylene. Propylene and styrene, in which the proportion of acid is at least 50% by weight.
- Terpolymers which contain two unsaturated acids and / or salts thereof as monomers and vinyl alcohol and / or a vinyl alcohol derivative or a carbohydrate as monomers can also be used as polymeric carboxylates or carboxylic acids.
- the first acidic monomer or its salt is derived from a monoethylenically unsaturated C 3 -C 8 carboxylic acid and preferably from a C 3 -C 4 monocarboxylic acid, in particular from (meth) acrylic acid.
- the second acidic monomer or its salt can be a derivative of a C 4 -C 8 dicarboxylic acid, maleic acid being preferred.
- the third monomeric unit is formed from vinyl alcohol and / or preferably an esterified vinyl alcohol.
- Vinyl alcohol derivatives which are an ester of short-chain carboxylic acids, for example of C 1 -C 4 -carboxylic acids, with vinyl alcohol are particularly preferred.
- Preferred terpolymers contain 60 to 95% by weight, in particular 70 to 90% by weight of (meth) acrylic acid or (meth) acrylate, particularly preferably acrylic acid or acrylate, and maleic acid or maleinate and 5 to 40% by weight, preferably 10 to 30 wt .-% vinyl alcohol and / or vinyl acetate.
- Terpolymers in which the weight ratio (meth) acrylic acid to maleic acid or maleate is between 1: 1 and 4: 1, preferably between 2: 1 and 3: 1 and in particular 2: 1 and 2.5: 1 are very particularly preferred.
- the second acidic monomer or its salt can also be a derivative of an allylsulfonic acid which, in the 2-position, has an alkyl radical, preferably a C 1 -C 4 -alkyl radical, or an aromatic radical which is preferably derived from benzene or benzene derivatives is substituted.
- Preferred terpolymers contain 40 to 60% by weight, in particular 45 to 55% by weight of (meth) acrylic acid or (meth) acrylate, particularly preferably acrylic acid or acrylate, 10% by weight to 30% by weight, preferably 15 % By weight to 25% by weight of methallylsulfonic acid or methallylsulfonate and, as the third monomer, 15% by weight to 40% by weight, preferably 20% by weight to 40% by weight, of a carbohydrate.
- This carbohydrate can be, for example, a mono-, di-, oligo- or polysaccharide, mono-, di- or oligosaccharides being preferred. Sucrose is particularly preferred.
- polymers which are either completely or at least partially, in particular to more than 50%, based on the carboxyl groups present, are also preferably used.
- Particularly preferred polymeric polycarboxylates are produced by processes which are described in German patent application DE 43 00 772 and German patent DE 42 21 381.
- polyacetal carboxylic acids such as are described, for example, in US Pat. Nos. 4,144,226 and 4,146,495, which are obtained by polymerizing esters of glycolic acid, introducing stable terminal end groups and saponifying to give the sodium or potassium salts.
- polymeric acids which are obtained by polymerizing acrolein and disproportionating the polymer according to Canizzaro using strong alkalis. They are essentially made up of acrylic acid units and vinyl alcohol units or acrolein units.
- the proportion of organic, carboxyl group-containing builder materials in the paste-like composition according to the invention up to 10% by weight, preferably 1 % By weight to 7.5% by weight and in particular 2% by weight to less than 5% by weight, the proportion of polymeric polycarboxylate is as low as possible and less than 5% by weight lies.
- these substances mentioned are also used in anhydrous form.
- crystalline alkali silicates and finely divided alkali alumosilicates are suitable as inorganic builders for use in agents according to the invention.
- Suitable zeolites normally have a calcium binding capacity in the range from 100 to 200 mg CaO / g, which can be determined according to the information in German patent DE 24 12 837.
- Their particle size is usually in the range from 1 ⁇ m to 10 ⁇ m. They are used in dry form. The water contained in bound form in the zeolites does not interfere in the present case.
- Such crystalline layered silicates are described, for example, in European patent application EP 164 514.
- both ⁇ - and ⁇ -sodium disilicate Na 2 Si 2 O 5 .yH 2 O are preferred, wherein ⁇ -sodium disilicate can be obtained, for example, by the method described in international patent application WO 91/08171.
