EP1004655A2 - Automatic dishwashing composition - Google Patents
Automatic dishwashing composition Download PDFInfo
- Publication number
- EP1004655A2 EP1004655A2 EP99120429A EP99120429A EP1004655A2 EP 1004655 A2 EP1004655 A2 EP 1004655A2 EP 99120429 A EP99120429 A EP 99120429A EP 99120429 A EP99120429 A EP 99120429A EP 1004655 A2 EP1004655 A2 EP 1004655A2
- Authority
- EP
- European Patent Office
- Prior art keywords
- weight
- machine dishwashing
- dishwashing detergent
- detergent according
- disilicate
- 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.)
- Ceased
Links
- 238000004851 dishwashing Methods 0.000 title claims abstract description 65
- 239000000203 mixture Substances 0.000 title description 9
- 239000003599 detergent Substances 0.000 claims abstract description 84
- BPQQTUXANYXVAA-UHFFFAOYSA-N Orthosilicate Chemical compound [O-][Si]([O-])([O-])[O-] BPQQTUXANYXVAA-UHFFFAOYSA-N 0.000 claims abstract description 32
- 239000007788 liquid Substances 0.000 claims abstract description 10
- 229910052783 alkali metal Inorganic materials 0.000 claims abstract description 6
- 150000001340 alkali metals Chemical class 0.000 claims abstract description 6
- 229910052784 alkaline earth metal Inorganic materials 0.000 claims abstract description 5
- 150000001342 alkaline earth metals Chemical class 0.000 claims abstract description 5
- 239000001257 hydrogen Substances 0.000 claims abstract description 5
- 229910052739 hydrogen Inorganic materials 0.000 claims abstract description 5
- 238000004519 manufacturing process Methods 0.000 claims abstract description 5
- 235000011837 pasties Nutrition 0.000 claims abstract description 5
- OQEVSCYDUYRAAM-UHFFFAOYSA-N disodium;oxido-[oxido(oxo)silyl]oxy-oxosilane Chemical compound [Na+].[Na+].[O-][Si](=O)O[Si]([O-])=O OQEVSCYDUYRAAM-UHFFFAOYSA-N 0.000 claims description 35
- 239000004615 ingredient Substances 0.000 claims description 24
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 21
- 239000006185 dispersion Substances 0.000 claims description 20
- 239000004094 surface-active agent Substances 0.000 claims description 20
- 239000002270 dispersing agent Substances 0.000 claims description 19
- PMYUVOOOQDGQNW-UHFFFAOYSA-N hexasodium;trioxido(trioxidosilyloxy)silane Chemical compound [Na+].[Na+].[Na+].[Na+].[Na+].[Na+].[O-][Si]([O-])([O-])O[Si]([O-])([O-])[O-] PMYUVOOOQDGQNW-UHFFFAOYSA-N 0.000 claims description 19
- 239000006254 rheological additive Substances 0.000 claims description 18
- 239000007844 bleaching agent Substances 0.000 claims description 16
- 238000000034 method Methods 0.000 claims description 13
- 238000004140 cleaning Methods 0.000 claims description 12
- 239000011521 glass Substances 0.000 claims description 12
- 235000019832 sodium triphosphate Nutrition 0.000 claims description 12
- 239000004115 Sodium Silicate Substances 0.000 claims description 11
- -1 aliphatic alcohols Chemical class 0.000 claims description 11
- 238000005260 corrosion Methods 0.000 claims description 10
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 10
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 claims description 9
- 239000003513 alkali Substances 0.000 claims description 9
- 230000007797 corrosion Effects 0.000 claims description 9
- 229910004298 SiO 2 Inorganic materials 0.000 claims description 8
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 claims description 8
- 230000000737 periodic effect Effects 0.000 claims description 8
- 229920005646 polycarboxylate Polymers 0.000 claims description 8
- 235000019351 sodium silicates Nutrition 0.000 claims description 8
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 claims description 7
- 229910019142 PO4 Inorganic materials 0.000 claims description 7
- 239000000460 chlorine Substances 0.000 claims description 7
- 229910052801 chlorine Inorganic materials 0.000 claims description 7
- 239000006260 foam Substances 0.000 claims description 7
- 235000021317 phosphate Nutrition 0.000 claims description 7
- IAYPIBMASNFSPL-UHFFFAOYSA-N Ethylene oxide Chemical compound C1CO1 IAYPIBMASNFSPL-UHFFFAOYSA-N 0.000 claims description 6
- ABLZXFCXXLZCGV-UHFFFAOYSA-N Phosphorous acid Chemical class OP(O)=O ABLZXFCXXLZCGV-UHFFFAOYSA-N 0.000 claims description 6
- GOOHAUXETOMSMM-UHFFFAOYSA-N Propylene oxide Chemical group CC1CO1 GOOHAUXETOMSMM-UHFFFAOYSA-N 0.000 claims description 6
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical class OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 claims description 5
- 229910052910 alkali metal silicate Inorganic materials 0.000 claims description 5
- 230000002401 inhibitory effect Effects 0.000 claims description 5
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 4
- 229910052796 boron Inorganic materials 0.000 claims description 4
- 229920001577 copolymer Polymers 0.000 claims description 4
- 235000014113 dietary fatty acids Nutrition 0.000 claims description 4
- 239000000194 fatty acid Substances 0.000 claims description 4
- 229930195729 fatty acid Natural products 0.000 claims description 4
- 239000000945 filler Substances 0.000 claims description 4
- 125000004435 hydrogen atom Chemical class [H]* 0.000 claims description 4
- 239000001301 oxygen Substances 0.000 claims description 4
- 229910052760 oxygen Inorganic materials 0.000 claims description 4
- 229910052698 phosphorus Inorganic materials 0.000 claims description 4
- 229920001522 polyglycol ester Polymers 0.000 claims description 4
- 229920000642 polymer Polymers 0.000 claims description 4
- 229910000029 sodium carbonate Inorganic materials 0.000 claims description 4
- ZOXJGFHDIHLPTG-UHFFFAOYSA-N Boron Chemical compound [B] ZOXJGFHDIHLPTG-UHFFFAOYSA-N 0.000 claims description 3
- 229920002134 Carboxymethyl cellulose Polymers 0.000 claims description 3
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 claims description 3
- 150000001412 amines Chemical class 0.000 claims description 3
- 239000012736 aqueous medium Substances 0.000 claims description 3
- 239000001768 carboxy methyl cellulose Substances 0.000 claims description 3
- 235000010948 carboxy methyl cellulose Nutrition 0.000 claims description 3
- 239000008112 carboxymethyl-cellulose Substances 0.000 claims description 3
- 239000008139 complexing agent Substances 0.000 claims description 3
- 239000000975 dye Substances 0.000 claims description 3
- 150000002170 ethers Chemical class 0.000 claims description 3
