EP0395970B1 - Washing and cleaning compositions - Google Patents
Washing and cleaning compositions Download PDFInfo
- Publication number
- EP0395970B1 EP0395970B1 EP90107599A EP90107599A EP0395970B1 EP 0395970 B1 EP0395970 B1 EP 0395970B1 EP 90107599 A EP90107599 A EP 90107599A EP 90107599 A EP90107599 A EP 90107599A EP 0395970 B1 EP0395970 B1 EP 0395970B1
- Authority
- EP
- European Patent Office
- Prior art keywords
- lactobionic acid
- compositions
- washing
- builder
- cleaning
- 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
- 239000000203 mixture Substances 0.000 title claims abstract description 90
- 238000005406 washing Methods 0.000 title claims abstract description 54
- 238000004140 cleaning Methods 0.000 title claims description 24
- UOQHWNPVNXSDDO-UHFFFAOYSA-N 3-bromoimidazo[1,2-a]pyridine-6-carbonitrile Chemical compound C1=CC(C#N)=CN2C(Br)=CN=C21 UOQHWNPVNXSDDO-UHFFFAOYSA-N 0.000 claims abstract description 81
- 229940099563 lactobionic acid Drugs 0.000 claims abstract description 64
- 239000003599 detergent Substances 0.000 claims abstract description 43
- 239000007844 bleaching agent Substances 0.000 claims abstract description 24
- 239000004094 surface-active agent Substances 0.000 claims abstract description 12
- 239000000470 constituent Substances 0.000 claims abstract description 6
- 239000000126 substance Substances 0.000 claims description 47
- 239000012459 cleaning agent Substances 0.000 claims description 26
- 238000000034 method Methods 0.000 claims description 14
- ZOXJGFHDIHLPTG-UHFFFAOYSA-N Boron Chemical compound [B] ZOXJGFHDIHLPTG-UHFFFAOYSA-N 0.000 claims description 8
- 229910052796 boron Inorganic materials 0.000 claims description 8
- 239000010457 zeolite Substances 0.000 claims description 7
- 239000002253 acid Substances 0.000 claims description 2
- 150000007513 acids Chemical class 0.000 claims description 2
- 238000004061 bleaching Methods 0.000 claims description 2
- 239000001509 sodium citrate Substances 0.000 claims description 2
- NLJMYIDDQXHKNR-UHFFFAOYSA-K sodium citrate Chemical compound O.O.[Na+].[Na+].[Na+].[O-]C(=O)CC(O)(CC([O-])=O)C([O-])=O NLJMYIDDQXHKNR-UHFFFAOYSA-K 0.000 claims description 2
- 150000002927 oxygen compounds Chemical class 0.000 claims 5
- 150000001638 boron Chemical class 0.000 claims 1
- 239000003795 chemical substances by application Substances 0.000 abstract description 2
- 238000012360 testing method Methods 0.000 description 25
- 239000004744 fabric Substances 0.000 description 19
- 229910021538 borax Inorganic materials 0.000 description 16
- 150000003839 salts Chemical class 0.000 description 16
- 235000010339 sodium tetraborate Nutrition 0.000 description 16
- 239000004328 sodium tetraborate Substances 0.000 description 15
- 238000002474 experimental method Methods 0.000 description 13
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 description 12
- 235000019832 sodium triphosphate Nutrition 0.000 description 12
- 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 11
- 230000008569 process Effects 0.000 description 10
- 101710194948 Protein phosphatase PhpP Proteins 0.000 description 9
- LBZRRXXISSKCHV-UHFFFAOYSA-N [B].[O] Chemical class [B].[O] LBZRRXXISSKCHV-UHFFFAOYSA-N 0.000 description 9
- 229920000742 Cotton Polymers 0.000 description 8
- MGFYIUFZLHCRTH-UHFFFAOYSA-N nitrilotriacetic acid Chemical compound OC(=O)CN(CC(O)=O)CC(O)=O MGFYIUFZLHCRTH-UHFFFAOYSA-N 0.000 description 8
- 239000004753 textile Substances 0.000 description 8
- 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 7
- XGCTUKUCGUNZDN-UHFFFAOYSA-N [B].O=O Chemical compound [B].O=O XGCTUKUCGUNZDN-UHFFFAOYSA-N 0.000 description 7
- 238000009472 formulation Methods 0.000 description 7
- 239000000243 solution Substances 0.000 description 7
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 7
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 6
- 125000000217 alkyl group Chemical group 0.000 description 6
- 230000005540 biological transmission Effects 0.000 description 6
- 230000000694 effects Effects 0.000 description 6
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 5
- KCXVZYZYPLLWCC-UHFFFAOYSA-N EDTA Chemical compound OC(=O)CN(CC(O)=O)CCN(CC(O)=O)CC(O)=O KCXVZYZYPLLWCC-UHFFFAOYSA-N 0.000 description 5
- 230000009471 action Effects 0.000 description 5
- 239000007864 aqueous solution Substances 0.000 description 5
- 239000011575 calcium Substances 0.000 description 5
- 125000004432 carbon atom Chemical group C* 0.000 description 5
- 230000000052 comparative effect Effects 0.000 description 5
- 239000008139 complexing agent Substances 0.000 description 5
- 239000010439 graphite Substances 0.000 description 5
- 229910002804 graphite Inorganic materials 0.000 description 5
- 238000005342 ion exchange Methods 0.000 description 5
- 150000002500 ions Chemical class 0.000 description 5
- 229960001922 sodium perborate Drugs 0.000 description 5
- YKLJGMBLPUQQOI-UHFFFAOYSA-M sodium;oxidooxy(oxo)borane Chemical compound [Na+].[O-]OB=O YKLJGMBLPUQQOI-UHFFFAOYSA-M 0.000 description 5
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 description 4
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 4
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 4
- 150000001875 compounds Chemical class 0.000 description 4
- 239000002736 nonionic surfactant Substances 0.000 description 4
- 229910052760 oxygen Inorganic materials 0.000 description 4
- 239000001301 oxygen Substances 0.000 description 4
- 238000004062 sedimentation Methods 0.000 description 4
- 102000005701 Calcium-Binding Proteins Human genes 0.000 description 3
- 108010045403 Calcium-Binding Proteins Proteins 0.000 description 3
- 235000008733 Citrus aurantifolia Nutrition 0.000 description 3
- IAYPIBMASNFSPL-UHFFFAOYSA-N Ethylene oxide Chemical group C1CO1 IAYPIBMASNFSPL-UHFFFAOYSA-N 0.000 description 3
- 101100399296 Mus musculus Lime1 gene Proteins 0.000 description 3
- 235000011941 Tilia x europaea Nutrition 0.000 description 3
- 229910021536 Zeolite Inorganic materials 0.000 description 3
- 239000012190 activator Substances 0.000 description 3
- 239000003945 anionic surfactant Substances 0.000 description 3
- 229910052791 calcium Inorganic materials 0.000 description 3
- 239000003093 cationic surfactant Substances 0.000 description 3
- 150000001768 cations Chemical class 0.000 description 3
- 239000013078 crystal Substances 0.000 description 3
- 235000014113 dietary fatty acids Nutrition 0.000 description 3
- HNPSIPDUKPIQMN-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Al]O[Al]=O HNPSIPDUKPIQMN-UHFFFAOYSA-N 0.000 description 3
- 239000006185 dispersion Substances 0.000 description 3
- 239000000194 fatty acid Substances 0.000 description 3
- 229930195729 fatty acid Natural products 0.000 description 3
- 230000002349 favourable effect Effects 0.000 description 3
- 239000004571 lime Substances 0.000 description 3
- 239000000463 material Substances 0.000 description 3
- NLKNQRATVPKPDG-UHFFFAOYSA-M potassium iodide Chemical compound [K+].[I-] NLKNQRATVPKPDG-UHFFFAOYSA-M 0.000 description 3
- 239000000523 sample Substances 0.000 description 3
- 239000012418 sodium perborate tetrahydrate Substances 0.000 description 3
- IBDSNZLUHYKHQP-UHFFFAOYSA-N sodium;3-oxidodioxaborirane;tetrahydrate Chemical compound O.O.O.O.[Na+].[O-]B1OO1 IBDSNZLUHYKHQP-UHFFFAOYSA-N 0.000 description 3
- BJEPYKJPYRNKOW-REOHCLBHSA-N (S)-malic acid Chemical compound OC(=O)[C@@H](O)CC(O)=O BJEPYKJPYRNKOW-REOHCLBHSA-N 0.000 description 2
- 108090000790 Enzymes Proteins 0.000 description 2
- 102000004190 Enzymes Human genes 0.000 description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 2
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 2
- GUBGYTABKSRVRQ-QKKXKWKRSA-N Lactose Natural products OC[C@H]1O[C@@H](O[C@H]2[C@H](O)[C@@H](O)C(O)O[C@@H]2CO)[C@H](O)[C@@H](O)[C@H]1O GUBGYTABKSRVRQ-QKKXKWKRSA-N 0.000 description 2
- 229910019142 PO4 Inorganic materials 0.000 description 2
- 239000004698 Polyethylene Substances 0.000 description 2
- 239000002202 Polyethylene glycol Substances 0.000 description 2
- 239000004115 Sodium Silicate Substances 0.000 description 2
- 229910052783 alkali metal Inorganic materials 0.000 description 2
- 150000001340 alkali metals Chemical class 0.000 description 2
- -1 alkyl ether sulfates Chemical class 0.000 description 2
- BJEPYKJPYRNKOW-UHFFFAOYSA-N alpha-hydroxysuccinic acid Natural products OC(=O)C(O)CC(O)=O BJEPYKJPYRNKOW-UHFFFAOYSA-N 0.000 description 2
- 125000000129 anionic group Chemical group 0.000 description 2
- 239000002585 base Substances 0.000 description 2
- 239000012496 blank sample Substances 0.000 description 2
- 150000001642 boronic acid derivatives Chemical class 0.000 description 2
- 229910001424 calcium ion Inorganic materials 0.000 description 2
- 125000002057 carboxymethyl group Chemical group [H]OC(=O)C([H])([H])[*] 0.000 description 2
- 230000009918 complex formation Effects 0.000 description 2
- MTHSVFCYNBDYFN-UHFFFAOYSA-N diethylene glycol Chemical compound OCCOCCO MTHSVFCYNBDYFN-UHFFFAOYSA-N 0.000 description 2
- 150000002170 ethers Chemical class 0.000 description 2
- 150000004665 fatty acids Chemical class 0.000 description 2
- 150000002191 fatty alcohols Chemical class 0.000 description 2
- 125000000524 functional group Chemical group 0.000 description 2
- 125000002768 hydroxyalkyl group Chemical group 0.000 description 2
- 239000004615 ingredient Substances 0.000 description 2
- RBTARNINKXHZNM-UHFFFAOYSA-K iron trichloride Chemical compound Cl[Fe](Cl)Cl RBTARNINKXHZNM-UHFFFAOYSA-K 0.000 description 2
- JVTAAEKCZFNVCJ-UHFFFAOYSA-N lactic acid Chemical compound CC(O)C(O)=O JVTAAEKCZFNVCJ-UHFFFAOYSA-N 0.000 description 2
- 239000008101 lactose Substances 0.000 description 2
- 239000007788 liquid Substances 0.000 description 2
- 239000001630 malic acid Substances 0.000 description 2
- 235000011090 malic acid Nutrition 0.000 description 2
- 229910052751 metal Inorganic materials 0.000 description 2
- 239000002184 metal Substances 0.000 description 2
- 230000003287 optical effect Effects 0.000 description 2
- 230000003647 oxidation Effects 0.000 description 2
- 238000007254 oxidation reaction Methods 0.000 description 2
- 235000021317 phosphate Nutrition 0.000 description 2
- 150000003013 phosphoric acid derivatives Chemical class 0.000 description 2
- 229920000728 polyester Polymers 0.000 description 2
- 229920001223 polyethylene glycol Polymers 0.000 description 2
- 229920000151 polyglycol Polymers 0.000 description 2
- 239000010695 polyglycol Substances 0.000 description 2
- 239000000843 powder Substances 0.000 description 2
- 239000002244 precipitate Substances 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- 239000000344 soap Substances 0.000 description 2
- 239000011734 sodium Substances 0.000 description 2
- 229910052708 sodium Inorganic materials 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
- 238000003860 storage Methods 0.000 description 2
- 238000004383 yellowing Methods 0.000 description 2
- XSVSPKKXQGNHMD-UHFFFAOYSA-N 5-bromo-3-methyl-1,2-thiazole Chemical compound CC=1C=C(Br)SN=1 XSVSPKKXQGNHMD-UHFFFAOYSA-N 0.000 description 1
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 description 1
- NLZUEZXRPGMBCV-UHFFFAOYSA-N Butylhydroxytoluene Chemical compound CC1=CC(C(C)(C)C)=C(O)C(C(C)(C)C)=C1 NLZUEZXRPGMBCV-UHFFFAOYSA-N 0.000 description 1
- 229910021532 Calcite Inorganic materials 0.000 description 1
- BHPQYMZQTOCNFJ-UHFFFAOYSA-N Calcium cation Chemical compound [Ca+2] BHPQYMZQTOCNFJ-UHFFFAOYSA-N 0.000 description 1
- UXVMQQNJUSDDNG-UHFFFAOYSA-L Calcium chloride Chemical compound [Cl-].[Cl-].[Ca+2] UXVMQQNJUSDDNG-UHFFFAOYSA-L 0.000 description 1
- 206010006956 Calcium deficiency Diseases 0.000 description 1