- Usable crystalline silicates are commercially available under the names SKS-6 (manufacturer Hoechst) and Nabion® 15 (manufacturer Rhone-Poulenc).
- the content of inorganic builder material in the paste can be up to 35% by weight, preferably up to 25% by weight and in particular 10% by weight to 25% by weight.
- agents according to the invention 5% by weight to 25 % By weight, in particular 10% by weight to 20% by weight, of builder substances, the Amount of polymeric polycarboxylates not more than 5% by weight, in particular 0% by weight, and the amount of phosphonates not more than 0.5% by weight, especially not more than 0.2% by weight.
- a paste-like agent according to the invention can contain an oxygen-containing oxidizing agent and optionally a bleach activator.
- Inorganic peroxygen compounds in particular are used as the oxidizing agent, the sodium perborate tetrahydrate and the sodium perborate monohydrate being of particular importance in addition to sodium percarbonate.
- Other suitable oxidizing agents are, for example, persulfates, peroxypyrophosphates, citrate perhydrates and H 2 O 2 -producing peracid salts or peracids, such as perbenzoates, peroxophthalates, diperoxyazelaic acid or diperoxydodecanedioic acid.
- Sodium percarbonate, sodium persulfate and / or sodium perborate monohydrate are preferably used.
- Oxidizing agents can be present in agents according to the invention preferably in amounts of up to 25% by weight and in particular from 10% by weight to 20% by weight.
- the oxidizing power of such oxidizing agents can be achieved by using bleach activators be improved, which form peroxocarboxylic acids under perhydrolysis conditions.
- bleach activators especially from the substance classes the N- or O-acyl compounds, for example multiple acylated alkylenediamines, especially tetraacetylethylenediamine, acylated glycolurils, especially tetraacetylglycoluril, N-acylated hydantoins, hydrazides, triazoles, hydrotriazines, urazoles, diketopiperazines, Sulfurylamides and cyanurates, also carboxylic anhydrides, in particular Phthalic anhydride, carboxylic acid esters, especially sodium nonanoyloxy-benzenesulfonate, Sodium isononanoyl oxybenzenesulfonate and triacetin (glycerol triacetate), and Acylated sugar derivatives
- a bleach activator is preferably used which contains peracetic acid under the washing conditions forms, with tetraacetylethylenediamine being particularly preferred.
- Agents according to the invention preferably contain up to 10% by weight, in particular of 3% to 8% bleach activator by weight.
- the addition of bleach activators can the bleaching effect of aqueous peroxide liquors can be increased so far that already at Temperatures around 60 ° C essentially the same effects as with the peroxide liquor enter at 95 ° C alone.
- transition metal salts and complexes such as in European patent applications EP 0 392 592, EP 0 443 651, EP 0 458 397, EP 0 544 490, EP 0 549 271, EP 0 630 964 or EP 0 693 550 proposed as so-called bleach catalysts in addition to or instead of the conventional bleach activators, result in an increase in bleaching performance.
- transition metal salts and complexes such as in European patent applications EP 0 392 592, EP 0 443 651, EP 0 458 397, EP 0 544 490, EP 0 549 271, EP 0 630 964 or EP 0 693 550 proposed as so-called bleach catalysts in addition to or instead of the conventional bleach activators, result in an increase in bleaching performance.
- German patent applications DE 195 29 905, DE 195 36 082, DE 196 05 688, DE 196 20 411 and DE 196 20 267 as bleach activating catalysts known transition metal complexes.
- Bleach-activating transition metal complexes in particular with the central atoms Mn, Fe, Co, Cu, Mo, V, Ti and / or Ru, are in the invention Averages in amounts of preferably not more than 1% by weight, contain in particular from 0.0025% by weight to 0.25% by weight.
- an agent according to the invention can contain further washing auxiliaries which normally in amounts up to about 15% by weight, based on the finished product, can be present.
- Enzymes, graying inhibitors, soil release agents, optical brighteners, foam regulators and / or colors and fragrances are used.
- fragrances are contained in the are generally liquid, they go into the liquid phase of agents according to the invention about. Because of their small amount, however, they have an impact on the flow behavior of the pastes no noteworthy influence.