- 150000002191 fatty alcohols Chemical class 0.000 claims description 3
- 239000003112 inhibitor Substances 0.000 claims description 3
- 239000002304 perfume Substances 0.000 claims description 3
- 150000003013 phosphoric acid derivatives Chemical class 0.000 claims description 3
- 239000011574 phosphorus Substances 0.000 claims description 3
- 239000010695 polyglycol Substances 0.000 claims description 3
- 229920000151 polyglycol Polymers 0.000 claims description 3
- 150000008050 dialkyl sulfates Chemical class 0.000 claims description 2
- 229910052615 phyllosilicate Inorganic materials 0.000 claims description 2
- 239000000654 additive Substances 0.000 claims 1
- 230000000996 additive effect Effects 0.000 claims 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 abstract 1
- 229910021478 group 5 element Inorganic materials 0.000 abstract 1
- 239000011734 sodium Substances 0.000 description 13
- 229910052708 sodium Inorganic materials 0.000 description 12
- 239000000047 product Substances 0.000 description 10
- 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 9
- 239000000969 carrier Substances 0.000 description 9
- NTHWMYGWWRZVTN-UHFFFAOYSA-N sodium silicate Chemical compound [Na+].[Na+].[O-][Si]([O-])=O NTHWMYGWWRZVTN-UHFFFAOYSA-N 0.000 description 9
- 239000013530 defoamer Substances 0.000 description 7
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 6
- 230000000694 effects Effects 0.000 description 6
- 239000002253 acid Substances 0.000 description 5
- 229910052573 porcelain Inorganic materials 0.000 description 5
- 239000005708 Sodium hypochlorite Substances 0.000 description 4
- 150000007513 acids Chemical class 0.000 description 4
- 239000008187 granular material Substances 0.000 description 4
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 description 4
- 239000010452 phosphate Substances 0.000 description 4
- 235000019353 potassium silicate Nutrition 0.000 description 4
- SUKJFIGYRHOWBL-UHFFFAOYSA-N sodium hypochlorite Chemical compound [Na+].Cl[O-] SUKJFIGYRHOWBL-UHFFFAOYSA-N 0.000 description 4
- 239000000243 solution Substances 0.000 description 4
- 239000013543 active substance Substances 0.000 description 3
- 150000001335 aliphatic alkanes Chemical class 0.000 description 3
- 239000003795 chemical substances by application Substances 0.000 description 3
- 239000013065 commercial product Substances 0.000 description 3
- 150000001875 compounds Chemical class 0.000 description 3
- 229920001495 poly(sodium acrylate) polymer Polymers 0.000 description 3
- 229920001296 polysiloxane Polymers 0.000 description 3
- 150000004760 silicates Chemical class 0.000 description 3
- 239000000377 silicon dioxide Substances 0.000 description 3
- 235000012239 silicon dioxide Nutrition 0.000 description 3
- KKCBUQHMOMHUOY-UHFFFAOYSA-N sodium oxide Chemical compound [O-2].[Na+].[Na+] KKCBUQHMOMHUOY-UHFFFAOYSA-N 0.000 description 3
- NNMHYFLPFNGQFZ-UHFFFAOYSA-M sodium polyacrylate Chemical compound [Na+].[O-]C(=O)C=C NNMHYFLPFNGQFZ-UHFFFAOYSA-M 0.000 description 3
- 229910052911 sodium silicate Inorganic materials 0.000 description 3
- 239000007787 solid Substances 0.000 description 3
- BDHFUVZGWQCTTF-UHFFFAOYSA-M sulfonate Chemical compound [O-]S(=O)=O BDHFUVZGWQCTTF-UHFFFAOYSA-M 0.000 description 3
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 description 2
- NIXOWILDQLNWCW-UHFFFAOYSA-N 2-Propenoic acid Natural products OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 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 2
- KRHYYFGTRYWZRS-UHFFFAOYSA-N Fluorane Chemical compound F KRHYYFGTRYWZRS-UHFFFAOYSA-N 0.000 description 2
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 description 2
- OFOBLEOULBTSOW-UHFFFAOYSA-N Propanedioic acid Natural products OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 0.000 description 2
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 2
- 239000012190 activator Substances 0.000 description 2
- 239000000440 bentonite Substances 0.000 description 2
- 229910000278 bentonite Inorganic materials 0.000 description 2
- SVPXDRXYRYOSEX-UHFFFAOYSA-N bentoquatam Chemical compound O.O=[Si]=O.O=[Al]O[Al]=O SVPXDRXYRYOSEX-UHFFFAOYSA-N 0.000 description 2
- 239000011575 calcium Substances 0.000 description 2
- 239000003054 catalyst Substances 0.000 description 2
- 239000002734 clay mineral Substances 0.000 description 2
- SNRUBQQJIBEYMU-UHFFFAOYSA-N dodecane Chemical compound CCCCCCCCCCCC SNRUBQQJIBEYMU-UHFFFAOYSA-N 0.000 description 2
- 239000010794 food waste Substances 0.000 description 2
- 150000004687 hexahydrates Chemical class 0.000 description 2
- 229910052749 magnesium Inorganic materials 0.000 description 2
- 239000011777 magnesium Substances 0.000 description 2
- VZCYOOQTPOCHFL-UPHRSURJSA-N maleic acid Chemical compound OC(=O)\C=C/C(O)=O VZCYOOQTPOCHFL-UPHRSURJSA-N 0.000 description 2
- 239000011976 maleic acid Substances 0.000 description 2
- 239000002245 particle Substances 0.000 description 2
- 150000003009 phosphonic acids Chemical class 0.000 description 2
- 229920005606 polypropylene copolymer Polymers 0.000 description 2
- 229910052700 potassium Inorganic materials 0.000 description 2
- 239000000843 powder Substances 0.000 description 2
- 102000004169 proteins and genes Human genes 0.000 description 2
- 108090000623 proteins and genes Proteins 0.000 description 2
- 150000003839 salts Chemical class 0.000 description 2
- 239000002562 thickening agent Substances 0.000 description 2
- VZCYOOQTPOCHFL-UHFFFAOYSA-N trans-butenedioic acid Natural products OC(=O)C=CC(O)=O VZCYOOQTPOCHFL-UHFFFAOYSA-N 0.000 description 2
- 238000005406 washing Methods 0.000 description 2
- 102000013142 Amylases Human genes 0.000 description 1
- 108010065511 Amylases Proteins 0.000 description 1
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 description 1
- KXDHJXZQYSOELW-UHFFFAOYSA-N Carbamic acid Chemical class NC(O)=O KXDHJXZQYSOELW-UHFFFAOYSA-N 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
- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical compound [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 description 1
- 108091005804 Peptidases Proteins 0.000 description 1
- 229920000388 Polyphosphate Polymers 0.000 description 1
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 description 1
- 102100037486 Reverse transcriptase/ribonuclease H Human genes 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
- 229920002125 Sokalan® Polymers 0.000 description 1