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 1
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical group OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 1
- 229910021578 Iron(III) chloride Inorganic materials 0.000 description 1
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 description 1
- JLVVSXFLKOJNIY-UHFFFAOYSA-N Magnesium ion Chemical compound [Mg+2] JLVVSXFLKOJNIY-UHFFFAOYSA-N 0.000 description 1
- 229910000503 Na-aluminosilicate Inorganic materials 0.000 description 1
- 239000004435 Oxo alcohol Substances 0.000 description 1
- GOOHAUXETOMSMM-UHFFFAOYSA-N Propylene oxide Chemical compound CC1CO1 GOOHAUXETOMSMM-UHFFFAOYSA-N 0.000 description 1
- PMZURENOXWZQFD-UHFFFAOYSA-L Sodium Sulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=O PMZURENOXWZQFD-UHFFFAOYSA-L 0.000 description 1
- 229920002472 Starch Polymers 0.000 description 1
- 239000004480 active ingredient Substances 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 230000002411 adverse Effects 0.000 description 1
- 150000007824 aliphatic compounds Chemical class 0.000 description 1
- 125000001931 aliphatic group Chemical group 0.000 description 1
- 150000001412 amines Chemical class 0.000 description 1
- 125000003277 amino group Chemical group 0.000 description 1
- 230000000844 anti-bacterial effect Effects 0.000 description 1
- 239000002216 antistatic agent Substances 0.000 description 1
- 238000010420 art technique Methods 0.000 description 1
- 125000003118 aryl group Chemical group 0.000 description 1
- 239000003899 bactericide agent Substances 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 159000000007 calcium salts Chemical class 0.000 description 1
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 1
- 150000001732 carboxylic acid derivatives Chemical class 0.000 description 1
- 239000000969 carrier Substances 0.000 description 1
- 125000002091 cationic group Chemical group 0.000 description 1
- 239000002738 chelating agent Substances 0.000 description 1
- 239000000460 chlorine Substances 0.000 description 1
- 229910052801 chlorine Inorganic materials 0.000 description 1
- 230000000536 complexating effect Effects 0.000 description 1
- 238000009833 condensation Methods 0.000 description 1
- 230000005494 condensation Effects 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- REZZEXDLIUJMMS-UHFFFAOYSA-M dimethyldioctadecylammonium chloride Chemical compound [Cl-].CCCCCCCCCCCCCCCCCC[N+](C)(C)CCCCCCCCCCCCCCCCCC REZZEXDLIUJMMS-UHFFFAOYSA-M 0.000 description 1
- 229940042400 direct acting antivirals phosphonic acid derivative Drugs 0.000 description 1
- 238000004851 dishwashing Methods 0.000 description 1
- 239000004664 distearyldimethylammonium chloride (DHTDMAC) Substances 0.000 description 1
- YRIUSKIDOIARQF-UHFFFAOYSA-N dodecyl benzenesulfonate Chemical compound CCCCCCCCCCCCOS(=O)(=O)C1=CC=CC=C1 YRIUSKIDOIARQF-UHFFFAOYSA-N 0.000 description 1
- 229940071161 dodecylbenzenesulfonate Drugs 0.000 description 1
- 239000000975 dye Substances 0.000 description 1
- 238000004453 electron probe microanalysis Methods 0.000 description 1
- 230000008030 elimination Effects 0.000 description 1
- 238000003379 elimination reaction Methods 0.000 description 1
- 239000003623 enhancer Substances 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- UFZOPKFMKMAWLU-UHFFFAOYSA-N ethoxy(methyl)phosphinic acid Chemical compound CCOP(C)(O)=O UFZOPKFMKMAWLU-UHFFFAOYSA-N 0.000 description 1
- 238000012851 eutrophication Methods 0.000 description 1
- 239000003925 fat Substances 0.000 description 1
- 239000000835 fiber Substances 0.000 description 1
- 239000006260 foam Substances 0.000 description 1
- 238000005187 foaming Methods 0.000 description 1
- 239000008187 granular material Substances 0.000 description 1
- 239000003676 hair preparation Substances 0.000 description 1
- 229910001385 heavy metal Inorganic materials 0.000 description 1
- 229930195733 hydrocarbon Natural products 0.000 description 1
- 150000002430 hydrocarbons Chemical class 0.000 description 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- MTNDZQHUAFNZQY-UHFFFAOYSA-N imidazoline Chemical class C1CN=CN1 MTNDZQHUAFNZQY-UHFFFAOYSA-N 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 238000009776 industrial production Methods 0.000 description 1
- 239000003112 inhibitor Substances 0.000 description 1
- 238000011835 investigation Methods 0.000 description 1
- 239000002563 ionic surfactant Substances 0.000 description 1
- 238000009533 lab test Methods 0.000 description 1
- 239000004310 lactic acid Substances 0.000 description 1
- 235000014655 lactic acid Nutrition 0.000 description 1
- JYTUSYBCFIZPBE-AMTLMPIISA-N lactobionic acid Chemical compound OC(=O)[C@H](O)[C@@H](O)[C@@H]([C@H](O)CO)O[C@@H]1O[C@H](CO)[C@H](O)[C@H](O)[C@H]1O JYTUSYBCFIZPBE-AMTLMPIISA-N 0.000 description 1
- 239000011777 magnesium Substances 0.000 description 1
- 229910052749 magnesium Inorganic materials 0.000 description 1
- 229910001425 magnesium ion Inorganic materials 0.000 description 1
- 159000000003 magnesium salts Chemical class 0.000 description 1
- YLGXILFCIXHCMC-JHGZEJCSSA-N methyl cellulose Chemical compound COC1C(OC)C(OC)C(COC)O[C@H]1O[C@H]1C(OC)C(OC)C(OC)OC1COC YLGXILFCIXHCMC-JHGZEJCSSA-N 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 150000004712 monophosphates Chemical class 0.000 description 1
- 150000002894 organic compounds Chemical class 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 150000004965 peroxy acids Chemical class 0.000 description 1
- 125000000864 peroxy group Chemical group O(O*)* 0.000 description 1
- JRKICGRDRMAZLK-UHFFFAOYSA-L peroxydisulfate Chemical compound [O-]S(=O)(=O)OOS([O-])(=O)=O JRKICGRDRMAZLK-UHFFFAOYSA-L 0.000 description 1
- 150000003007 phosphonic acid derivatives Chemical class 0.000 description 1
- XYFCBTPGUUZFHI-UHFFFAOYSA-O phosphonium Chemical compound [PH4+] XYFCBTPGUUZFHI-UHFFFAOYSA-O 0.000 description 1
- 239000000049 pigment Substances 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- BIRNWOIQDVFTSP-WWNCWODVSA-M potassium (2R,3R,4R,5R)-2,3,5,6-tetrahydroxy-4-[(2S,3R,4S,5R,6R)-3,4,5-trihydroxy-6-(hydroxymethyl)oxan-2-yl]oxyhexanoate Chemical compound [K+].OC[C@@H](O)[C@@H](O[C@@H]1O[C@H](CO)[C@H](O)[C@H](O)[C@H]1O)[C@H](O)[C@@H](O)C([O-])=O BIRNWOIQDVFTSP-WWNCWODVSA-M 0.000 description 1
- XAEFZNCEHLXOMS-UHFFFAOYSA-M potassium benzoate Chemical compound [K+].[O-]C(=O)C1=CC=CC=C1 XAEFZNCEHLXOMS-UHFFFAOYSA-M 0.000 description 1
- 238000001556 precipitation Methods 0.000 description 1
- 239000002243 precursor Substances 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 230000002265 prevention Effects 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 210000002374 sebum Anatomy 0.000 description 1
- 238000002791 soaking Methods 0.000 description 1
- 235000012217 sodium aluminium silicate Nutrition 0.000 description 1
- 229910000029 sodium carbonate Inorganic materials 0.000 description 1
- FQENQNTWSFEDLI-UHFFFAOYSA-J sodium diphosphate Chemical compound [Na+].[Na+].[Na+].[Na+].[O-]P([O-])(=O)OP([O-])([O-])=O FQENQNTWSFEDLI-UHFFFAOYSA-J 0.000 description 1
- NVIFVTYDZMXWGX-UHFFFAOYSA-N sodium metaborate Chemical compound [Na+].[O-]B=O NVIFVTYDZMXWGX-UHFFFAOYSA-N 0.000 description 1
- 159000000000 sodium salts Chemical class 0.000 description 1
- 229910052938 sodium sulfate Inorganic materials 0.000 description 1
- 235000011152 sodium sulphate Nutrition 0.000 description 1
- AKHNMLFCWUSKQB-UHFFFAOYSA-L sodium thiosulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=S AKHNMLFCWUSKQB-UHFFFAOYSA-L 0.000 description 1
- 235000019345 sodium thiosulphate Nutrition 0.000 description 1
- MWNQXXOSWHCCOZ-UHFFFAOYSA-L sodium;oxido carbonate Chemical compound [Na+].[O-]OC([O-])=O MWNQXXOSWHCCOZ-UHFFFAOYSA-L 0.000 description 1
- 239000003381 stabilizer Substances 0.000 description 1
- 239000008107 starch Substances 0.000 description 1
- 235000019698 starch Nutrition 0.000 description 1
- 125000001424 substituent group Chemical group 0.000 description 1
- 150000003871 sulfonates Chemical class 0.000 description 1
- RWSOTUBLDIXVET-UHFFFAOYSA-O sulfonium group Chemical group [SH3+] RWSOTUBLDIXVET-UHFFFAOYSA-O 0.000 description 1
- 239000003760 tallow Substances 0.000 description 1
- 239000012085 test solution Substances 0.000 description 1
- 150000004685 tetrahydrates Chemical class 0.000 description 1
- 238000002560 therapeutic procedure Methods 0.000 description 1
- 238000004448 titration Methods 0.000 description 1
- 231100000027 toxicology Toxicity 0.000 description 1
- JSPLKZUTYZBBKA-UHFFFAOYSA-N trioxidane Chemical compound OOO JSPLKZUTYZBBKA-UHFFFAOYSA-N 0.000 description 1
- BSVBQGMMJUBVOD-UHFFFAOYSA-N trisodium borate Chemical compound [Na+].[Na+].[Na+].[O-]B([O-])[O-] BSVBQGMMJUBVOD-UHFFFAOYSA-N 0.000 description 1
- RYFMWSXOAZQYPI-UHFFFAOYSA-K trisodium phosphate Chemical compound [Na+].[Na+].[Na+].[O-]P([O-])([O-])=O RYFMWSXOAZQYPI-UHFFFAOYSA-K 0.000 description 1
- 239000003643 water by type Substances 0.000 description 1
- 238000005303 weighing Methods 0.000 description 1
- 239000004711 α-olefin 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
- C11D3/046—Salts
-
- C—CHEMISTRY; METALLURGY
- C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
- C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
- C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
- C11D3/16—Organic compounds
- C11D3/20—Organic compounds containing oxygen
- C11D3/22—Carbohydrates or derivatives thereof
- C11D3/221—Mono, di- or trisaccharides or derivatives thereof
-
- C—CHEMISTRY; METALLURGY
- C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
- C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
- C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
- C11D3/39—Organic or inorganic per-compounds
- C11D3/3942—Inorganic per-compounds
Definitions
- the invention relates to compositions for washing and cleaning applications which contain biodegradable and ecologically compatible builder substances, to the use of these builder substances and to a method for washing and / or cleaning.
- Builders are of central importance for the course of the washing and cleaning process.
- the function of the builders is mainly that they are partly from water, partly from dirt or e.g. Eliminate textiles from calcium and magnesium ions by complex formation or ion exchange from the washing or cleaning process and to support the surfactant effect.
- Modern builders therefore have to meet a number of eligibility criteria.
- builders should have a certain primary washing or cleaning action. This means, for example, a good specific washing and cleaning action against pigments and fats or, for example, a good washing action against certain textile fibers, the improvement of the surfactant properties and a favorable influence on the foaming behavior.
- they should make a major contribution to dispersing dirt in washing and cleaning liquors. In this way, for example, graying and yellowing of the textiles to be washed pushed back, which is very important for good washing results.
- builders should have good dirt-bearing capacity and e.g. prevent incrustation on textiles. In addition, they should also prevent corresponding deposits in washing machines and cheap, i.e. show no correspondence behavior.
- the builder substances should continue to be chemically stable, technically easy to process, non-hygroscopic, stable in storage and compatible with the other detergents and cleaning agents. They should also have perfect color and smell qualities and be based on a secure raw material base.
- the builder substances should also be harmless to the environment, be biodegradable and, last but not least, also meet economic requirements.