- the paste-like detergents according to the invention are essentially free of Water and organic solvents.
- “essentially free of water” is a To understand state in which the content of free, that is, not in the form of Water of hydration and constitutional water less than 3% by weight, preferably is below 2% by weight and in particular below 1% by weight. Higher water contents are disadvantageous because they increase the viscosity of the agent disproportionately and especially its Reduce stability.
- Organic solvents which are commonly found in liquid concentrates used low molecular weight and low boiling alcohols and ether alcohols count, as well as hydrotropic compounds are apart from traces associated with individual active ingredients can also be introduced, also not available.
- Enzymes which may be present in the agents according to the invention are in particular those from the class of proteases, lipases, cutinases, amylases, pullulanases, Xylanases, hemicellulases, cellulases, peroxidases and oxidases or their mixtures in question, the use of protease, amylase, Lipase and / or cellulase is particularly preferred.
- the proportion is preferably 0.2 % By weight to 1.5% by weight, in particular 0.5% by weight to 1% by weight.
- the enzymes can be found in be adsorbed onto carrier substances and / or embedded in coating substances in the usual way or as concentrated, water-free liquid formulations in the pastes be incorporated.
- Proteases that can be used are, for example, from the international Patent applications WO 91/02792, WO 92/21760, WO 93/05134, WO 93/07276, WO 93/18140, WO 93/24623, WO 94/02618, WO 94/23053, WO 94/25579, WO 94/25583, WO 95/0204/1, WO 95/05477, WO 95/07350, WO 95/10592, WO 95/10615, WO 95/20039, WO 95/20663, WO 95/23211, WO 95/27049, WO 95/30010, WO 95/30011, WO 95/30743 and WO 95/34627 are known.
- Prefers enzymes are stabilized against oxidative damage, for example those under the trade names Durazym® or Purafect® Oxp or Duramyl® or Purafect® OxAm known proteases or amylases.
- Suitable graying inhibitors or soil release agents are Cellulose ethers, such as carboxymethyl cellulose, methyl cellulose, hydroxyalkyl celluloses and mixed cellulose ethers, such as methylhydroxyethyl cellulose, Methyl hydroxypropyl cellulose and methyl carboxymethyl cellulose. Preferably are sodium carboxymethyl cellulose and their mixtures with methyl cellulose used. Soil release agents commonly used include Copolyester, the dicarboxylic acid units, alkylene glycol units and polyalkylene glycol units contain. Soil-removing copolyesters of the type mentioned as well their use in detergents has been known for a long time.
- German Offenlegungsschrift DT 16 17 141 a washing process using Polyethylene terephthalate-polyoxyethylene glycol copolymers.
- the German published application DT 22 00 911 relates to detergents made from nonionic surfactant and a copolymer Contain polyoxyethylene glycol and polyethylene terephthalate.
- acidic textile finishing agents called a copolymer from a dibasic carboxylic acid and an alkylene or cycloalkylene polyglycol and optionally contain an alkylene or cycloalkylene glycol.
- the European Patent EP 066 944 relates to textile treatment agents which contain a copolyester of ethylene glycol, Polyethylene glycol, aromatic dicarboxylic acid and sulfonated aromatic dicarboxylic acid contained in certain molar ratios.
- From the European patent EP 185 427 are methyl or ethyl end-capped polyesters with ethylene and / or propylene terephthalate and polyethylene oxide terephthalate units and Detergents containing such soil release polymer are known.
- the European patent EP 241 984 relates to a polyester which, in addition to oxyethylene groups and terephthalic acid units also contains substituted ethylene units and glycerol units.
- the Proportion of graying inhibitors and / or soil release active ingredients in Agents according to the invention are generally not more than 2% by weight and are preferably 0.5% to 1.5% by weight. In a preferred embodiment of the Invention is the agent free of such active ingredients.
- optical brightener for in particular textiles made of cellulose fibers (for example Cotton) can, for example, derivatives of diaminostilbenedisulfonic acid or their alkali metal salts may be included.