- HRKAMJBPFPHCSD-UHFFFAOYSA-N Tri-isobutylphosphate Chemical compound CC(C)COP(=O)(OCC(C)C)OCC(C)C HRKAMJBPFPHCSD-UHFFFAOYSA-N 0.000 description 1
- XTXRWKRVRITETP-UHFFFAOYSA-N Vinyl acetate Chemical compound CC(=O)OC=C XTXRWKRVRITETP-UHFFFAOYSA-N 0.000 description 1
- 229920004482 WACKER® Polymers 0.000 description 1
- MPTNZBNHPVUNQP-UHFFFAOYSA-N [Si]([O-])([O-])(O)O[Si](O)(O)O.[K+].[Na+] Chemical compound [Si]([O-])([O-])(O)O[Si](O)(O)O.[K+].[Na+] MPTNZBNHPVUNQP-UHFFFAOYSA-N 0.000 description 1
- 150000004973 alkali metal peroxides Chemical class 0.000 description 1
- 150000004974 alkaline earth metal peroxides Chemical class 0.000 description 1
- 229910052782 aluminium Inorganic materials 0.000 description 1
- 229910052787 antimony Inorganic materials 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 229910052785 arsenic Inorganic materials 0.000 description 1
- 229910052788 barium Inorganic materials 0.000 description 1
- 229910052790 beryllium Inorganic materials 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 229910052797 bismuth Inorganic materials 0.000 description 1
- 238000004061 bleaching Methods 0.000 description 1
- 229910052791 calcium Inorganic materials 0.000 description 1
- 229910001424 calcium ion Inorganic materials 0.000 description 1
- BVKZGUZCCUSVTD-UHFFFAOYSA-N carbonic acid Chemical class OC(O)=O BVKZGUZCCUSVTD-UHFFFAOYSA-N 0.000 description 1
- 150000004649 carbonic acid derivatives Chemical class 0.000 description 1
- 239000003518 caustics Substances 0.000 description 1
- 239000012459 cleaning agent Substances 0.000 description 1
- 239000003086 colorant Substances 0.000 description 1
- 230000000052 comparative effect Effects 0.000 description 1
- 238000011109 contamination Methods 0.000 description 1
- ZSRDPISMHNGBDJ-UHFFFAOYSA-N cyclononane-1,4,7-triamine Chemical class NC1CCC(N)CCC(N)CC1 ZSRDPISMHNGBDJ-UHFFFAOYSA-N 0.000 description 1
- CEJLBZWIKQJOAT-UHFFFAOYSA-N dichloroisocyanuric acid Chemical compound ClN1C(=O)NC(=O)N(Cl)C1=O CEJLBZWIKQJOAT-UHFFFAOYSA-N 0.000 description 1
- VTIIJXUACCWYHX-UHFFFAOYSA-L disodium;carboxylatooxy carbonate Chemical compound [Na+].[Na+].[O-]C(=O)OOC([O-])=O VTIIJXUACCWYHX-UHFFFAOYSA-L 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 238000011156 evaluation Methods 0.000 description 1
- 150000004665 fatty acids Chemical class 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 229910052733 gallium Inorganic materials 0.000 description 1
- 239000000499 gel Substances 0.000 description 1
- 150000004679 hydroxides Chemical class 0.000 description 1
- 229910052738 indium Inorganic materials 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 230000002427 irreversible effect Effects 0.000 description 1
- NLYAJNPCOHFWQQ-UHFFFAOYSA-N kaolin Chemical compound O.O.O=[Al]O[Si](=O)O[Si](=O)O[Al]=O NLYAJNPCOHFWQQ-UHFFFAOYSA-N 0.000 description 1
- 229940094522 laponite Drugs 0.000 description 1
- 239000003446 ligand Substances 0.000 description 1
- 229910052744 lithium Inorganic materials 0.000 description 1
- XCOBTUNSZUJCDH-UHFFFAOYSA-B lithium magnesium sodium silicate Chemical compound [Li+].[Li+].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[Na+].[Na+].[Mg+2].[Mg+2].[Mg+2].[Mg+2].[Mg+2].[Mg+2].[Mg+2].[Mg+2].[Mg+2].[Mg+2].[Mg+2].[Mg+2].[Mg+2].[Mg+2].[Mg+2].[Mg+2].O1[Si](O2)([O-])O[Si]3([O-])O[Si]1([O-])O[Si]2([O-])O3.O1[Si](O2)([O-])O[Si]3([O-])O[Si]1([O-])O[Si]2([O-])O3.O1[Si](O2)([O-])O[Si]3([O-])O[Si]1([O-])O[Si]2([O-])O3.O1[Si](O2)([O-])O[Si]3([O-])O[Si]1([O-])O[Si]2([O-])O3.O1[Si](O2)([O-])O[Si]3([O-])O[Si]1([O-])O[Si]2([O-])O3.O1[Si](O2)([O-])O[Si]3([O-])O[Si]1([O-])O[Si]2([O-])O3 XCOBTUNSZUJCDH-UHFFFAOYSA-B 0.000 description 1
- 230000007774 longterm Effects 0.000 description 1
- 229910001425 magnesium ion Inorganic materials 0.000 description 1
- 230000014759 maintenance of location Effects 0.000 description 1
- 229910052748 manganese Inorganic materials 0.000 description 1
- 239000011572 manganese Substances 0.000 description 1
- 239000000178 monomer Substances 0.000 description 1
- VXAPDXVBDZRZKP-UHFFFAOYSA-N nitric acid phosphoric acid Chemical compound O[N+]([O-])=O.OP(O)(O)=O VXAPDXVBDZRZKP-UHFFFAOYSA-N 0.000 description 1
- 230000003287 optical effect Effects 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
- UEZVMMHDMIWARA-UHFFFAOYSA-M phosphonate Chemical compound [O-]P(=O)=O UEZVMMHDMIWARA-UHFFFAOYSA-M 0.000 description 1
- 150000003014 phosphoric acid esters Chemical class 0.000 description 1
- 239000001205 polyphosphate Substances 0.000 description 1
- 235000011176 polyphosphates Nutrition 0.000 description 1
- 239000011591 potassium Substances 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 229910000275 saponite Inorganic materials 0.000 description 1
- 229940045872 sodium percarbonate Drugs 0.000 description 1
- 229910052938 sodium sulfate Inorganic materials 0.000 description 1
- 235000011152 sodium sulphate Nutrition 0.000 description 1
- SZHIIIPPJJXYRY-UHFFFAOYSA-M sodium;2-methylprop-2-ene-1-sulfonate Chemical compound [Na+].CC(=C)CS([O-])(=O)=O SZHIIIPPJJXYRY-UHFFFAOYSA-M 0.000 description 1
- MWNQXXOSWHCCOZ-UHFFFAOYSA-L sodium;oxido carbonate Chemical compound [Na+].[O-]OC([O-])=O MWNQXXOSWHCCOZ-UHFFFAOYSA-L 0.000 description 1
- 239000013042 solid detergent Substances 0.000 description 1
- 229910001220 stainless steel Inorganic materials 0.000 description 1
- 239000010935 stainless steel Substances 0.000 description 1
- 229910052712 strontium Inorganic materials 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 230000003319 supportive effect Effects 0.000 description 1
- FRPJTGXMTIIFIT-UHFFFAOYSA-N tetraacetylethylenediamine Chemical group CC(=O)C(N)(C(C)=O)C(N)(C(C)=O)C(C)=O FRPJTGXMTIIFIT-UHFFFAOYSA-N 0.000 description 1
- 229910052716 thallium Inorganic materials 0.000 description 1
- 230000009974 thixotropic effect Effects 0.000 description 1
- AZJYLVAUMGUUBL-UHFFFAOYSA-A u1qj22mc8e Chemical compound [F-].[F-].[F-].[F-].[F-].[F-].[F-].[F-].[F-].[F-].[F-].[F-].[F-].[F-].[F-].[F-].[F-].[F-].[Na+].[Na+].[Na+].[Na+].[Na+].[Na+].[Na+].[Na+].[Na+].[Na+].[Mg+2].[Mg+2].[Mg+2].[Mg+2].[Mg+2].[Mg+2].[Mg+2].[Mg+2].[Mg+2].[Mg+2].[Mg+2].[Mg+2].[Mg+2].[Mg+2].[Mg+2].[Mg+2].O=[Si]=O.O=[Si]=O.O=[Si]=O.O1[Si](O2)([O-])O[Si]3([O-])O[Si]1([O-])O[Si]2([O-])O3.O1[Si](O2)([O-])O[Si]3([O-])O[Si]1([O-])O[Si]2([O-])O3.O1[Si](O2)([O-])O[Si]3([O-])O[Si]1([O-])O[Si]2([O-])O3.O1[Si](O2)([O-])O[Si]3([O-])O[Si]1([O-])O[Si]2([O-])O3.O1[Si](O2)([O-])O[Si]3([O-])O[Si]1([O-])O[Si]2([O-])O3.O1[Si](O2)([O-])O[Si]3([O-])O[Si]1([O-])O[Si]2([O-])O3 AZJYLVAUMGUUBL-UHFFFAOYSA-A 0.000 description 1