- Builder substances known in the prior art are e.g. certain washing alkalis (such as soda, sodium silicate or sodium monophosphate), complexing agents (such as e.g. sodium diphosphate, sodium triphosphate, phosphonic acid derivatives, nitrilotriacetic acid (NTA), ethylenediaminetetraacetic acid (EDTA), citric acid, O- (carboxymethyl) malic acid) or ionol exchanger (e.g. zeolite exchanger).
- washing alkalis such as soda, sodium silicate or sodium monophosphate
- complexing agents such as e.g. sodium diphosphate, sodium triphosphate, phosphonic acid derivatives, nitrilotriacetic acid (NTA), ethylenediaminetetraacetic acid (EDTA), citric acid, O- (carboxymethyl) malic acid
- ionol exchanger e.g. zeolite exchanger
- Alkaline detergents such as soda or monophosphate are now considered technically obsolete, since they form precipitates with the calcium and magnesium salts (so-called hardness formers) of service water, which deposit on laundry and appliances as undesirable and annoying deposits.
- the builder substances currently used no longer precipitate the hardness formers of the water, but instead eliminate them through complex formation or ion exchange.
- the phosphates used as complexing agents contribute Eutrophication of standing or slowly flowing waters. The ecological side effect of the phosphates is undesirable and has led to an intensive search worldwide for suitable substitutes.
- EP-AO 107 159 discloses hair treatment compositions which contain lactic acid as active ingredients in hair cosmetics.
- the object was therefore to provide washing and cleaning agent compositions which avoid or at least reduce the disadvantages of the prior art with regard to the builder substances contained in the compositions.
- a further task was to specify builders which can be used in compositions for washing and cleaning purposes or in washing and cleaning processes and which, in addition to having sufficient calcium binding capacity, ecological compatibility and biodegradability, are characterized above all by very good dispersing behavior, which is necessary to achieve a good washing and cleaning effect is required.
- the invention proposes detergent and cleaning agent compositions which contain surfactants and, if appropriate, further constituents customary in detergents and cleaning agents, and lactobionic acid and / or lactobionic acid salts in the presence of a boron oxygen compound as builder substances.
- Lactobionic acid (4- (beta-D-galactosido) -D-gluconic acid) is already known as such and can be obtained, for example, by oxidation of lactose. So far, the lactobionic acid in the form of the calcium salt has been used pharmaceutically in the so-called calcium preparations for the prevention and therapy of calcium deficiency states. The use as a builder in washing and cleaning agents, however, has not been described so far.
- both the free lactobionic acid itself and its salts with environmentally compatible, non-hardness-forming metal cations or mixtures of these substances can be used as builder substance in the compositions according to the invention.
- Alkali metal lactobionates, in particular sodium and potassium lactobionate, are preferably used here.
- lactobionic acid and / or lactobionic acid salts can be present in the compositions according to the invention in amounts which are conventional per se for builder substances.
- the lactobionic acid and its salts can then be present in the detergent and cleaning agent compositions in an amount based on the total composition of up to 40% by weight.
- the amount of builder substances contained in the compositions according to the invention is preferably up to 35% by weight.
- these compositions contain a further component which consists of one or more boron oxygen compounds consists.
- the builder action of lactobionic acid or its salts is increased in an unexpected and surprising manner by the presence of the boron oxygen compound.
- the boron oxygen compounds are generally present in the compositions in an amount such that at least 1 mol of boron is contained for 1 mol of lactobionic acid and / or lactobionic acid salt.
- boron oxygen compounds are suitable for this purpose, for example conventional borates known in the prior art, such as sodium borate, sodium metaborate, borax, pentaborate, etc., or mixtures thereof. Boron oxygen compounds of the aforementioned type are contained in particular in those compositions which contain no bleaching agent or no perborate bleaching agent.
- Peroxy group-containing boron oxygen compounds i.e. boron-containing peroxygen bleach
- boron oxygen compounds can also be used as boron oxygen compounds, e.g. those perborates known per se in the prior art, which are usually contained as bleaching agents in detergent and cleaning agent compositions.
- the perborates are used in the washing and cleaning compositions in amounts customary for bleaching agents and, in this case, no further addition of boron oxygen compounds of the type described above (i.e. borates etc.) is therefore required.
- lactobionic acid and its salts per se can be used as builders for any detergent and cleaning agent compositions, for example also in liquid detergents and cleaning agents (for example liquid detergents), but the advantages which can be achieved with these builder substances are particularly evident in powdered detergents. and detergent compositions, for example in so-called powdered universal detergents, or in hand and machine dishwashing detergents.
- lactobionic acid and / or their salts as cobuilders in combination with further organic and / or inorganic builders which have been customary in the prior art in the detergent and cleaning agent compositions.
- Typical examples of customary builders known in the prior art which may be present in the compositions as builders with the builders used according to the invention are sodium aluminosilicates (e.g. zeolites), sodium citrate or salts of aminopolycarboxylic acids such as nitrilotriacetic acid and ethylenediaminetetraacetic acid.
- lactobionic acid and / or its salts can also be present in combination with lactobionic acid and / or its salts in detergent and cleaning agent compositions.
- lactobionic acid and / or its salts are present as cobuilders in amounts of up to 25% by weight, based on the total composition.
- compositions of the invention can contain any bleaching agent or bleaching agent mixture customary in the art, for example chlorine bleaching agent or peroxygen bleaching agent.
- the bleaching agent is a peroxygen bleaching agent, such as persulfate, percarbonate or perborates.
- perborates such as sodium perborate tetrahydrate or sodium perborate monohydrate are particularly preferred.
- compositions according to the invention can be formulated in a manner known per se.
- all the usual materials that are usually used for the formulation of detergent and detergent compositions per se can be used in the compositions according to the invention usual amounts are used.
- the compositions according to the invention contain surfactants as an essential constituent, and, if appropriate, other customary auxiliaries.
- compositions according to the invention can contain any surface-active organic compounds, such as anionic, cationic, ampholytic or non-ionic surfactants or mixtures thereof, as surfactants.
- Anionic surfactants are e.g. synthetic surface-active compounds with one or more functional groups that ionize in aqueous solution to form negatively charged ions.
- Suitable anionic surfactants are, for example, alkali metal, ammonium or alkanolamine salts of alkylbenzenesulfonates having 10 to 18 carbon atoms in the alkyl group; Alkyl and alkyl ether sulfates with 10 to 24 carbon atoms in the alkyl group and with 1 to 5 ethylene oxide groups; C10- to C12- ⁇ -olefin sulfonates, ⁇ -sulfo fatty acid esters.
- Cationic surfactants are surfactants with one or more functional groups that ionize in aqueous solution to form positively charged organic ions.
- cationic surfactants are aliphatic or aromatic higher-alkyl-di-lower-alkyl-ammonium halides, for example dialkyl-dimethylammonium chlorides such as distearyl-dimethylammonium chloride; Alkyl dimethyl benzyl ammonium chloride; Imidazolinium salts.
- ampholytic (zwitterionic) surfactants include derivatives of straight-chain or branched aliphatic compounds with usually 8 to 24 carbon atoms, which contain aliphatic quaternary ammonium, phosphonium or sulfonium groups and at least one anionic water-soluble group and optionally also other substituents.
- Examples are C12- to C18-alkyl betaines of the formula R-N+ (CH3) 2CH2-COO ⁇ and C12- to C18-alkyl sulfobetaines of the formula R-N+ (CH3) 2-SO3 ⁇ .
- Non-ionic surfactants are usually cocondensates of ethylene oxide or propylene oxide with hydrocarbons which carry reactive groups such as hydroxyl, carboxyl or amino groups.
- Examples are alkylphenol polyglycol ethers with C8-C12 alkyl radicals and 5 to 10 ethylene glycol units; Alkyl polyglycol ethers such as fatty alcohol polyethylene glycol ether and oxo alcohol polyethylene glycol ether; Fatty acid alkanolamides, e.g. of the fatty acid ethanolamide type.
- non-ionic surfactants are the semi-polar non-ionic surfactants, e.g. water-soluble amine oxides with alkyl or hydroxyalkyl units with 8 to 28 C atoms, it being possible for two of these alkyl or hydroxyalkyl units to be linked to form a ring structure with 1 to 3 C atoms.
- the detergent and cleaning agent compositions of the present invention can contain further customary auxiliaries for the formulation of detergents and cleaning agents.
- auxiliaries include enhancers, detergent enzymes, enzyme stabilizers, dirt carriers and / or compatibilizers, complexing agents and chelating agents, soap foam regulators and additives such as optical brighteners, opacifying agents, corrosion inhibitors, Antistatic agents, dyes, bactericides, bleach activators, peracid bleach precursors.
- the invention also relates to compositions for washing and cleaning purposes or for bleaching purposes in washing and cleaning processes which contain lactobionic acid and / or lactobionic acid salts as builder substances in the presence of a boron oxygen compound, but in themselves are not yet complete washing and cleaning agent compositions in the above described senses, since they contain only a part of the ingredients usually contained in a complete detergent composition suitable for use.
- Such partial compositions according to the invention can serve on the one hand for the industrial production of complete detergent and cleaning agent compositions.
- the partial compositions are well suited as components for so-called modular detergent and cleaning agent systems.
- the constituents are not already mixed with one another as in conventional (complete) detergent and cleaning agent compositions, but instead lie as separate system components, for example as surfactant, bleach and builder components. in front.
- the individual components are only coordinated by the user depending on the individual requirements (such as the type of material to be washed or cleaned; type of washing or cleaning process, e.g. hot or delicate laundry, etc .; water hardness etc.).
- the components can either be mixed with one another before use or metered separately into the wash water.
- the boron oxygen compound contained therein can be a peroxygen bleaching agent, in analogy to that described above in connection with the washing and cleaning compositions.
- Preferred peroxygen bleaches are perborates.
- Such partial compositions for example in the form of powders or granules, which contain lactobionic acid and / or lactobionic acid salts in the presence of perborate, are suitable, for example, for use as so-called dry bleach in washing and cleaning processes.
- the invention further relates to the use of lactobionic acid and / or lactobionic acid salts as builder substances in compositions for washing and cleaning purposes.
- lactobionic acid and / or lactobionic acid salts as builder substances in compositions for washing and cleaning purposes.
- Both the free lactobionic acid itself and its salts with environmentally compatible, non-hardness-forming metal cations or mixtures of these substances can be used as builder substances in the manner described above for compositions according to the invention.
- preference is given in particular to using the sodium or potassium salt of lactobionic acid.
- the invention further relates to a method for washing and cleaning, which is characterized in that lactobionic acid and / or lactobionic acid salts are used as builder substances in the presence of boron oxygen compounds.
- compositions according to the invention, the use according to the invention and the method according to the invention offer a surprising and problem-free solution to the widespread desire for suitable environmentally compatible and biodegradable builder substances which, in addition to good calcium binding capacity, in particular show very good dispersing behavior.
- the very good dispersibility of lactobionic acid and its salts results in the presence a boron oxygen compound to suppress graying and yellowing. This property is of paramount importance for washing and cleaning processes and is excellently fulfilled by lactobionic acid and its salts.
- incrustations for example on textiles or in washing machines, are prevented to an unexpectedly favorable extent.
- Lactobionic acid and its salts also show the so-called threshold effect, i.e. they are able to delay, reduce, or at least cause the precipitation of insoluble salts even when using substoichiometric amounts of builders, or at least to cause the insoluble salts to occur predominantly in amorphous form and that Formation of sharp-edged, fiber-damaging crystals (eg calcite crystals) is largely suppressed.
- the compounds are chemically stable, not hygroscopic, stable in storage and easy to process technically. Furthermore, they are well compatible with common detergent and cleaning agent ingredients.
- the compounds can be easily obtained from lactose by oxidation on the basis of a secure raw material base and are also economically advantageous.
- the biological origin and complete biodegradability of the substances guarantee harmlessness to humans and favorable environmental behavior.
- the lime binding capacity of lactobionic acid in the presence of boron oxygen compounds (2.13 g borax and / or 2 g sodium perborate in 100 ml solution) was determined at pH 10 by mixing 100 ml of an aqueous solution of 1% by weight lactobionic acid, 0.4% by weight % Sodium carbonate and optionally 0.1% by weight TAED as bleach activator with an aqueous 0.1 N calcium chloride solution until occurrence a permanent cloudiness titrated. Under these test conditions, lactobionic acid is present as the sodium salt in the test solution.
- the measured number for the lime binding capacity is the gram number of calcium ions which can be kept in solution per 100 g of lactobionic acid as builder substance under the aforementioned conditions.
- aqueous dispersions were prepared from 0.1% by weight of the builder substance to be tested and 4% by weight powder graphite as dispersa by weighing the substances into a 100 ml shaking measuring cylinder, making up to 100 ml with water and shook vigorously for a minute.
- the sedimentation volume of the graphite particles was determined as a measure of the dispersing capacity and, for additional tests, a sample was additionally taken from the dispersion at the level of the 70 ml measuring mark of the shaking measuring cylinder and sent to a photometric test.
- the transmission of the samples was measured here in comparison to corresponding blank samples without graphite (transmission 100%), with smaller transmission values indicating better dispersibility.