- diaminostilbenedisulfonic acid for example, are suitable Salts of 4,4'-bis (2-anilino-4-morpholino-1,3,5-triazin-6-yl-amino) stilbene-2,2'-disulfonic acid or compounds of the same structure that replace the morpholino group a diethanolamino group, a methylamino group or a 2-methoxyethylamino group wear.
- brighteners of the type of substituted 4,4'-distyryl diphenyl may be present, for example 4,4'-bis (4-chloro-3-sulfostyryl) diphenyl. Mixtures of brighteners can also be used.
- Polyamide fibers are particularly suitable for brighteners of the 1,3-diaryl-2-pyrazoline type, for example 1- (p-sulfoamoylphenyl) -3- (p-chlorophenyl) -2-pyrazoline and similar connections.
- the content of the agent in optical brighteners or brightener mixtures is generally not more than 1% by weight, preferably 0.05 % By weight to 0.5% by weight. In a preferred embodiment of the invention that is Agents free from such active ingredients.
- the usual foam regulators which can be used in the agents according to the invention include, for example, polysiloxane / silica mixtures, the finely divided silica contained therein preferably being silanated.
- the polysiloxanes can consist of both linear compounds and crosslinked polysiloxane resins and mixtures thereof.
- Further defoamers are paraffin hydrocarbons, in particular microparaffins and paraffin waxes, whose melting point is above 40 ° C, saturated fatty acids or soaps with in particular 20 to 22 C atoms, for example sodium behenate, and alkali metal salts of phosphoric acid mono- and / or dialkyl esters, in which the alkyl chains each have 12 to 22 carbon atoms.
- Sodium monoalkyl phosphate and / or dialkyl phosphate with C 16 to C 18 alkyl groups is particularly preferably used.
- the proportion of foam regulators can preferably be 0.2% by weight to 2% by weight.
- the propensity to foam can be reduced by a suitable selection of the nonionic surfactants, so that the use of defoaming active substances can be completely dispensed with in a preferred embodiment of the invention.
- dehydrating agents can also be used, for example in the form of salts which bind water of crystallization, such as anhydrous sodium acetate, calcium sulfate, calcium chloride, sodium hydroxide, magnesium silicate, or metal oxides such as CaO, MgO, P 4 O 10 or Al 2 O 3 can be used.
- Such dehydrating agents with which the water content of agents according to the invention can be reduced to particularly low values, are present in the agents in amounts of preferably 1% by weight to 10% by weight and in particular 2% by weight to 8% by weight of the invention.
- the surfactant components that is the nonionic Surfactants of the formulas I and II and the alcohols or ethers of the formula III and optionally soap and synthetic anionic surfactants to a homogeneous
- the premix is mixed and the solids and optionally in this premix other components can be incorporated. If the particulate solids are not are sufficiently finely divided, one or more grinding steps can be inserted.
- a paste-like agent according to the invention preferably has a viscosity at 25 ° C. in the range from 80,000 mPas to 250,000 mPas, in particular 100,000 mPas to 250,000 mPas, measured with a Brookfield rotary viscometer (spindle no. 7) at 5 revolutions per minute. Under otherwise identical conditions, the viscosity at 50 revolutions per minute is preferably 20,000 mPa ⁇ s to 80,000 mPa ⁇ s.
- the paste-like detergent and cleaning agent preferably has a viscosity at room temperature such that it is not flowable under the action of gravity.
- an agent according to the invention preferably has a viscosity which is considerably lower, as a rule 100 to 2000 times lower, which is at a shear rate of 10 s -1 and otherwise identical measuring conditions, in particular in the range from 40 mPas to 60 mPas.
- the numerical values for viscosity refer to the reading after a measuring time of 3 minutes, in order to take into account any thixotropy effect of the paste.
- the reduction in viscosity during shear is largely reversible, that is to say after the shear has ended, the agent returns to its original physical state without segregation occurring.
- viscosities mentioned do not refer to measurements directly after the paste has been made, but to stored pastes that are, so to speak, in equilibrium, since the shear forces acting in the course of the manufacturing process lead to a lower paste viscosity, which only occurs in the Increased over time to the definitive final viscosity. Storage times of 1 month are usually completely sufficient for this.