- 238000011179 visual inspection Methods 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
- C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
- C11D17/00—Detergent materials or soaps characterised by their shape or physical properties
- C11D17/0008—Detergent materials or soaps characterised by their shape or physical properties aqueous liquid non soap compositions
- C11D17/003—Colloidal solutions, e.g. gels; Thixotropic solutions or pastes
-
- C—CHEMISTRY; METALLURGY
- C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
- C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
- C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
- C11D3/02—Inorganic compounds ; Elemental compounds
- C11D3/04—Water-soluble compounds
- C11D3/08—Silicates
-
- 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
- C11D3/12—Water-insoluble compounds
- C11D3/124—Silicon containing, e.g. silica, silex, quartz or glass beads
- C11D3/1246—Silicates, e.g. diatomaceous earth
- C11D3/1253—Layer silicates, e.g. talcum, kaolin, clay, bentonite, smectite, montmorillonite, hectorite or attapulgite
- C11D3/1273—Crystalline layered silicates of type NaMeSixO2x+1YH2O
-
- C—CHEMISTRY; METALLURGY
- C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
- C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
- C11D1/00—Detergent compositions based essentially on surface-active compounds; Use of these compounds as a detergent
- C11D1/02—Anionic compounds
- C11D1/12—Sulfonic acids or sulfuric acid esters; Salts thereof
- C11D1/14—Sulfonic acids or sulfuric acid esters; Salts thereof derived from aliphatic hydrocarbons or mono-alcohols
- C11D1/143—Sulfonic acid esters
-
- C—CHEMISTRY; METALLURGY
- C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
- C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
- C11D1/00—Detergent compositions based essentially on surface-active compounds; Use of these compounds as a detergent
- C11D1/02—Anionic compounds
- C11D1/12—Sulfonic acids or sulfuric acid esters; Salts thereof
- C11D1/14—Sulfonic acids or sulfuric acid esters; Salts thereof derived from aliphatic hydrocarbons or mono-alcohols
- C11D1/146—Sulfuric acid esters
-
- C—CHEMISTRY; METALLURGY
- C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
- C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
- C11D1/00—Detergent compositions based essentially on surface-active compounds; Use of these compounds as a detergent
- C11D1/66—Non-ionic compounds
- C11D1/72—Ethers of polyoxyalkylene glycols
-
- C—CHEMISTRY; METALLURGY
- C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
- C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
- C11D1/00—Detergent compositions based essentially on surface-active compounds; Use of these compounds as a detergent
- C11D1/66—Non-ionic compounds
- C11D1/75—Amino oxides
-
- C—CHEMISTRY; METALLURGY
- C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
- C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
- C11D1/00—Detergent compositions based essentially on surface-active compounds; Use of these compounds as a detergent
- C11D1/66—Non-ionic compounds
- C11D1/755—Sulfoxides
Definitions
- the invention relates to a liquid to pasty dishwasher detergent, a method for its manufacture and its use.
- Liquid dishwashing detergents such as those used especially in the area of large-scale commercial consumption, are unsuitable for use in automatic household dishwashing machines in the household area, primarily because of their insufficiently low viscosity and high alkalinity, since these products come with must be labeled "caustic" and therefore pose a great security risk in the household. In addition, retention of the dishwashing liquid in the usual household dosing devices is not guaranteed in most cases.
- the commercially available gel-like or thixotropic dishwashing detergents contain more or less large amounts of alkali silicates, generally in the form of aqueous solutions (water glass), for example in the ratio Na 2 O: SiO 2 of 1: 2 to 1: 3.3, to achieve the desired alkalinity and to serve as anti-corrosion agents for the glaze and decor of porcelain.
- dishwashing detergents with such decorative and glaze protection have the disadvantage that they are on the rest of the dishes, preferably on glasses Deposits of different thicknesses form, which are initially in bright tarnish colors, later in whitish-cloudy, bluish-tinged, sticky toppings and only with extremely strong ones Acids, for example a hydrofluoric acid / sulfuric acid mixture, are removed can.
- Such dishwashing detergents are therefore not suitable for long-term use.
- the invention is therefore based on the object of a non-solid dishwasher detergent to make available that compared to the prior art with a good cleaning effect a reduced degree of corrosion, especially on glasses and porcelain plates as well results in a reduced level of deposits.
- a dishwasher detergent of the type mentioned at the beginning characterized in that, in addition to the usual dishwasher detergent ingredients, it is a crystalline, layered silicate of the general formula a A 2 O ⁇ b BO ⁇ c C 2 O 3 ⁇ d D 2 O 5 ⁇ e SiO 2 ⁇ f H 2 O contains, in which A is an alkali metal and / or hydrogen, B is an alkaline earth metal, C is an element of the third main group of the periodic table and D is an element of the fifth main group of the periodic table and furthermore applies: 0 ⁇ a ⁇ 1; 0 ⁇ b ⁇ 0.5; 0 ⁇ c / e ⁇ 0.05; 0 ⁇ d / e ⁇ 0.25; 1.9 ⁇ e ⁇ 4; 0 ⁇ f ⁇ 20.
- the machine dishwashing detergent particularly preferably contains 5 to 30% by weight of the crystalline layered silicate.
- the crystalline layered silicate is preferably essentially Disodium disilicate.
- the layered crystalline disodium disilicate is preferably present (the following information refer to% by weight) from 1 to 40% of alpha disodium disilicate:, 0 to 50% of beta disodium disilicate, 50 to 98% of delta disodium disilicate and 0 to 40% of non-layer silicate Sodium silicates.
- layered crystalline disodium disilicate from 0 to 40% of alpha disodium disilicate, 20 to 98% of beta disodium disilicate, 0 to 40% of delta disodium disilicate and 0 to 50% of non-layer silicate Sodium silicates.