- the washing performance was determined by washing tests on test fabrics in two standard washing machines (type: Miele W 180). For this purpose, 2 kg of test fabric was washed with 155 g of detergent in the short program (washing time 1 h). A standardized heavy-duty detergent formulation was used as the detergent, which contained 30% by weight of the builder system to be tested.
- composition of the standardized heavy-duty detergent formulation 30.0% by weight builder system (see table) 11.9% by weight of dodecylbenzenesulfonate 4.0% by weight of tallow fatty alcohol ethoxylate with 11 moles of ethylene oxide 4.0% by weight of sebum soap 4.0% by weight sodium silicate 32.9% by weight sodium perborate tetrahydrate 11.9% by weight sodium sulfate 1.3 wt% tylose.
- the experiments were carried out at pH 10 and 18 ° dH at 30 and 60 ° C. The fleet ratio was 1:12.
- the washing performance was determined by measuring the lightening of soiled test fabrics (cotton fabric and cotton blended fabrics) as the reflectance difference (reflectance of the dry test fabric after the wash test minus the reflectance test fabric before the wash test) at 530 nm. The larger remission difference indicates the better washing performance. Lactobionic acid alone, lactobionic acid with zeolite (in a 1: 1 ratio) and STPP as a comparison were used as builder systems in the heavy-duty detergent formulations. The experiments according to the invention of this example (No.
- lactobionic acid as builder substance prevents the graying of textiles
- washing tests were carried out on bleached test fabrics without artificial soiling and without optical brighteners.
- the test fabrics were allowed to run through a total of 25 washing cycles analogous to the washing conditions specified in Example 4 at 60 ° C. in the normal program (soaking process, 2 h).
- the graying of the test fabrics was then determined by measuring the reflectance at 530 nm.
- Lactobionic acid was used as the builder in the standardized heavy-duty detergent formulation (see Example 4) and STPP as a comparison.
- the remission is indirectly proportional to the graying.
- the experiments according to the invention of this example show that when lactobionic acid is used as builder in detergent and cleaning agent compositions, the graying of textiles is also prevented in an excellent manner by the known builders of the prior art (comparative experiments Nos. 37 and 39 ).
- test fabrics were run through a total of 25 washing cycles analogous to the washing conditions given in Example 4. After completion of the washing cycles, the test fabrics were incinerated according to standard conditions known per se and the remaining ash content in% by weight (based on the test fabric used) was determined as a measure of the inorganic incrustation. Lactobionic acid was used as the builder in the standardized heavy-duty detergent formulation (see Example 4) and STPP as a comparison. The smaller the remaining ash content, the lower the incrustation.
- the experiments according to the invention of this example Nos.
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Abstract
Description
Die Erfindung bezieht sich auf Zusammensetzungen für Wasch- und Reinigungsanwendungen, die biologisch abbaubare und ökologisch verträgliche Buildersubstanzen enthalten, auf die Verwendung dieser Buildersubstanzen sowie auf ein Verfahren zum Waschen und/oder Reinigen.The invention relates to compositions for washing and cleaning applications which contain biodegradable and ecologically compatible builder substances, to the use of these builder substances and to a method for washing and / or cleaning.
Builder (Gerüststoffe, sogenannte Waschmittelverstärker) besitzen für den Ablauf des Wasch- und Reinigungsvorganges eine zentrale Bedeutung. Die Funktion der Builder besteht vorwiegend darin, die teils aus dem Wasser, teils aus Schmutz oder z.B. Textilien stammenden Calcium- und Magnesiumionen durch Komplexbildung oder Ionenaustausch aus dem Wasch- bzw. Reinigungsvorgang zu eliminieren und die Tensidwirkung zu unterstützen. Moderne Builder müssen daher eine Reihe von Eignungskriterien erfüllen.Builders (builders, so-called detergent boosters) are of central importance for the course of the washing and cleaning process. The function of the builders is mainly that they are partly from water, partly from dirt or e.g. Eliminate textiles from calcium and magnesium ions by complex formation or ion exchange from the washing or cleaning process and to support the surfactant effect. Modern builders therefore have to meet a number of eligibility criteria.
Außer der schon erwähnten Komplexierungs- oder Ionenaustauschfunktion für Erdalkaliionen sollten Builder eine gewisse Primärwasch- bzw. Reinigungswirkung aufweisen. Hierunter versteht man z.B. eine gute spezifische Wasch- und Reinigungswirkung gegenüber Pigmenten und Fetten oder z.B. eine gute Waschwirkung gegenüber bestimmten Textilfasern, die Verbesserung der Tensideigenschaften und eine günstige Beeinflussung des Schaumverhaltens. Insbesondere sollten sie zusätzlich zu den genannten Funktionen in hohem Maße zu Dispergierung von Schmutz in Wasch- und Reinigungsflotten beitragen. Hierdurch werden z.B. Vergrauungen und Vergilbungen der zu waschenden Textilien zurückgedrängt, was für einen guten Wascherfolg sehr wichtig ist.In addition to the complexing or ion exchange function for alkaline earth ions already mentioned, builders should have a certain primary washing or cleaning action. This means, for example, a good specific washing and cleaning action against pigments and fats or, for example, a good washing action against certain textile fibers, the improvement of the surfactant properties and a favorable influence on the foaming behavior. In particular, in addition to the functions mentioned, they should make a major contribution to dispersing dirt in washing and cleaning liquors. In this way, for example, graying and yellowing of the textiles to be washed pushed back, which is very important for good washing results.
Als Sekundäreigenschaften sollten Builder ein gutes Schmutztragevermögen zeigen und z.B. die Inkrustation auf Textilien verhindern. Darüber hinaus sollten sie auch entsprechende Ablagerungen in Waschmaschinen unterbinden und günstiges, d.h. kein Korrisonsverhalten zeigen.As secondary properties, builders should have good dirt-bearing capacity and e.g. prevent incrustation on textiles. In addition, they should also prevent corresponding deposits in washing machines and cheap, i.e. show no correspondence behavior.
Die Buildersubstanzen sollten weiterhin chemisch beständig, technisch gut zu verarbeiten, nicht hygroskopisch, lagerstabil und mit den anderen Wasch- und Reinigungsmittelinhaltsstoffen verträglich sein. Auch sollten sie einwandfreie Farb- und Geruchsqualitäten aufweisen und auf einer gesicherten Rohstoffbasis beruhen.The builder substances should continue to be chemically stable, technically easy to process, non-hygroscopic, stable in storage and compatible with the other detergents and cleaning agents. They should also have perfect color and smell qualities and be based on a secure raw material base.
Neben humantoxikologischer Unbedenklichkeit sollten sich die Buildersubstanzen ferner gegenüber der Umwelt unschädlich verhalten, biologisch abbaubar sein und nicht zuletzt auch wirtschaftliche Anforderungen erfüllen.In addition to being harmless to human toxicology, the builder substances should also be harmless to the environment, be biodegradable and, last but not least, also meet economic requirements.
Im Stand der Technik bekannte Buildersubstanzen sind z.B. bestimmte Waschalkalien (wie Soda, Natriumsilikat oder Natriummonophosphat), Komplexbildner (wie z.B. Natriumdiphosphat, Natriumtriphosphat, Phosphonsäurederivate, Nitrilotriessigsäure (NTA), Ethylendiamintetraessigsäure (EDTA), Citronensäure, O-(Carboxymethyl)-äpfelsäure) oder Ionenaustauscher (z.B. Zeolithe).Builder substances known in the prior art are e.g. certain washing alkalis (such as soda, sodium silicate or sodium monophosphate), complexing agents (such as e.g. sodium diphosphate, sodium triphosphate, phosphonic acid derivatives, nitrilotriacetic acid (NTA), ethylenediaminetetraacetic acid (EDTA), citric acid, O- (carboxymethyl) malic acid) or ionol exchanger (e.g. zeolite exchanger).
Waschalkalien wie Soda oder Monophosphat gelten heute als technisch überholt, da sie mit den Calcium- und Magnesiumsalzen (sogenannte Härtebildner) von Gebrauchswasser Fällungen ergeben, die sich auf Wäsche und Geräten als unerwünschte und störende Ablagerungen festsetzen. Die zur Zeit verwendeten Buildersubstanzen fällen demgegenüber die Härtebildner des Wassers nicht mehr aus, sondern eliminieren sie durch Komplexbildung oder Ionenaustausch. Die als Komplexbildner verwendeten Phosphate tragen jedoch zur Eutrophierung stehender oder langsam fließender Gewässer bei. Die ökologische Begleiterscheinung der Phosphate ist unerwünscht und führte weltweit zu einer intensiven Suche nach geeigneten Ersatzstoffen. Aber auch bekannte Ersatzstoffe weisen noch eine Reihe von Nachteilen auf, da sie einerseits wie NTA oder EDTA z.B. schlecht biologisch abbaubar sind oder andererseits wie Citronensäure oder O-(Carboxymethyl)-äpfelsäure vergleichsweise geringes Dispergiervermögen und nur mäßiges Primärwaschvermögen aufweisen. Ionenaustauscher wie Zeolithe wiederum zeigen sehr ausgeprägtes Ionenaustauschvermögen, welches im Hinblick auf Schwermetallionen jedoch unter ökologischen Gesichtspunkten bedenklich sein kann. Darüber hinaus ist es zur Unterstützung des in heterogener Phase stattfindenden Ionenaustausches nötig, die Zeolithe in Kombination mit wasserlöslichen Komplexbildnern (z.B. den oben angegebenen, aber bedenklichen Komplexbildnern wie NTA oder EDTA) oder Carboxylsäurepolymeren zu verwenden (Ausnutzung des sogenannten Carrier-Effektes). Nachteilig ist auch, daß Zeolithkristalle als Kondensationsboden für schwerlösliche Verbindungen in der Wasch- bzw. Reinigungsflotte wirken können und daß sie kaum Dispergierverhalten zeigen.Alkaline detergents such as soda or monophosphate are now considered technically obsolete, since they form precipitates with the calcium and magnesium salts (so-called hardness formers) of service water, which deposit on laundry and appliances as undesirable and annoying deposits. The builder substances currently used, on the other hand, no longer precipitate the hardness formers of the water, but instead eliminate them through complex formation or ion exchange. However, the phosphates used as complexing agents contribute Eutrophication of standing or slowly flowing waters. The ecological side effect of the phosphates is undesirable and has led to an intensive search worldwide for suitable substitutes. However, known substitutes also have a number of disadvantages, since on the one hand they are poorly biodegradable like NTA or EDTA or on the other hand like citric acid or O- (carboxymethyl) malic acid they have comparatively low dispersing power and only moderate primary washing power. Ion exchangers such as zeolites, on the other hand, show a very pronounced ion exchange capacity, which, however, can be dangerous from an ecological point of view with regard to heavy metal ions. In addition, to support the ion exchange taking place in the heterogeneous phase, it is necessary to use the zeolites in combination with water-soluble complexing agents (e.g. the above-mentioned but questionable complexing agents such as NTA or EDTA) or carboxylic acid polymers (exploitation of the so-called carrier effect). Another disadvantage is that zeolite crystals can act as condensation bottoms for poorly soluble compounds in the washing or cleaning liquor and that they hardly show any dispersion behavior.
Aus der EP-A-O 107 159 sind Haarbehandlungsmittel bekannt, welche Lactionsäure als haarkosmetische Wirkstoffe enthalten.EP-AO 107 159 discloses hair treatment compositions which contain lactic acid as active ingredients in hair cosmetics.
Es bestand daher die Aufgabe, solche Wasch- und Reinigungsmittelzusammensetzungen zur Verfügung zu stellen, die die Nachteile des Standes der Technik im Hinblick auf die in den Zusammensetzungen enthaltenen Buildersubstanzen vermeiden bzw. wenigstens vermindern. Eine weitere Aufgabe bestand darin, in Zusammensetzungen für Wasch- und Reinigungszwecke bzw. in Wasch- und Reinigungsverfahren verwendbare Buildersubstanzen anzugeben, die sich außer durch ausreichend gutes Calciumbindevermögen, ökologische Verträglichkeit und biologische Abbaubarkeit vor allem durch ein sehr gutes Dispergierverhalten auszeichnen, welches zur Erzielung einer guten Wasch- und Reinigungswirkung erforderlich ist.The object was therefore to provide washing and cleaning agent compositions which avoid or at least reduce the disadvantages of the prior art with regard to the builder substances contained in the compositions. A further task was to specify builders which can be used in compositions for washing and cleaning purposes or in washing and cleaning processes and which, in addition to having sufficient calcium binding capacity, ecological compatibility and biodegradability, are characterized above all by very good dispersing behavior, which is necessary to achieve a good washing and cleaning effect is required.
Als Lösung dieser Aufgabe schlägt die Erfindung Wasch- und Reinigungsmittelzusammensetzungen vor, die Tenside und ggf. weitere in Wasch- und Reinigungsmitteln übliche Bestandteile, sowie als Buildersubstanzen Lactobionsäure und/oder Lactobionsäuresalze in Gegenwart einer Borsauerstoffverbindung enthalten.To achieve this object, the invention proposes detergent and cleaning agent compositions which contain surfactants and, if appropriate, further constituents customary in detergents and cleaning agents, and lactobionic acid and / or lactobionic acid salts in the presence of a boron oxygen compound as builder substances.