- An agent according to the invention normally has a density in the range of 1.3 kg / l up to 1.6 kg / l.
- the agent according to the invention can be used with conventional devices Dosing of pastes can be dosed, as for example in the international Patent application WO 95/29282, German patent application DE 196 05 906, the German patent specification DE 44 30 418 or the European patent specifications EP 0 295 525 and EP 0 356 707 have been described. One for them Dosage of structurally viscous pasty detergents is particularly suitable
- the device is, for example, from international patent application WO 95/09263 is known and is preferred for metering pseudoplastic pastes according to the invention used.
- the detergents and cleaning agents according to the invention can optionally can also be filled pre-portioned into water-soluble films in particular. Such films are, for example, in European patent application EP 253 151 described.
- composition of detergents according to the invention had a very good storage stability and, despite the absence of synthetic anionic surfactant, had an excellent cleaning performance.
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Applications Claiming Priority (3)
Application Number | Priority Date | Filing Date | Title |
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DE19636035A DE19636035A1 (de) | 1996-09-05 | 1996-09-05 | Pastenförmiges Wasch- und Reinigungsmittel |
DE19636035 | 1996-09-05 | ||
PCT/EP1997/004690 WO1998010049A1 (de) | 1996-09-05 | 1997-08-28 | Pastenförmiges wasch- und reinigungsmittel |
Publications (2)
Publication Number | Publication Date |
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EP0929630A1 EP0929630A1 (de) | 1999-07-21 |
EP0929630B1 true EP0929630B1 (de) | 2001-12-12 |
Family
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Application Number | Title | Priority Date | Filing Date |
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EP97944804A Expired - Lifetime EP0929630B1 (de) | 1996-09-05 | 1997-08-28 | Pastenförmiges wasch- und reinigungsmittel |
Country Status (9)
Country | Link |
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US (1) | US6248708B1 (no) |
EP (1) | EP0929630B1 (no) |
AT (1) | ATE210717T1 (no) |
CA (1) | CA2264838A1 (no) |
DE (2) | DE19636035A1 (no) |
DK (1) | DK0929630T3 (no) |
NO (1) | NO319284B1 (no) |
PL (1) | PL331858A1 (no) |
WO (1) | WO1998010049A1 (no) |
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-
1996
- 1996-09-05 DE DE19636035A patent/DE19636035A1/de not_active Withdrawn
-
1997
- 1997-08-28 CA CA002264838A patent/CA2264838A1/en not_active Abandoned
- 1997-08-28 PL PL97331858A patent/PL331858A1/xx unknown
- 1997-08-28 EP EP97944804A patent/EP0929630B1/de not_active Expired - Lifetime
- 1997-08-28 DK DK97944804T patent/DK0929630T3/da active
- 1997-08-28 WO PCT/EP1997/004690 patent/WO1998010049A1/de active IP Right Grant
- 1997-08-28 US US09/254,355 patent/US6248708B1/en not_active Expired - Lifetime
- 1997-08-28 DE DE59705800T patent/DE59705800D1/de not_active Expired - Fee Related
- 1997-08-28 AT AT97944804T patent/ATE210717T1/de not_active IP Right Cessation
-
1999
- 1999-03-04 NO NO19991069A patent/NO319284B1/no not_active IP Right Cessation
Cited By (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN103255001A (zh) * | 2013-05-10 | 2013-08-21 | 国家电网公司 | 一种防污闪涂层清洗剂 |
Also Published As
Publication number | Publication date |
---|---|
NO319284B1 (no) | 2005-07-11 |
WO1998010049A1 (de) | 1998-03-12 |
NO991069L (no) | 1999-03-04 |
CA2264838A1 (en) | 1998-03-12 |
PL331858A1 (en) | 1999-08-16 |
DE19636035A1 (de) | 1998-03-12 |
DE59705800D1 (de) | 2002-01-24 |
NO991069D0 (no) | 1999-03-04 |
DK0929630T3 (da) | 2002-04-22 |
ATE210717T1 (de) | 2001-12-15 |
US6248708B1 (en) | 2001-06-19 |
EP0929630A1 (de) | 1999-07-21 |
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