- the layered crystalline disodium disilicate is present from 20 to 98% of alpha disodium disilicate, 0 to 40% of beta disodium disilicate, 0 to 50% of delta disodium disilicate and 0 to 50% of non-layer silicate Sodium silicates.
- alpha, beta and delta disodium disilicate are known and can be used, for example can be found in EP 0 164 514.
- the crystalline layered silicate in the dishwasher detergent according to the invention preferably contains up to 10 mol% boron, based on SiO 2 .
- the crystalline layered silicate in the dishwasher detergent according to the invention preferably contains up to 50 mol% of phosphorus, based on SiO 2 .
- the machine dishwashing detergent preferably also contains at least one surfactant and / or one Bleaching agent and / or a rheological additive and / or a dispersing agent and / or one Dispersion carrier.
- the machine dishwashing detergent preferably contains long-chain block polymers as surfactants aliphatic alcohols with ethylene oxide or propylene oxide groups, modified fatty alcohol polyglycol ethers, Mono- and dialkyl sulfates, alkanesulfonates, amine oxides and / or fatty acid methyl polyglycol esters.
- the machine dishwashing detergent preferably contains active chlorine carriers as bleaching agents and / or active oxygen carriers.
- the machine dishwashing detergent preferably contains as a rheological additive and / or dispersant Carboxymethyl cellulose, polycarboxylates, phosphonates and / or synthetic Tone.
- the machine dishwashing detergent preferably contains ethylene glycols as the dispersion carrier, Cooligo / copolymers of propylene oxide and ethylene oxide and / or water.
- compositions mentioned above are sodium disilicate essentially disodium disilicate.
- the machine dishwashing detergent according to the invention preferably has corrosion-inhibiting properties on.
- the machine dishwashing detergent according to the invention particularly preferably has corrosion-inhibiting agents Properties especially on glasses.
- the machine dishwashing detergent according to the invention preferably has an increased cleaning performance on.
- the invention also relates to a method for producing a dishwasher detergent, characterized in that in a submitted aqueous medium and / or Dispersion carriers first dissolve alkali carriers, then rheological additives and / or dispersants admixed, cools to room temperature, adds the other components and on The crystalline layered silicate is added at the end of the mixing process.
- the alkali carrier is preferably sodium carbonate, sodium hydroxide, potassium hydroxide and / or around water-soluble alkali silicates.
- the components are preferably surfactants, bleaches, fillers, builders, Cobuilders, phosphates, organic complexing agents, foam inhibitors, perfumes and / or dyes and / or possibly other ingredients for machine dishwashing detergents.
- the invention also relates to the use of the dishwasher detergent according to the invention for automatic dishwashing.
- the layered silicate contained in the machine dishwashing detergent according to the invention which has the general formula as described above a A 2 O ⁇ b BO ⁇ c C 2 O 3 ⁇ d D 2 O 5 ⁇ e SiO 2 ⁇ f H 2 O in which A is an alkali metal and / or hydrogen, B is an alkaline earth metal, C is an element of the third main group of the periodic table and D is an element of the fifth main group of the periodic table (and the following also applies: 0 ⁇ a ⁇ 1; 0 ⁇ b ⁇ 0 , 5; 0 ⁇ c / e ⁇ 0.05; 0 ⁇ d / e ⁇ 0.25; 1.9 ⁇ e ⁇ 4; 0 ⁇ f ⁇ 20), may in particular also contain calcium and magnesium ions.
- ions are those of the third and fifth main group of the periodic table, these include above all boron or phosphorus. This is especially true if a disodium disilicate as layered silicate, as described above and below is used.
- the layered silicate can also be a sodium potassium disilicate, in which the Sodium to potassium ratio can be varied within a wide range.
- layered silicates of the above formula which are essentially Contain alkali metals (Li, Na, K) and / or hydrogen, and in those low Shares in the above-mentioned alkaline earth metals (Be, Mg, Ca, Sr, Ba) and elements of third (B, Al, Ga, In, Tl) and fifth main group (P, As, Sb, Bi) of the periodic table are.
- the aforementioned silicate is either used in a finely ground form, i.e. as a powder with an average particle diameter from 1 to 200 microns, or in easily dispersible form e.g. as pressed granules, that when working into the dishwashing dispersion into microscopic particles crushed.
- Sodium disilicate with polycarboxylates are also particularly preferred Sodium disilicate with polycarboxylates, as described in DE-OS 197 19 888 are.
- Preferred polycarboxylates are homo- or any combination of copolymers the monomers acrylic acid and / or maleic acid and / or vinyl acetate and / or methallylsulfonate.
- the preferred compound of polycarboxylates and crystalline, layered Sodium disilicate consists of 50 to 98% by weight of said silicate and 2 to 50% by weight polycarboxylate.
- dishwasher components some of which have already been mentioned above, such as Fillers, alkali carriers, surfactants, builders, bleaches, rheological additives and dispersants, Foam inhibitors and possibly perfumes and dyes and others can Substances that are already well known for these purposes.
- Sodium sulfate can be used as a filler e.g. Sodium sulfate.
- Oxides, hydroxides, carbonates and silicates of the alkali metals are preferred as alkali carriers Sodium carbonate and / or sodium hydroxide and / or potassium hydroxide or water soluble Called alkali silicates.
- Chlorine-stable block polymers of long-chain aliphatic alcohols are also included as surfactants Ethylene oxide or propylene oxide groups or modified fatty alcohol polyglycol ethers or Mono- and di-alkyl sulfates or alkanesulfonates or amine oxides or fatty acid methyl polyglycol esters suitable.
- alkali phosphates preferably Pentaalkali nitrate phosphate, anhydrous and / anhydrated and / or hexahydrate used become.
- Organic complexing agents such as Mono-, di-, tri-, oligo- and / or polycarboxylic acids, hydroxycarboxylic acids, aminocarboxylic acids and phosphonic acids, preferably in the form of their water-soluble salts.
- Preferred Oligocarboxylic acids are citric, tartaric, maleic, etc. These are preferred used together with the crystalline, layered silicate as press granulate.
- Active chlorine carriers such as sodium dichloroisocyanurate or come as preferred bleaching agents
- Sodium hypochlorite solution (chlorine bleach) and active oxygen carriers such as hydrogen peroxide, Alkali metal peroxides, alkaline earth metal peroxides, alkali perborate, persulfate, percarbonate, -perphosphate and peroxycarboxylic acids and their salts such as dodecane peroxidicarboxylic acid or magnesium peroxiphthalate.
- Bleach activators or catalysts can also be used.
- a common one Bleach activator is tetraacetylethylene diamine.
- Common bleaching catalysts are complexes of Manganese with special ligands e.g. Derivatives of 1,4,7-triaminocyclononane.
- Preferred rheological additives and dispersing agents are carboxymethyl cellulose, Polycarboxylates, phosphonates or synthetic clays.
- Clays which can be used according to the invention are naturally occurring activated and partly modified Clay minerals such as Bentone grades from Rheox or synthetic clay minerals such as the Laponite grades from Laporte or synthetic hectorite from the SKS-21 type Hoechst and synthetic saponite type SKS-20 from Hoechst. More suitable Clays are known to the person skilled in the art and can be found in the manufacturer's catalogs.