Lactobionsäure (4-(beta-D-Galactosido)-D-gluconsäure) ist als solche zwar bereits bekannt und kann beispielsweise durch Oxidation von Lactose erhalten werden. Bisher fand die Lactobionsäure in Form des Calciumsalzes in den sogenannten Calciumpräparaten zur Vorbeugung und Therapie von Calciummangelzuständen pharmzeutische Verwendung. Der Einsatz als Builder in Wasch- und Reinigungsmitteln ist dagegen bisher nicht beschrieben.Lactobionic acid (4- (beta-D-galactosido) -D-gluconic acid) is already known as such and can be obtained, for example, by oxidation of lactose. So far, the lactobionic acid in the form of the calcium salt has been used pharmaceutically in the so-called calcium preparations for the prevention and therapy of calcium deficiency states. The use as a builder in washing and cleaning agents, however, has not been described so far.
Prinzipiell können sowohl die freie Lactobionsäure selbst als auch deren Salze mit umweltverträglichen, nicht härtebildenden Metallkationen bzw. Gemische dieser Substanzen in den erfindungsgemäßen Zusammensetzungen als Buildersubstanz eingesetzt werden. Bevorzugt werden hierbei Alkalimetall-Lactobionate, insbesondere Natrium- und Kaliumlactobionat, eingesetzt.In principle, both the free lactobionic acid itself and its salts with environmentally compatible, non-hardness-forming metal cations or mixtures of these substances can be used as builder substance in the compositions according to the invention. Alkali metal lactobionates, in particular sodium and potassium lactobionate, are preferably used here.
Die Lactobionsäure und/oder Lactobionsäuresalze können in an sich für Buildersubstanzen üblichen Mengen in den erfindungsgemäßen Zusammensetzungen enthalten sein. Im allgemeinen können die Lactobionsäure und deren Salze dann in einer auf die Gesamtzusammensetzung bezogenen Menge bis 40 Gew.-% in den Wasch- und Reinigungsmittelzusammensetzungen vorliegen. Vorzugsweise beträgt die Menge der erfindungsgemäß in den Zusammensetzungen enthaltenen Buildersubstanzen aber bis 35 Gew.-%.The lactobionic acid and / or lactobionic acid salts can be present in the compositions according to the invention in amounts which are conventional per se for builder substances. In general, the lactobionic acid and its salts can then be present in the detergent and cleaning agent compositions in an amount based on the total composition of up to 40% by weight. However, the amount of builder substances contained in the compositions according to the invention is preferably up to 35% by weight.
Zusätzlich zur Lactobionsäure und/oder deren Salze, die als Buildersubstanzen in den erfindungsgemäßen Wasch- und Reinigungsmittelzusammensetzungen eingesetzt sind, enthalten diese Zusammensetzungen eine weitere Komponente, die aus einer oder mehreren Borsauerstoffverbindungen besteht. Durch die Gegenwart der Borsauerstoffverbindung wird die Builderwirkung der Lactobionsäure oder deren Salze in unerwarteter und überraschender Weise verstärkt. Die Borsauerstoffverbindungen liegen im allgemeinen in einer solchen Menge in den Zusammensetzungen vor, daß für 1 Mol Lactobionsäure und/oder Lactobionsäuresalz wenigstens 1 Mol Bor enthalten ist. Geeignet sind hierfür an sich beliebige Borsauerstoffverbindungen, z.B. übliche im Stand der Technik bekannte Borate wie Natriumborat, Natriummetaborat, Borax, Pentaborat usw. oder Gemische davon. Borsauerstoffverbindungen der vorgenannten Art sind insbesondere in solchen Zusammensetzungen enthalten, die kein Bleichmittel oder kein Perboratbleichmittel enthalten.In addition to lactobionic acid and / or its salts, which are used as builder substances in the washing and cleaning agent compositions according to the invention, these compositions contain a further component which consists of one or more boron oxygen compounds consists. The builder action of lactobionic acid or its salts is increased in an unexpected and surprising manner by the presence of the boron oxygen compound. The boron oxygen compounds are generally present in the compositions in an amount such that at least 1 mol of boron is contained for 1 mol of lactobionic acid and / or lactobionic acid salt. Any boron oxygen compounds are suitable for this purpose, for example conventional borates known in the prior art, such as sodium borate, sodium metaborate, borax, pentaborate, etc., or mixtures thereof. Boron oxygen compounds of the aforementioned type are contained in particular in those compositions which contain no bleaching agent or no perborate bleaching agent.
Als Borsauerstoffverbindungen können weiterhin auch Peroxidgruppen enthaltende Borsauerstoffverbindungen (d.h. Bor-haltige Persauerstoffbleichmittel) eingesetzt werden, z.B. solche an sich im Stand der Technik bekannte Perborate, die üblicherweise als Bleichmittel in Wasch-und Reinigungsmittelzusammensetzungen enthalten sind. Die Perborate werden hierbei in für Bleichmittel an sich üblichen Mengen in den Wasch- und Reinigungszusammensetzungen eingesetzt und es bedarf daher in diesem Falle keines weiteren Zusatzes von Borsauerstoffverbindungen der oben beschriebenen Art (d.h. Borate usw.).Peroxy group-containing boron oxygen compounds (i.e. boron-containing peroxygen bleach) can also be used as boron oxygen compounds, e.g. those perborates known per se in the prior art, which are usually contained as bleaching agents in detergent and cleaning agent compositions. The perborates are used in the washing and cleaning compositions in amounts customary for bleaching agents and, in this case, no further addition of boron oxygen compounds of the type described above (i.e. borates etc.) is therefore required.
Zwar können gemäß der Erfindung Lactobionsäure und deren Salze an sich für beliebige Wasch- und Reinigungsmittelzusammensetzungen als Builder eingesetzt werden, z.B. auch in flüssigen Wasch- und Reinigungsmitteln (bspw. Flüssigwaschmittel), doch zeigen sich die mit diesen Buildersubstanzen erzielbaren Vorteile insbesondere in pulverförmigen Wasch- und Reinigungsmittelzusammensetzungen, z.B. in sogenannten pulverförmigen Universalwaschmitteln, oder in Hand- und Maschinengeschirrspülmitteln.According to the invention, lactobionic acid and its salts per se can be used as builders for any detergent and cleaning agent compositions, for example also in liquid detergents and cleaning agents (for example liquid detergents), but the advantages which can be achieved with these builder substances are particularly evident in powdered detergents. and detergent compositions, for example in so-called powdered universal detergents, or in hand and machine dishwashing detergents.
Darüber hinaus kann es auch zweckmäßig sein, die erfindungsgemäßen Buildersubstanzen Lactobionsäure und/oder deren Salze als Cobuilder in Kombination mit weiteren, bisher im Stand der Technik üblichen organischen und/oder anorganischen Buildern in den Wasch- und Reinigungsmittelzusammensetzungen einzusetzen. Dieses ist insbesondere für solche Anwendungen vorteilhaft, die nur einen begrenzten Ersatz der üblichen Buildersubstanzen erlauben oder wünschenswert erscheinen lassen. Typische Beispiele für übliche im Stand der Technik bekannte Builder, die mit den erfindungsgemäß eingesetzten Buildern als Cobuilder in den Zusammensetzungen enthalten sein können sind Natriumaluminosilikate (z.B. Zeolithe), Natriumcitrat oder Salze von Aminopolycarbonsäuren wie Nitrilotriessigsäure und Ethylendiamintetraessigsäure. Aber auch andere bekannte Buildersubstanzen können in Kombination mit Lactobionsäure und/oder deren Salze in Wasch- und Reinigungsmittelzusammensetzungen enthalten sein. In den vorgenannten Zusammensetzungen liegen Lactobionsäure und/oder deren Salze als Cobuilder in Mengen bis zu 25 Gew.-% vor, bezogen auf die Gesamtzusammensetzung.In addition, it can also be expedient to use the builder substances according to the invention lactobionic acid and / or their salts as cobuilders in combination with further organic and / or inorganic builders which have been customary in the prior art in the detergent and cleaning agent compositions. This is particularly advantageous for those applications which only allow a limited replacement of the usual builder substances or make them appear desirable. Typical examples of customary builders known in the prior art which may be present in the compositions as builders with the builders used according to the invention are sodium aluminosilicates (e.g. zeolites), sodium citrate or salts of aminopolycarboxylic acids such as nitrilotriacetic acid and ethylenediaminetetraacetic acid. However, other known builder substances can also be present in combination with lactobionic acid and / or its salts in detergent and cleaning agent compositions. In the aforementioned compositions, lactobionic acid and / or its salts are present as cobuilders in amounts of up to 25% by weight, based on the total composition.
Die Zusammensetzungen der Erfindung können außer den weiter oben bereits erwähnten Perboraten an sich beliebige, im Stand der Technik übliche Bleichmittel oder Bleichmittelgemische enthalten, z.B. Chlorbleichmittel oder Persauerstoffbleichmittel. In bevorzugten erfindungsgemäßen Zusammensetzungen ist das Bleichmittel jedoch ein Persauerstoffbleichmittel, wie z.B. Persulfat, Percarbonat oder Perborate. In besonders günstiger Weise entfalten sich die vorteilhaften Wirkungen der in den erfindungsgemäßen Zusammensetzungen enthaltenen Buildersubstanzen, wenn die Zusammensetzungen als Bleichmittel ein Perborat enthalten. Bevorzugt sind dann insbesondere Perborate wie Natriumperborat-Tetrahydrat oder Natriumperborat-Monohydrat.In addition to the perborates already mentioned above, the compositions of the invention can contain any bleaching agent or bleaching agent mixture customary in the art, for example chlorine bleaching agent or peroxygen bleaching agent. In preferred compositions according to the invention, however, the bleaching agent is a peroxygen bleaching agent, such as persulfate, percarbonate or perborates. The advantageous effects of the builder substances contained in the compositions according to the invention develop particularly favorably if the compositions contain a perborate as the bleaching agent. Perborates such as sodium perborate tetrahydrate or sodium perborate monohydrate are particularly preferred.
Die erfindungsgemäßen Zusammensetzungen können in an sich bekannter Weise formuliert werden. Neben den bereits oben beschriebenen, in den Wasch- und Reinigungsmittelzusammensetzungen erfindungsgemäß enthaltenen Buildersubstanzen und der Borsauerstoffverbindung oder dem ggf. anwesenden Bleichmittel können in den erfindungsgemäßen Zusammensetzungen an sich alle gebräuchlichen Materialien, die üblicherweise zur Formulierung von Wasch- und Reinigungsmittelzusammensetzungen Verwendung finden, in an sich üblichen Mengen eingesetzt werden. Insbesondere enthalten die erfindungsgemäßen Zusammensetzungen außer den genannten Komponenten als wesentlichen Bestandteil Tenside, sowie ggf. weitere übliche Hilfstoffe.The compositions according to the invention can be formulated in a manner known per se. In addition to the builder substances according to the invention and the boron oxygen compound or the bleaching agent that may be present in the detergent and cleaning agent compositions already described above, all the usual materials that are usually used for the formulation of detergent and detergent compositions per se can be used in the compositions according to the invention usual amounts are used. In particular, in addition to the components mentioned, the compositions according to the invention contain surfactants as an essential constituent, and, if appropriate, other customary auxiliaries.
Die erfindungsgemäßen Zusammensetzungen können als Tenside beliebige grenzflächenaktive organische Verbindungen, wie anionische, kationische, ampholytische oder nicht-ionische Tenside oder Mischungen davon enthalten.The compositions according to the invention can contain any surface-active organic compounds, such as anionic, cationic, ampholytic or non-ionic surfactants or mixtures thereof, as surfactants.
Anionische Tenside sind z.B. synthetische oberflächenaktive Verbindungen mit einer oder mehreren funktionellen Gruppen, die in wäßriger Lösung unter Bildung negativ geladener Ionen ionisieren. Geeignete anionische Tenside sind beispielsweise Alkalimetall-, Ammonium- oder Alkanolaminsalze von Alkylbenzolsulfonaten mit 10 bis 18 C-Atomen in der Alkylgruppe; Alkyl- und Alkylethersulfate mit 10 bis 24 C-Atomen in der Alkylgruppe und mit 1 bis 5 Ethylenoxidgruppen; C₁₀- bis C₁₂-α-Olefinsulfonate, α-Sulfo-Fettsäureester.Anionic surfactants are e.g. synthetic surface-active compounds with one or more functional groups that ionize in aqueous solution to form negatively charged ions. Suitable anionic surfactants are, for example, alkali metal, ammonium or alkanolamine salts of alkylbenzenesulfonates having 10 to 18 carbon atoms in the alkyl group; Alkyl and alkyl ether sulfates with 10 to 24 carbon atoms in the alkyl group and with 1 to 5 ethylene oxide groups; C₁₀- to C₁₂-α-olefin sulfonates, α-sulfo fatty acid esters.