- Dissolved alkali silicates or mono-, oligo- and polyphosphates can be used in the dispersion act supportive.
- Monomeric, oligomeric or polymeric can be used as the dispersion carrier (liquid component)
- Ethylene glycol or cooligo / copolymers of propylene oxide and ethylene oxide and / or water be used.
- Foam in dishwashers mostly caused by foam-producing surfactants or food residues containing protein causes a reduction in cleaning performance. Therefore, it is necessary to use a foam presser or foam damper to clean the dishes to add, for example chlorine-stable phosphoric acid esters, such as triisobutyl phosphate (Defoamer TIP from Clariant GmbH), or well-known silicones like the SP types from Wacker Chemie GmbH.
- chlorine-stable phosphoric acid esters such as triisobutyl phosphate (Defoamer TIP from Clariant GmbH), or well-known silicones like the SP types from Wacker Chemie GmbH.
- the aforementioned components can be used in the dishwasher detergent according to the invention individually or in mixtures in addition to the crystalline layered silicates, in particular Sodium disilicates (e.g. type SKS-6 from Clariant GmbH) may be included.
- Sodium disilicates e.g. type SKS-6 from Clariant GmbH
- the consistency of the mixtures according to the invention can be of low viscosity / liquid until pasty / gelatinous.
- Machine dishwashing detergents according to the invention can contain phosphate as well be phosphate free.
- alkali carriers such as sodium carbonate and / or sodium hydroxide and / or sodium water glass
- rheological additives and / or dispersants preferably polycarboxylates and / or phosphonic acids
- Components such as bleach, surfactant and builder (phosphate)
- the crystalline layered silicate is added.
- the mixing is preferably carried out under the action of strong shear forces e.g. With usual dispensers, high-shear mixers from Haake & Kunkel (Ultraturrax (TM)) or Impeller, propeller or turbine stirrers.
- strong shear forces e.g. with usual dispensers, high-shear mixers from Haake & Kunkel (Ultraturrax (TM)) or Impeller, propeller or turbine stirrers.
- the machine dishwashing detergents according to the invention are notable for good cleaning properties even with critical soiling such as burnt-on protein-containing food residues out. Furthermore, they show a high chlorine or active oxygen stability.
- the dishwasher detergents according to the invention are preferably used in household dishwashers used, but can also be used in commercial dishwashers.
- Standard tableware cleaner gels are used as a comparison based on phosphate and a test mixture without adding (according to the invention) crystalline layered silicate.
- the pH value of the cleaning liquors became immediately after filtering off the contamination then determined using a glass electrode.
- Example 1 formation of deposits on wash ware
- compositions D to H according to the invention became shaped and shaped in comparison to the commercial products B and C checked for irreversible damage.
- Porcelain plates and cups as well Stainless steel cutlery served as ballast for filling the prescribed amount of wash ware 12 place settings.
- the test is carried out according to DIN V ENV 12875-1: April 1998, mechanical Dishwasher resistance of household goods, part 1.
- the dosage of Test cleaner deviates from the pre-standard, there were 40 g of liquid test mixture in each Cleaning cycle and 3 ml of rinse aid dosed in the final rinse cycle of the test dishwasher.
- Method 1 Determination of the deposits on the wash ware
- the number of rinses is determined after which a visible cloudiness occurs for the first time.
- grade daylight Black box " 0 no cloudiness no cloudiness 1 no cloudiness very slight turbidity / iridescence 2nd no cloudiness slight clouding / iridescence 3rd very slight turbidity / iridescence clear cloudiness 4th slight clouding / iridescence ------ 5 clear cloudiness ------
- the arithmetic mean formed from the sum of the ratings and the number of glasses, gives the grade for the damage occurred.
- the machine dishwashing detergents A to I were tested for their cleaning effect in three household dishwashers Miele G 688 SC based on DIN standard draft 44990 and the IKW method.
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Abstract
Description
Die Erfindung betrifft ein flüssiges bis pastöses Maschinengeschirrspülmittel, ein Verfahren zu seiner Herstellung und seine Verwendung.The invention relates to a liquid to pasty dishwasher detergent, a method for its manufacture and its use.
Feste Reinigungsmittel für das maschinelle Geschirrspülen werden überwiegend in Pulver- bzw. Granulatform (Agglomerate) angeboten. Ein gravierender Nachteil dieser Art fester Reinigungsmittel besteht darin, daß wegen der Hygroskopizität einzelner Rohstoffe bei Zutritt von geringen Mengen an Feuchtigkeit eine starke Neigung zum Verbacken oder Verklumpen besteht. Dies kann teilweise zu einem Verlust der Reinigungswirkung führen und wirkt zudem auf den Anwender aus optischen Gründen qualitätsmindernd.Solid detergents for automatic dishwashing are mainly used in powder or Granular form (agglomerates) offered. A serious disadvantage of this type of solid cleaning agent is that due to the hygroscopicity of individual raw materials upon entry from small amounts of moisture a strong tendency to cake or clump consists. This can sometimes lead to a loss of the cleaning effect and also works on the user for optical reasons quality-reducing.
Flüssige Geschirrspülmittel, wie sie speziell im Bereich des gewerblichen Großverbrauchs verwendet werden, sind vor allem wegen ihrer unzureichend geringen Viskosität und ihrer hohen Alkalität für den Einsatz in automatischen Haushaltsgeschirrspülmaschinen im Haushaltsbereich ungeeignet, da diese Produkte mit ätzend" gekennzeichnet werden müssen und somit im Haushalt ein großes Sicherheitsrisiko darstellen. Daneben ist die Rückhaltung des Geschirrspülmittels in den haushaltsüblichen Dosiergeräten in den meisten Fällen nicht gewährleistet.Liquid dishwashing detergents, such as those used especially in the area of large-scale commercial consumption, are unsuitable for use in automatic household dishwashing machines in the household area, primarily because of their insufficiently low viscosity and high alkalinity, since these products come with must be labeled "caustic" and therefore pose a great security risk in the household. In addition, retention of the dishwashing liquid in the usual household dosing devices is not guaranteed in most cases.
Die handelsüblichen gelförmigen oder thixotropen Geschirreinigungsmittel enthalten mehr oder weniger große Mengen Alkalisilikate, im allgemeinen in Form wäßriger Lösungen (Wasserglas), beispielsweise im Verhältnis Na2O: SiO2 von 1: 2 bis 1: 3,3, die zum Erreichen der gewünschten Alkalität und als Korrosionschutzmittel für die Glasur und das Dekor von Porzellan dienen sollen.The commercially available gel-like or thixotropic dishwashing detergents contain more or less large amounts of alkali silicates, generally in the form of aqueous solutions (water glass), for example in the ratio Na 2 O: SiO 2 of 1: 2 to 1: 3.3, to achieve the desired alkalinity and to serve as anti-corrosion agents for the glaze and decor of porcelain.
Es hat sich aber gezeigt, daß Geschirreinigungsmittel mit einem derartigen Dekor- und Glasurschutz den Nachteil haben, daß sie auf dem übrigen Geschirrgut, bevorzugt auf Gläsern unterschiedlich starke Ablagerungen bilden, die sich zunächst in bunten Anlauffarben, später in weißlich-trüben blaustichigen festhaftenden Belägen darstellen und nur mit extrem starken Säuren, beispielsweise einem Fluorwasserstoffsäure- / Schwefelsäure- Gemisch, entfernt werden können. Solche Geschirreinigungsmittel sind also für den Dauergebrauch nicht geeignet.However, it has been shown that dishwashing detergents with such decorative and glaze protection have the disadvantage that they are on the rest of the dishes, preferably on glasses Deposits of different thicknesses form, which are initially in bright tarnish colors, later in whitish-cloudy, bluish-tinged, sticky toppings and only with extremely strong ones Acids, for example a hydrofluoric acid / sulfuric acid mixture, are removed can. Such dishwashing detergents are therefore not suitable for long-term use.
Der Erfindung liegt daher die Aufgabe zugrunde, ein nichtfestes Maschinengeschirrspülmittel zur Verfügung zu stellen, das gegenüber dem Stand der Technik bei guter Reinigungswirkung ein verringertes Ausmaß von Korrosion, insbesondere an Gläsern und Porzellantellern sowie ein verringertes Ausmaß an Ablagerungen ergibt.The invention is therefore based on the object of a non-solid dishwasher detergent to make available that compared to the prior art with a good cleaning effect a reduced degree of corrosion, especially on glasses and porcelain plates as well results in a reduced level of deposits.
Diese Aufgabe wird gelöst durch ein Maschinengeschirrspülmittel der eingangs genannten
Art; dadurch gekennzeichnet, daß es neben üblichen Maschinengeschirrspülmittelinhaltsstoffen
ein kristallines, schichtförmiges Silikat der allgemeinen Formel
Bevorzugt enthält das Maschinengeschirrspülmittel 1 bis 50 Gew.-% des kristallinen schichtförmigen Silikats.The machine dishwashing detergent preferably contains 1 to 50% by weight of the crystalline layered Silicate.
Besonders bevorzugt enthält das Maschinengeschirrspülmittel 5 bis 30 Gew.-% des kristallinen schichtförmigen Silikats.The machine dishwashing detergent particularly preferably contains 5 to 30% by weight of the crystalline layered silicate.
Bevorzugt handelt es sich bei dem kristallinen schichtförmigen Silikat im wesentlichen um Dinatriumdisilikat.The crystalline layered silicate is preferably essentially Disodium disilicate.
Bevorzugt handelt es sich bei dem Dinatriumdisilikat um schichtförmiges kristallines Dinatriumdisilikat, das aus mindestens einer der polymorphen Phasen des Dinatriumdisilikates sowie aus Natriumsilikaten nicht schichtsilikatischer Natur besteht.The disodium disilicate is preferably a layered crystalline disodium disilicate, that from at least one of the polymorphic phases of the disodium disilicate and consists of sodium silicates of a non-phyllosilicate nature.
Bevorzugt besteht das schichtförmige kristalline Dinatriumdisilikat (die nachfolgenden Angaben beziehen sich auf Gew.-%) aus 1 bis 40% an alpha-Dinatriumdisilikat:, 0 bis 50% an beta-Dinatriumdisilikat, 50 bis 98% an delta-Dinatriumdisilikat und 0 bis 40% an nichtschichtsilikatischen Natriumsilikaten.The layered crystalline disodium disilicate is preferably present (the following information refer to% by weight) from 1 to 40% of alpha disodium disilicate:, 0 to 50% of beta disodium disilicate, 50 to 98% of delta disodium disilicate and 0 to 40% of non-layer silicate Sodium silicates.
In einer anderen Ausführungsform der Erfindung besteht das schichtförmige kristalline Dinatriumdisilikat aus 0 bis 40% an alpha-Dinatriumdisilikat, 20 bis 98% an beta-Dinatriumdisilikat, 0 bis 40% an delta-Dinatriumdisilikat und 0 bis 50% an nichtschichtsilikatischen Natriumsilikaten.In another embodiment of the invention there is the layered crystalline disodium disilicate from 0 to 40% of alpha disodium disilicate, 20 to 98% of beta disodium disilicate, 0 to 40% of delta disodium disilicate and 0 to 50% of non-layer silicate Sodium silicates.
In einer weiteren Ausführungsform der Erfindung besteht das schichtförmige kristalline Dinatriumdisilikat aus 20 bis 98% an alpha-Dinatriumdisilikat, 0 bis 40 % an beta-Dinatriumdisilikat, 0 bis 50% an delta-Dinatriumdisilikat und 0 bis 50% an nichtschichtsilikatischen Natriumsilikaten.In a further embodiment of the invention, the layered crystalline disodium disilicate is present from 20 to 98% of alpha disodium disilicate, 0 to 40% of beta disodium disilicate, 0 to 50% of delta disodium disilicate and 0 to 50% of non-layer silicate Sodium silicates.
Die Definitionen von alpha, beta- und delta-Dinatriumdisilkat sind bekannt und können beispielsweise der EP 0 164 514 entnommen werden.The definitions of alpha, beta and delta disodium disilicate are known and can be used, for example can be found in EP 0 164 514.
Bevorzugt enthält das kristalline schichtförmige Silikat im erfindungsgemäßen Maschinengeschirrspülmittel bis zu 10 Mol-% Bor, bezogen auf SiO2.The crystalline layered silicate in the dishwasher detergent according to the invention preferably contains up to 10 mol% boron, based on SiO 2 .
Bevorzugt enthält das kristalline schichtförmige Silikat im erfindungsgemäßen Maschinengeschirrspülmittel bis zu 50 Mol-% Phosphor, bezogen auf SiO2.The crystalline layered silicate in the dishwasher detergent according to the invention preferably contains up to 50 mol% of phosphorus, based on SiO 2 .
Bevorzugt enthält das Maschinengeschirrspülmittel mindestens noch ein Tensid und/oder ein Bleichmittel und/oder ein rheoligisches Additiv und/oder ein Dispergiermittel und/oder einen Dispersionsträger.The machine dishwashing detergent preferably also contains at least one surfactant and / or one Bleaching agent and / or a rheological additive and / or a dispersing agent and / or one Dispersion carrier.
Bevorzugt enthält das Maschinengeschirrspülmittel als Tenside Blockpolymerisate langkettiger aliphatischer Alkohole mit Ethylenoxid- oder Propylenoxidgruppen, modifizierte Fettalkoholpolyglykolether, Mono- und Dialkylsulfate, Alkansulfonate, Aminoxide und/oder Fettsäuremethylpolyglykolester.The machine dishwashing detergent preferably contains long-chain block polymers as surfactants aliphatic alcohols with ethylene oxide or propylene oxide groups, modified fatty alcohol polyglycol ethers, Mono- and dialkyl sulfates, alkanesulfonates, amine oxides and / or fatty acid methyl polyglycol esters.
Bevorzugt enthält das Maschinengeschirrspülmittel als Bleichmittel Aktivchlorträger und/oder Aktivsauerstoffträger. The machine dishwashing detergent preferably contains active chlorine carriers as bleaching agents and / or active oxygen carriers.