Kationische Tenside sind Tenside mit einer oder mehreren funktionellen Gruppen, die in wäßriger Lösung unter Bildung positiv geladener organischer Ionen ionisieren. Beispiele kationischer Tenside sind aliphatische oder aromatische höher-Alkyl-di-niedrig-alkyl-ammoniumhalogenide, z.B. Dialkyl-dimethylammoniumchloride wie Distearyl-dimethylammoniumchlorid; Alkyl-dimethylbenzyl-ammoniumchloride; Imidazolinium-salze.Cationic surfactants are surfactants with one or more functional groups that ionize in aqueous solution to form positively charged organic ions. Examples of cationic surfactants are aliphatic or aromatic higher-alkyl-di-lower-alkyl-ammonium halides, for example dialkyl-dimethylammonium chlorides such as distearyl-dimethylammonium chloride; Alkyl dimethyl benzyl ammonium chloride; Imidazolinium salts.
Zu den ampholytischen (zwitterionischen) Tensiden gehören Derivate von geradkettigen oder verzweigten aliphatischen Verbindungen mit gewöhnlich 8 bis 24 C-Atomen, die aliphatische quartäre Ammonium-, Phosphonium- oder Sulfonium-Gruppen und wenigstens eine anionische wasserlösliche Gruppe sowie gegebenenfalls noch andere Substituenten enthalten. Beispiele sind C₁₂- bis C₁₈-Alkylbetaine der Formel R-N⁺ (CH₃)₂CH₂-COO⁻ und C₁₂-bis C₁₈-Alkyl-sulfobetaine der Formel R-N⁺ (CH₃)₂-SO₃⁻.The ampholytic (zwitterionic) surfactants include derivatives of straight-chain or branched aliphatic compounds with usually 8 to 24 carbon atoms, which contain aliphatic quaternary ammonium, phosphonium or sulfonium groups and at least one anionic water-soluble group and optionally also other substituents. Examples are C₁₂- to C₁₈-alkyl betaines of the formula R-N⁺ (CH₃) ₂CH₂-COO⁻ and C₁₂- to C₁₈-alkyl sulfobetaines of the formula R-N⁺ (CH₃) ₂-SO₃⁻.
Nicht-ionische Tenside sind gewöhnlich Cokondensate von Ethylenoxid oder Propylenoxid mit Kohlenwasserstoffen, die reaktive Gruppen wie Hydroxyl-, Carboxyl- oder Amino-Gruppen tragen. Beispiele sind Alkylphenol-polyglykolether mit C₈-C₁₂-Alkylresten und 5 bis 10 Ethylenglykoleinheiten; Alkylpolyglykolether wie Fettalkohol-polyethylenglykolether und Oxoalkohol-polyethylenglykolether; Fettsäure-alkanolamide, z.B. vom Typ der Fettsäure-ethanolamide.Non-ionic surfactants are usually cocondensates of ethylene oxide or propylene oxide with hydrocarbons which carry reactive groups such as hydroxyl, carboxyl or amino groups. Examples are alkylphenol polyglycol ethers with C₈-C₁₂ alkyl radicals and 5 to 10 ethylene glycol units; Alkyl polyglycol ethers such as fatty alcohol polyethylene glycol ether and oxo alcohol polyethylene glycol ether; Fatty acid alkanolamides, e.g. of the fatty acid ethanolamide type.
Weitere nicht-ionische Tenside sind die semi-polaren nicht-ionischen Tenside, z.B. wasserlösliche Aminoxide mit Alkyl- oder Hydroxyalkyleinheiten mit 8 bis 28 C-Atomen, wobei zwei dieser Alkyl- oder Hydroxyalkyleinheiten gegebenenfalls zu einer Ringstruktur mit 1 bis 3 C-Atomen verknüpft sein können.Other non-ionic surfactants are the semi-polar non-ionic surfactants, e.g. water-soluble amine oxides with alkyl or hydroxyalkyl units with 8 to 28 C atoms, it being possible for two of these alkyl or hydroxyalkyl units to be linked to form a ring structure with 1 to 3 C atoms.
Die Wasch- und Reinigungsmittelzusammensetzungen der vorliegenden Erfindung können weitere übliche Hilfsstoffe für die Formulierung von Wasch- und Reinigungsmitteln enthalten. Zu solchen Hilfsstoffen gehören Verstärker, Waschmittelenzyme, Enzymstabilisatoren, Schmutzträger und/oder Kompatibilisierungsmittel, Komplex- und Chelatbildner, Seifenschaumregulatoren und Zusatzstoffe wie optische Aufheller, Opazifizierungsmittel, Korrosionsinhibitoren, Antielektrostatika, Farbstoffe, Bakterizide, Bleichaktivatoren, Persäurebleichmittelvorstufen.The detergent and cleaning agent compositions of the present invention can contain further customary auxiliaries for the formulation of detergents and cleaning agents. Such auxiliaries include enhancers, detergent enzymes, enzyme stabilizers, dirt carriers and / or compatibilizers, complexing agents and chelating agents, soap foam regulators and additives such as optical brighteners, opacifying agents, corrosion inhibitors, Antistatic agents, dyes, bactericides, bleach activators, peracid bleach precursors.
So enthalten erfindungsgemäße Waschmittelzusammensetzungen in typischer beispielhafter Zusammensetzung
- a) wenigstens 5 Gew.-% eines Tensids oder Tensidgemisches,
- b) bis 40 Gew.-% Lactobionsäure und/oder Lactobionsäuresalz als Builder, ggf. einschließlich des Anteils der in der Zusammensetzung enthaltenen weiteren Buildersubstanzen,
- c) bis 40 Gew.-% eines Natriumperborates und
- d) weitere Bestandteile wie Hilfsstoffe etc. ad 100 Gew.-%.
- a) at least 5% by weight of a surfactant or surfactant mixture,
- b) up to 40% by weight of lactobionic acid and / or lactobionic acid salt as a builder, if appropriate including the proportion of the further builder substances contained in the composition,
- c) up to 40 wt .-% of a sodium perborate and
- d) further components such as auxiliaries, etc. ad 100 wt .-%.
Die Erfindung betrifft in einer weiteren Variante auch solche Zusammensetzungen für Wasch- und Reinigungszwecke oder für Bleichzwecke in Wasch- und Reinigungsverfahren, die Lactobionsäure und/oder Lactobionsäuresalze als Buildersubstanzen in Gegenwart einer Borsauerstoffverbindung enthalten, aber an sich noch keine vollständigen Wasch- und Reinigungsmittelzusammensetzungen im vorstehend beschriebenen Sinne sind, da sie nur einen Teil der üblicherweise in einer vollständigen, für die Anwendung geeigneten Wasch- und Reinigungsmittelzusammensetzung enthaltenen Bestandteile enthalten. Solche erfindungsgemäßen Teilzusammensetzungen können einerseits zur industriellen Herstellung vollständiger Wasch- und Reinigungsmittelzusammensetzungen dienen. Andererseits sind die Teilzusammensetzungen als Komponenten für sogenannte Wasch- und Reinigungsmittel-Baukastensysteme gut geeignet. In solchen Baukastensystemen sind die Bestandteile nicht wie in herkömmlichen (vollständigen) Wasch- und Reinigungsmittelzusammensetzungen bereits miteinander vermischt, sondern liegen als getrennte Systemkomponenten, z.B. als Tensid-, Bleichmittel- und Builderkomponente, vor. Die einzelnen Komponenten werden erst vom Anwender je nach den individuellen Erfordernissen (wie Art des zu waschenden oder zu reinigenden Materials; Art des Wasch- oder Reinigungsverfahrens, z.B. Koch- oder Feinwäsche etc.; Wasserhärte etc.) in ihrer Menge aufeinander abgestimmt. Die Komponenten können dabei sowohl vor ihrem Einsatz miteinander vermischt als auch getrennt dem Waschwasser zudosiert werden.In a further variant, the invention also relates to compositions for washing and cleaning purposes or for bleaching purposes in washing and cleaning processes which contain lactobionic acid and / or lactobionic acid salts as builder substances in the presence of a boron oxygen compound, but in themselves are not yet complete washing and cleaning agent compositions in the above described senses, since they contain only a part of the ingredients usually contained in a complete detergent composition suitable for use. Such partial compositions according to the invention can serve on the one hand for the industrial production of complete detergent and cleaning agent compositions. On the other hand, the partial compositions are well suited as components for so-called modular detergent and cleaning agent systems. In such modular systems, the constituents are not already mixed with one another as in conventional (complete) detergent and cleaning agent compositions, but instead lie as separate system components, for example as surfactant, bleach and builder components. in front. The individual components are only coordinated by the user depending on the individual requirements (such as the type of material to be washed or cleaned; type of washing or cleaning process, e.g. hot or delicate laundry, etc .; water hardness etc.). The components can either be mixed with one another before use or metered separately into the wash water.
In einer vorteilhaften Ausgestaltung der erfindungsgemäßen Teilzusammensetzungen kann die darin enthaltende Borsauerstoffverbindung ein Persauerstoffbleichmittel sein, in Analogie wie dieses weiter oben im Zusammenhang mit den Wasch- und Reinigungszusammensetzungen beschrieben ist. Bevorzugte Persauerstoffbleichmittel sind Perborate. Solche Teilzusammensetzungen, beispielsweise in Form von Pulvern oder Granulaten, die Lactobionsäure und/ oder Lactobionsäuresalze in Gegenwart von Perborat enthalten, eignen sich z.B. für die Verwendung als sogenannte Trockenbleiche in Wasch- und Reinigungsverfahren.In an advantageous embodiment of the partial compositions according to the invention, the boron oxygen compound contained therein can be a peroxygen bleaching agent, in analogy to that described above in connection with the washing and cleaning compositions. Preferred peroxygen bleaches are perborates. Such partial compositions, for example in the form of powders or granules, which contain lactobionic acid and / or lactobionic acid salts in the presence of perborate, are suitable, for example, for use as so-called dry bleach in washing and cleaning processes.
Die Erfindung betrifft weiterhin die Verwendung von Lactobionsäure und/oder Lactobionsäuresalzen als Buildersubstanzen in Zusammensetzungen für Wasch- und Reinigungszwecke. Hierbei können sowohl die freie Lactobionsäure selbst als auch deren Salze mit umweltverträglichen, nicht härtebildenden Metallkationen bzw. Gemische dieser Substanzen als Buildersubstanzen in der oben beschriebenen Weise für erfindungsgemäße Zusammensetzungen verwendet werden. Bevorzugt verwendet man aber insbesondere das Natrium- oder Kaliumsalz der Lactobionsäure.The invention further relates to the use of lactobionic acid and / or lactobionic acid salts as builder substances in compositions for washing and cleaning purposes. Both the free lactobionic acid itself and its salts with environmentally compatible, non-hardness-forming metal cations or mixtures of these substances can be used as builder substances in the manner described above for compositions according to the invention. However, preference is given in particular to using the sodium or potassium salt of lactobionic acid.
Die Erfindung betrifft ferner ein Verfahren zum Waschen und Reinigen, welches sich dadurch auszeichnet, daß Lactobionsäure und/oder Lactobionsäuresalze als Buildersubstanzen in Gegenwart von Borsauerstoffverbindungen eingesetzt werden.The invention further relates to a method for washing and cleaning, which is characterized in that lactobionic acid and / or lactobionic acid salts are used as builder substances in the presence of boron oxygen compounds.
Die erfindungsgemäßen Zusammensetzungen, die erfindungsgemäße Verwendung sowie das erfindungsgemäße Verfahren bieten eine überraschende und problemlose Lösung für den vielfach vorhandenen Wunsch nach geeigneten umweltverträglichen und biologisch abbaubaren Buildersubstanzen, die außer gutem Calciumbindevermögen insbesondere sehr gutes Dispergierverhalten zeigen. Neben der Eliminierung von störenden Kationen wie Calcium und Magnesium und neben einer guten Primärwaschwirkung führt das sehr gute Dispergiervermögen der Lactobionsäure und deren Salze in Gegenwart einer Borsauerstoffverbindung zur Zurückdrängung von Vergrauungen und Vergilbungen. Diese Eigenschaft ist für Wasch- und Reinigungsprozesse von höchster Bedeutung und wird von Lactobionsäure und deren Salze in hervorragender Weise erfüllt. Darüber hinaus werden auch Inkrustationen z.B. auf Textilien oder in Waschmaschinen in unerwartet günstigem Ausmaß unterbunden. Weiterhin zeigen Lactobionsäure und deren Salze auch den sogenannten Threshold-Effekt, d.h. sie sind befähigt, die Ausfällung unlöslicher Salze auch bei Anwendung unterstöchiometrischer Mengen an Builder zu verzögern, zu vermindern oder zumindest zu bewirken, daß die unlöslichen Salze vorwiegend in amorpher Form anfallen und die Bildung von scharfkantigen, faserschädigenden Kristallen (z.B. Calcit-Kristalle) weitgehend zurückgedrängt wird. Die Verbindungen sind chemisch beständig, nicht hygroskopisch, lagerstabil und technisch gut zu verarbeiten. Weiterhin sind sie mit üblichen Wasch- und Reinigungsmittelinhaltsstoffen gut verträglich. Die Verbindungen können auf Grundlage einer gesicherten Rohstoffbasis leicht aus Lactose durch Oxidation gewonnen werden und sind auch in wirtschaftlicher Hinsicht vorteilhaft. Die biologische Herkunft und vollständige biologische Abbaubarkeit der Substanzen garantiert humantoxikologische Unbedenklichkeit und günstiges Umweltverhalten.The compositions according to the invention, the use according to the invention and the method according to the invention offer a surprising and problem-free solution to the widespread desire for suitable environmentally compatible and biodegradable builder substances which, in addition to good calcium binding capacity, in particular show very good dispersing behavior. In addition to the elimination of disruptive cations such as calcium and magnesium and a good primary washing action, the very good dispersibility of lactobionic acid and its salts results in the presence a boron oxygen compound to suppress graying and yellowing. This property is of paramount importance for washing and cleaning processes and is excellently fulfilled by lactobionic acid and its salts. In addition, incrustations, for example on textiles or in washing machines, are prevented to an unexpectedly favorable extent. Lactobionic acid and its salts also show the so-called threshold effect, i.e. they are able to delay, reduce, or at least cause the precipitation of insoluble salts even when using substoichiometric amounts of builders, or at least to cause the insoluble salts to occur predominantly in amorphous form and that Formation of sharp-edged, fiber-damaging crystals (eg calcite crystals) is largely suppressed. The compounds are chemically stable, not hygroscopic, stable in storage and easy to process technically. Furthermore, they are well compatible with common detergent and cleaning agent ingredients. The compounds can be easily obtained from lactose by oxidation on the basis of a secure raw material base and are also economically advantageous. The biological origin and complete biodegradability of the substances guarantee harmlessness to humans and favorable environmental behavior.
Die nachfolgenden Beispiele sollen die Erfindung weiter erläutern, ohne sie jedoch in ihrem Umfang zu begrenzen.The following examples are intended to explain the invention further, but without restricting its scope.
Das Kalkbindevermögen von Lactobionsäure in Gegenwart von Borsauerstoffverbindungen (2,13 g Borax und/oder 2 g Natriumperborat in 100 ml Lösung) wurde bei pH 10 ermittelt, indem man 100 ml einer wässrigen Lösung aus 1 Gew.-% Lactobionsäure, 0,4 Gew.-% Natriumcarbonat und gegebenenfalls 0,1 Gew.-% TAED als Bleichaktivator mit einer wässrigen 0,1 N Calciumchloridlösung bis zum Auftreten einer bleibenden Trübung titrierte. Unter diesen Versuchsbedingungen liegt die Lactobionsäure als Natriumsalz in der Testlösung vor. Als Meßzahl für das Kalkbindevermögen wird die Grammzahl der Calciumionen angegeben, die pro 100 g Lactobionsäure als Buildersubstanz unter den vorgenannten Bedingungen in Lösung gehalten werden kann.The lime binding capacity of lactobionic acid in the presence of boron oxygen compounds (2.13 g borax and / or 2 g sodium perborate in 100 ml solution) was determined at pH 10 by mixing 100 ml of an aqueous solution of 1% by weight lactobionic acid, 0.4% by weight % Sodium carbonate and optionally 0.1% by weight TAED as bleach activator with an aqueous 0.1 N calcium chloride solution until occurrence a permanent cloudiness titrated. Under these test conditions, lactobionic acid is present as the sodium salt in the test solution. The measured number for the lime binding capacity is the gram number of calcium ions which can be kept in solution per 100 g of lactobionic acid as builder substance under the aforementioned conditions.
Die in der nachfolgenden Tabelle angegebenen Versuche wurden bei Raumtemperatur durchgeführt.
Die Versuche zeigen, daß Buildersysteme mit Lactobionsäure deutliches Calciumbindevermögen, d.h. deutliches Sequestriervermögen, aufweisen.The tests given in the table below were carried out at room temperature.
The experiments show that builder systems with lactobionic acid have a clear calcium binding capacity, ie a clear ability to sequester.
Das Dispergiervermögen von Lactobionsäure in Gegenwart von Borax als Borsauerstoffverbindung (0,21 g in 100 ml Lösung) wurde im Vergleich zu anderen Buildersubstanzen untersucht. Zur Bestimmung des Dispergiervermögens wurden hierzu wässrige Dispersionen aus 0,1 Gew.-% der zu prüfenden Buildersubstanz und 4 Gew.-% Pudergraphit als Dispersa hergestellt, indem man die Substanzen in einen 100-ml-Schüttelmeßzylinder einwog, mit Wasser auf 100 ml auffüllte und eine Minute intensiv schüttelte. Als Maß für das Dispergiervermögen wurde nach 24 stündigem Stehen insbesondere das Sedimentationsvolumen der Graphitpartikel ermittelt und für ergänzende Untersuchungen zusätzlich eine Probe aus der Dispersion in Höhe der 70 ml-Meßmarke des Schüttelmeßzylinders entnommen und einer photometrischen Untersuchung zugeleitet. Gemessen wurde hierbei die Transmission der Proben im Vergleich zu entsprechenden Blindproben ohne Graphit (Transmission 100 %), wobei kleinere Transmissionswerte besseres Dispergiervermögen andeuten.The dispersibility of lactobionic acid in the presence of borax as boron oxygen compound (0.21 g in 100 ml solution) was investigated in comparison to other builder substances. To determine the dispersibility, aqueous dispersions were prepared from 0.1% by weight of the builder substance to be tested and 4% by weight powder graphite as dispersa by weighing the substances into a 100 ml shaking measuring cylinder, making up to 100 ml with water and shook vigorously for a minute. After 24 hours of standing, the sedimentation volume of the graphite particles, in particular, was determined as a measure of the dispersing capacity and, for additional tests, a sample was additionally taken from the dispersion at the level of the 70 ml measuring mark of the shaking measuring cylinder and sent to a photometric test. The transmission of the samples was measured here in comparison to corresponding blank samples without graphite (transmission 100%), with smaller transmission values indicating better dispersibility.
Die Versuche zeigen, daß bei erfindungsgemäßem Einsatz von Lactobionsäure als Buildersubstanz (Versuche Nr. 9 und 13) deutlich geringere Sedimentationsvolumina und kleinere Transmissionswerte als bei den Vergleichsversuchen 10 bis 12 und 14 bis 16 auftreten. Lactobionsäure als Buildersubstanz weist damit deutlich besseres Dispergiervermögen als Buildersubstanzen des Standes der Technik auf.
The experiments show that when lactobionic acid is used according to the invention as builder substance (Experiments Nos. 9 and 13), significantly lower sedimentation volumes and smaller transmission values than in the comparative experiments 10 to 12 and 14 to 16 occur. Lactobionic acid as builder substance thus has significantly better dispersing power than builder substances of the prior art.
a) Zur Prüfung des Einflusses des Builders auf die Perboratstabilität wurden 250 ml einer auf pH = 10 (mit 5 N NaOH) eingestellten wässrigen Lösung, die 5 g Buildersubstanz, 5 g Natriumperborat-Tetrahydrat, 0,02 g Eisen(III)chlorid und ggf. 10,25 g Borax enthielt, im Wasserbad auf 90 °C erhitzt. Zur Bestimmung des Aktivsauerstoffgehaltes wurden jeweils nach 30, 90 und 150 Minuten Proben von 50 ml für eine jodometrische Titration entnommen. Hierzu wurde die Probe von 50 ml Lösung mit 10 ml 4 N Salzsäure und 3 g Kaliumjodid versetzt und 10 Minuten im Dunkeln stehen gelassen. Anschließend wurde mit 1 molarer Natriumthiosulfatlösung gegen Stärke als Indikator titriert. Der Aktivsauerstoffgehalt der Proben in % bezieht sich auf jeweils gleichbehandelte Blindproben (100%) ohne Buildersubstanz, die ansonsten aber die gleiche Zusammensetzung wie die entsprechende Probe aufwiesen.
b) Die Versuche wurden analog zu a) mit wässrigen Lösungen wiederholt, die außer den oben unter a) angegebenen Bestandteilen noch 0,25 g TAED als Bleichmittelaktivator in 250 ml Lösung enthielten.
a) To test the influence of the builder on the perborate stability, 250 ml of an aqueous solution adjusted to pH = 10 (with 5 N NaOH), the 5 g builder substance, 5 g sodium perborate tetrahydrate, 0.02 g iron (III) chloride and optionally contained 10.25 g of borax, heated to 90 ° C. in a water bath. To determine the active oxygen content, 50 ml samples were taken for iodometric titration after 30, 90 and 150 minutes. For this purpose, the sample of 50 ml of solution was mixed with 10 ml of 4N hydrochloric acid and 3 g of potassium iodide and left to stand in the dark for 10 minutes. It was then titrated with 1 molar sodium thiosulfate solution against starch as an indicator. The active oxygen content of the samples in% relates to blank samples (100%) treated in the same way without builder substance, but which otherwise had the same composition as the corresponding sample.
b) The experiments were repeated analogously to a) with aqueous solutions which, in addition to the constituents given above under a), also contained 0.25 g of TAED as bleach activator in 250 ml of solution.
Wie der Vergleich mit dem bekannten Builder STPP (Vergleichsversuche Nr. 18 und 20) zeigt, wird durch den erfindungsgemäßen Einsatz von Lactobionsäure als Buildersubstanz (Versuche 17 und 19 dieses Beispiels) die Perboratstabilität nicht negativ beeinflußt. Lactobionsäure verhält sich hinsichtlich der Perboratstabilität gleichermaßen gut wie Builder im Stand der Technik.
Außer durch die voranstehenden Laborversuche der Beispiele 1 bis 3 werden die hervorragenden Eigenschaften der Lactobionsäure bezüglich ihres Einsatzes als Buildersubstanz in Wasch- und Reinigungsmittelzusammensetzungen insbesondere durch die Waschversuche der nachfolgenden Beispiele 4 bis 6 sehr deutlich.
As the comparison with the known builder STPP (Comparative Experiments No. 18 and 20) shows, the use of lactobionic acid as builder substance according to the invention (Experiments 17 and 19 of this example) does not adversely affect the perborate stability. Lactobionic acid behaves equally well in terms of perborate stability as builders in the prior art.
In addition to the laboratory tests of Examples 1 to 3 above, the excellent properties of lactobionic acid with regard to its use as builder in detergent and cleaning agent compositions are particularly evident in the washing tests of Examples 4 to 6 below.
Die Waschleistung wurde durch Waschversuche an Testgeweben in zwei Standardwaschmaschinen (Typ: Miele W 180) bestimmt. Hierzu wurden 2 kg Testgewebe mit 155 g Waschmittel im Kurzprogramm (Waschdauer 1 h) gewaschen. Als Waschmittel wurde eine standardisierte Vollwaschmittelformulierung eingesetzt, die 30 Gew.-% des zu testenden Buildersystems enthielt. Zusammensetzung der standardisierten Vollwaschmittelformulierung:
30,0 Gew.-% Buildersystem (siehe Tabelle)
11,9 Gew.-% Dodecylbenzolsulfonat
4,0 Gew.-% Talgfettalkoholethoxylat mit 11 Mol Ethylenoxid
4,0 Gew.-% Talgseife
4,0 Gew.-% Natriumsilikat
32,9 Gew.-% Natriumperborat-Tetrahydrat
11,9 Gew.-% Natriumsulfat
1,3 Gew.-% Tylose.
Die Versuche wurden bei pH 10 und 18 °dH bei 30 und 60 °C ausgeführt. Das Flottenverhältnis lag bei 1:12. Die Waschleistung wurde durch Messung der Aufhellung von angeschmutzten Testgeweben (Baumwollgewebe und Baumwollmischgewebe) als Remissionsdifferenz (Remission des trockenen Testgewebes nach dem Waschversuch abzüglich der Remission Testgewebes vor dem Waschversuch) bei 530 nm ermittelt. Die größere Remissionsdifferenz gibt hierbei die bessere Waschleistung an. Als Buildersysteme in den Vollwaschmittelformulierungen wurden Lactobionsäure allein, Lactobionsäure mit Zeolith (im Verhältnis 1:1) und als Vergleich STPP eingesetzt.
Die erfindungsgemäßen Versuche dieses Beispiels (Nr. 21, 22, 24, 25, 27, 28, 30, 31, 33 und 34) zeigen, daß Buildersysteme mit Lactobionsäure je nach Gewebeart vergleichbare, z.T. sogar bessere Waschleistungen verglichen mit guten Buildern gemäß Stand der Technik (Vergleichsversuche Nr. 23, 26, 29, 32 und 35) aufweisen.The washing performance was determined by washing tests on test fabrics in two standard washing machines (type: Miele W 180). For this purpose, 2 kg of test fabric was washed with 155 g of detergent in the short program (washing time 1 h). A standardized heavy-duty detergent formulation was used as the detergent, which contained 30% by weight of the builder system to be tested. Composition of the standardized heavy-duty detergent formulation:
30.0% by weight builder system (see table)
11.9% by weight of dodecylbenzenesulfonate
4.0% by weight of tallow fatty alcohol ethoxylate with 11 moles of ethylene oxide
4.0% by weight of sebum soap
4.0% by weight sodium silicate
32.9% by weight sodium perborate tetrahydrate
11.9% by weight sodium sulfate
1.3 wt% tylose.
The experiments were carried out at pH 10 and 18 ° dH at 30 and 60 ° C. The fleet ratio was 1:12. The washing performance was determined by measuring the lightening of soiled test fabrics (cotton fabric and cotton blended fabrics) as the reflectance difference (reflectance of the dry test fabric after the wash test minus the reflectance test fabric before the wash test) at 530 nm. The larger remission difference indicates the better washing performance. Lactobionic acid alone, lactobionic acid with zeolite (in a 1: 1 ratio) and STPP as a comparison were used as builder systems in the heavy-duty detergent formulations.
The experiments according to the invention of this example (No. 21, 22, 24, 25, 27, 28, 30, 31, 33 and 34) show that builder systems with lactobionic acid, depending on the type of fabric, have comparable, in some cases even better washing performance compared to good builders according to the prior art Technique (comparative experiments No. 23, 26, 29, 32 and 35).
Zur Verdeutlichung, inwieweit der Einsatz von Lactobionsäure als Buildersubstanz die Vergrauung von Textilien verhindert, wurden Waschversuche an gebleichten Testgeweben ohne künstliche Anschmutzung und ohne optische Aufheller durchgeführt. Hierzu ließ man die Testgewebe insgesamt 25 Waschzyklen analog zu den im Beispiel 4 angegebenen Waschbedingungen bei 60 °C im Normalprogramm (Einlaugenverfahren, 2 h) durchlaufen. Danach wurde die Vergrauung der Testgewebe (Baumwollgewebe, Frottee) durch Messung der Remission bei 530 nm ermittelt. Als Builder in der standardisierten Vollwaschmittelformulierung (siehe Beispiel 4) wurden Lactobionsäure und als Vergleich STPP eingesetzt. Die Remission ist indirekt proportional zur Vergrauung.
Die erfindungsgemäßen Versuche dieses Beispiels (Nr. 36 und 38) zeigen, daß bei Einsatz von Lactobionsäure als Buildersubstanz in Wasch- und Reinigungsmittelzusammensetzungen die Vergrauung von Textilien ebenso hervorragend verhindert wird die durch bekanntermaßen gute Builder des Standes der Technik (Vergleichsversuche Nr. 37 und 39).In order to clarify to what extent the use of lactobionic acid as builder substance prevents the graying of textiles, washing tests were carried out on bleached test fabrics without artificial soiling and without optical brighteners. For this purpose, the test fabrics were allowed to run through a total of 25 washing cycles analogous to the washing conditions specified in Example 4 at 60 ° C. in the normal program (soaking process, 2 h). The graying of the test fabrics (cotton fabric, terry cloth) was then determined by measuring the reflectance at 530 nm. Lactobionic acid was used as the builder in the standardized heavy-duty detergent formulation (see Example 4) and STPP as a comparison. The remission is indirectly proportional to the graying.
The experiments according to the invention of this example (Nos. 36 and 38) show that when lactobionic acid is used as builder in detergent and cleaning agent compositions, the graying of textiles is also prevented in an excellent manner by the known builders of the prior art (comparative experiments Nos. 37 and 39 ).
Zur Bestimmung der anorganischen Inkrustierung wurden Waschversuche an Testgeweben durchgeführt. Hierzu ließ man die Testgewebe insgesamt 25 Waschzyklen analog zu den im Beispiel 4 angegebenen Waschbedingungen durchlaufen. Nach Beendigung der Waschzyklen wurden die Testgewebe nach an sich bekannten Standardbedingungen verascht und als Maß für die anorganische Inkrustierung der verbliebene Aschegehalt in Gew.-% (bezogen auf eingesetztes Testgewebe) ermittelt. Als Builder in der standardisierten Vollwaschmittelformulierung (siehe Beispiel 4) wurden Lactobionsäure und als Vergleich STPP eingesetzt. Je kleiner der verbliebene Aschegehalt ist, desto geringer ist die Inkrustierung.
Die erfindungsgemäßen Versuche dieses Beispiels (Nr. 40 und 42) zeigen, daß bei Einsatz von Lactobionsäure in Wasch- und Reinigungsmittelzusammensetzungen die Inkrustierung von Textilien je nach Gewebeart etwas (Baumwolle) oder sogar viel besser (Frottee) als durch bekanntermaßen gute Builder des Standes der Technik (Vergleichsversuche 41 und 43) verhindert wird.To determine the inorganic incrustation, washing tests were carried out on test fabrics. For this purpose, the test fabrics were run through a total of 25 washing cycles analogous to the washing conditions given in Example 4. After completion of the washing cycles, the test fabrics were incinerated according to standard conditions known per se and the remaining ash content in% by weight (based on the test fabric used) was determined as a measure of the inorganic incrustation. Lactobionic acid was used as the builder in the standardized heavy-duty detergent formulation (see Example 4) and STPP as a comparison. The smaller the remaining ash content, the lower the incrustation.
The experiments according to the invention of this example (Nos. 40 and 42) show that when lactobionic acid is used in detergent and cleaning agent compositions, the incrustation of textiles, depending on the type of fabric, is somewhat (cotton) or even much better (terry cloth) than by known builders of the prior art Technology (comparative tests 41 and 43) is prevented.
- WFKWFK
- = Wäschereiforschung Krefeld= Krefeld laundry research
- PE/BW (20 C)PE / BW (20 C)
- = Polyester/Baumwolle (Typ 20 C)= Polyester / cotton (type 20 C)
- BW (10 C)BW (10 C)
- = Baumwolle (Typ 10 C)= Cotton (type 10 C)
- EMPAEMPA
- = Eidgenössische Materialprüfungsanstalt= Federal Materials Testing Institute
- PE/BW (104)PE / BW (104)
- = Polyester/Baumwolle (Typ 104)= Polyester / cotton (type 104)
- BW (101)BW (101)
- = Baumwolle (Typ 101)= Cotton (type 101)
- STPPSTPP
- = Natriumtripolyphosphat bzw. Natriumtriphosphat= Sodium tripolyphosphate or sodium triphosphate
- NTANTA
- = Nitrilotriessigsäure= Nitrilotriacetic acid
- TAEDTAED
- = Tetraacetylethylendiamin= Tetraacetylethylenediamine
Claims (13)
- Detergent and cleaning agent compositions containing tensides and optionally other conventional constituents found in detergent and cleaning agents, characterised in that they contain lactobionic acid and/or lactobionic acid salts as builder substances in the presence of a boron/oxygen compound.
- Compositions according to Claim 1, characterised in that the lactobionic acid and/or lactobionic acid salts are present in quantities of up to 40% by weight, relative to the total composition.
- Compositions according to Claim 1, characterised in that the boron/oxygen compound is present in the compositions in such a quantity that at least 1 mol boron is contained per 1 mol lactobionic acid and/or lactobionic acid salt.
- Compositions according to Claim 1, characterised in that the boron/oxygen compound is a peroxygen bleaching agent.
- Compositions according to Claim 4, characterised in that the peroxygen bleaching agent is a perborate.
- Compositions according to Claim 1, characterised in that the compositions are powdered detergent and cleaning agent compositions.
- Compositions according to Claim 1, characterised in that the compositions contain as the builder component a combination of conventional builder substances and lactobionic acid and/or lactobionic acid salts as a co-builder.
- Compositions according to Claim 7, characterised in that the conventional builder substances are selected from the group zeolites, sodium citrate and aminopolycarboxylic acids.
- Compositions according to Claim 7, characterised in that the lactobionic acid and/or the lactobionic acid salts are present as co-builders in quantities of up to 25% by weight, relative to the total composition.
- Compositions for washing, cleaning and bleaching purposes, characterised in that they contain lactobionic acid and/or lactobionic acid salts as builder substances in the presence of a boron/oxygen compound.
- Compositions according to Claim 10, characterised in that the boron/oxygen compound is a peroxygen bleaching agent, preferably a perborate.
- Use of lactobionic acid and/or lactobionic acid salts as builder substances in compositions for washing and cleaning purposes.
- Method for washing or cleaning, characterised in that lactobionic acid and/or lactobionic acid salts are used as builder substances in the presence of boron/oxygen compounds.
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| DE3914293 | 1989-04-29 | ||
| DE3914293A DE3914293A1 (en) | 1989-04-29 | 1989-04-29 | DETERGENT AND DETERGENT COMPOSITIONS |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| EP0395970A1 EP0395970A1 (en) | 1990-11-07 |
| EP0395970B1 true EP0395970B1 (en) | 1994-06-15 |
Family
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|---|---|---|---|
| EP90107599A Expired - Lifetime EP0395970B1 (en) | 1989-04-29 | 1990-04-21 | Washing and cleaning compositions |
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| US (1) | US5069808A (en) |
| EP (1) | EP0395970B1 (en) |
| JP (1) | JP2672175B2 (en) |
| AT (1) | ATE107348T1 (en) |
| CA (1) | CA2012836C (en) |
| DE (2) | DE3914293A1 (en) |
| DK (1) | DK0395970T3 (en) |
| ES (1) | ES2057245T3 (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP3156475B1 (en) | 2015-10-16 | 2018-06-06 | Hans Georg Hagleitner | Liquid cleaning concentrate |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| FR2659979B1 (en) * | 1990-03-23 | 1994-04-29 | Roquette Freres | WASHING PRODUCT WITH REDUCED OR ZERO PHOSPHATE CONTENT. |
| DE4215478A1 (en) * | 1992-05-11 | 1993-11-18 | Solvay Deutschland | Lactobionic acid amide compositions and their use |
| US5433883A (en) * | 1993-11-04 | 1995-07-18 | Lever Brothers Company, Division Of Conopco, Inc. | Toilet bar compositions comprising nonionic glycolipid surfactants and polyalkylene glycol structurant |
| DE4435817A1 (en) * | 1993-12-29 | 1996-04-11 | Solvay Interox Gmbh | Coated alkali metal peroxy salts and process for their preparation |
| WO2006131503A2 (en) * | 2005-06-10 | 2006-12-14 | Novozymes A/S | Detergents with enzymatic builder and bleach systems |
| CN106496618B (en) * | 2016-10-18 | 2022-02-08 | 浙江伟星实业发展股份有限公司 | Laser hollow-out processing liquid for fruit buttons and laser hollow-out fruit buttons |
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|---|---|---|---|---|
| GB852958A (en) * | 1956-08-07 | 1960-11-02 | Union Starch And Refining Comp | Sequestering composition comprising polyhydroxy carboxylic acids and process of making same |
| US3062878A (en) * | 1959-10-05 | 1962-11-06 | Olin Mathieson | Sugar sequestering agent |
| US3256203A (en) * | 1963-11-18 | 1966-06-14 | Nalco Chemical Co | Cooling water treatment and compositions useful therein |
| US3634392A (en) * | 1969-03-28 | 1972-01-11 | Procter & Gamble | Carboxymethylated derivatives of diand tri-saccharide compounds and detergent compositions containing them |
| GB1355998A (en) * | 1970-09-30 | 1974-06-12 | Unilever Ltd | Builders for detergent compositions |
| US4000083A (en) * | 1974-05-06 | 1976-12-28 | B°V° Chemie Combinatie Amsterdam C°C°A° | Sequestering agents |
| US4539131B1 (en) * | 1982-06-25 | 1990-09-04 | Lever Brothers Ltd | Solid detergent composition containing sodium perborate monohydrate having specified surface area |
| US4938961A (en) * | 1989-04-28 | 1990-07-03 | Geoffrey Collins | Organ preservation solution containing pokyethylene gycol and method of performing cardioplegia |
-
1989
- 1989-04-29 DE DE3914293A patent/DE3914293A1/en not_active Withdrawn
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1990
- 1990-03-22 CA CA002012836A patent/CA2012836C/en not_active Expired - Fee Related
- 1990-04-06 US US07/505,569 patent/US5069808A/en not_active Expired - Fee Related
- 1990-04-21 AT AT90107599T patent/ATE107348T1/en not_active IP Right Cessation
- 1990-04-21 EP EP90107599A patent/EP0395970B1/en not_active Expired - Lifetime
- 1990-04-21 ES ES90107599T patent/ES2057245T3/en not_active Expired - Lifetime
- 1990-04-21 DK DK90107599.4T patent/DK0395970T3/en active
- 1990-04-21 DE DE59006100T patent/DE59006100D1/en not_active Expired - Fee Related
- 1990-04-23 JP JP2105500A patent/JP2672175B2/en not_active Expired - Lifetime
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP3156475B1 (en) | 2015-10-16 | 2018-06-06 | Hans Georg Hagleitner | Liquid cleaning concentrate |
Also Published As
| Publication number | Publication date |
|---|---|
| DE59006100D1 (en) | 1994-07-21 |
| US5069808A (en) | 1991-12-03 |
| JP2672175B2 (en) | 1997-11-05 |
| DK0395970T3 (en) | 1994-07-04 |
| ES2057245T3 (en) | 1994-10-16 |
| ATE107348T1 (en) | 1994-07-15 |
| CA2012836A1 (en) | 1990-10-29 |
| JPH02305899A (en) | 1990-12-19 |
| CA2012836C (en) | 1999-06-29 |
| DE3914293A1 (en) | 1990-10-31 |
| EP0395970A1 (en) | 1990-11-07 |
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