Bevorzugt enthält das Maschinengeschirrspülmittel als rheoligisches Additiv und/oder Dispergiermittel Carboxymethylcellulose, Polycarboxylate, Phosphonate und/oder synthetische Tone.The machine dishwashing detergent preferably contains as a rheological additive and / or dispersant Carboxymethyl cellulose, polycarboxylates, phosphonates and / or synthetic Tone.
Bevorzugt enthält das Maschinengeschirrspülmittel als Dispersionsträger Ethylenglykole, Cooligo-/Copolymere von Propylenoxid und Ethylenoxid und/oder Wasser.The machine dishwashing detergent preferably contains ethylene glycols as the dispersion carrier, Cooligo / copolymers of propylene oxide and ethylene oxide and / or water.
Bevorzugt enthält das Maschinengeschirrspülmittel neben den üblichen Maschinengeschirrspülmittelinhaltsstoffen
- 2,5 bis 50 Gew.-%
- kristallines schichtförmiges Natriumdisilikat
- 0 bis 20 Gew. -%
- Tensid
- 0 bis 40 Gew.-%
- Natriumtripolyphosphat
- 0 bis 20 Gew.-%
- Bleichmittel
- 0,1 bis 15 Gew. -%
- rheologisches Additiv und /oder Dispergiermittel
- 50 bis 80 Gew.-%
- Dispersionsträger
- 2.5 to 50% by weight
- crystalline layered sodium disilicate
- 0 to 20% by weight
- Surfactant
- 0 to 40% by weight
- Sodium tripolyphosphate
- 0 to 20% by weight
- Bleach
- 0.1 to 15% by weight
- rheological additive and / or dispersant
- 50 to 80% by weight
- Dispersion carrier
Bevorzugt enthält das Maschinengeschirrspülmittel neben den üblichen Maschinengeschirrspülmittelinhaltsstoffen
- 5 bis 30 Gew.-%
- kristallines schichtförmiges Natriumdisilikat
- 0 bis 20 Gew.-%
- Tensid
- 15 bis 30 Gew.-%
- Natriumtripolyphosphat
- 5 bis 15 Gew.-%
- Bleichmittel
- 0,1 bis 10 Gew.-%
- rheologisches Additiv und /oder Dispergiermittel
- 50 bis 70 Gew.-%
- Dispersionsträger
- 5 to 30% by weight
- crystalline layered sodium disilicate
- 0 to 20% by weight
- Surfactant
- 15 to 30% by weight
- Sodium tripolyphosphate
- 5 to 15% by weight
- Bleach
- 0.1 to 10% by weight
- rheological additive and / or dispersant
- 50 to 70% by weight
- Dispersion carrier
Bevorzugt enthält das Maschinengeschirrspülmittel neben den üblichen Maschinengeschirrspülmittelinhaltsstoffen
- 5 bis 30 Gew.-%
- kristallines schichtförmiges Natriumdisilikat
- 5 bis 15 Gew.-%
- Bleichmittel
- 0 bis 20 Gew.-%
- Tensid
- 0,1 bis 10 Gew.-%
- rheologisches Additiv und /oder Dispergiermittel
- 30 bis 70 Gew.-%
- Dispersionsträger
- 5 to 30% by weight
- crystalline layered sodium disilicate
- 5 to 15% by weight
- Bleach
- 0 to 20% by weight
- Surfactant
- 0.1 to 10% by weight
- rheological additive and / or dispersant
- 30 to 70% by weight
- Dispersion carrier
Bevorzugt enthält das Maschinengeschirrspülmittel es neben den üblichen Maschinengeschirrspülmittelinhaltsstoffen
- 10 bis 40 Gew.-%
- kristallines schichtförmiges Natriumdisilikat
- 0 bis 20 Gew.-%
- Tensid
- 15 bis 30 Gew.-%
- Natriumtripolyphosphat
- 0,1 bis 15 Gew.-%
- rheologisches Additiv und /oder Dispergiermittel
- 30 bis 70 Gew.-%
- Dispersionsträger
- 10 to 40% by weight
- crystalline layered sodium disilicate
- 0 to 20% by weight
- Surfactant
- 15 to 30% by weight
- Sodium tripolyphosphate
- 0.1 to 15% by weight
- rheological additive and / or dispersant
- 30 to 70% by weight
- Dispersion carrier
Bevorzugt enthält das Maschinengeschirrspülmittel neben den üblichen Maschinengeschirrspülmittelinhaltsstoffen
- 10 bis 50 Gew.-%
- kristallines schichtförmiges Natriumdisilikat
- 0 bis 20 Gew.-%
- Tensid
- 0,1 bis 15 Gew.-%
- rheologisches Additiv und /oder Dispergiermittel
- 30 bis 70 Gew.-%
- Dispersionsträger
- 10 to 50% by weight
- crystalline layered sodium disilicate
- 0 to 20% by weight
- Surfactant
- 0.1 to 15% by weight
- rheological additive and / or dispersant
- 30 to 70% by weight
- Dispersion carrier
Bei den vorgenannten bevorzugten Zusammensetzungen handelt es sich bei dem Natriumdisilikat im wesentlichen um Dinatriumdisilikat.The preferred compositions mentioned above are sodium disilicate essentially disodium disilicate.
Bevorzugt weist das erfindungsgemäße Maschinengeschirrspülmittel korrosionhemmende Eigenschaften auf.The machine dishwashing detergent according to the invention preferably has corrosion-inhibiting properties on.
Besonders bevorzugt weist das erfindungsgemäße Maschinengeschirrspülmittel korrosionshemmende Eigenschaften an silikatischen Oberflächen des Spülgutes auf.The machine dishwashing detergent according to the invention particularly preferably has corrosion-inhibiting agents Properties on silicate surfaces of the wash ware.
Besonders bevorzugt weist das erfindungsgemäße Maschinengeschirrspülmittel korrosionshemmende Eigenschaften insbesondere an Gläsern auf. The machine dishwashing detergent according to the invention particularly preferably has corrosion-inhibiting agents Properties especially on glasses.
Bevorzugt weist das erfindungsgemäße Maschinengeschirrspülmittel eine erhöhte Reinigungsleistung auf.The machine dishwashing detergent according to the invention preferably has an increased cleaning performance on.
Bevorzugt weist das erfindungsgemäße Maschinengeschirrspülmittel ein geringeres Ausmaß an Ablagerungen, insbesondere an Gläsern auf.The machine dishwashing detergent according to the invention preferably has a smaller extent on deposits, especially on glasses.
Die Erfindung betrifft ebenfalls ein Verfahren zur Herstellung eines Maschinengeschirrspülmittels, dadurch gekennzeichnet, daß man in einem vorgelegten wäßrigen Medium und /oder Dispersionsträger zuerst Alkaliträger auflöst, dann rheologische Additive und/oder Dispergiermittel zumischt, auf Raumtemperatur abkühlt, die weiteren Komponenten zugibt und am Ende des Mischvorgangs das kristalline schichtförmige Silikat zusetzt.The invention also relates to a method for producing a dishwasher detergent, characterized in that in a submitted aqueous medium and / or Dispersion carriers first dissolve alkali carriers, then rheological additives and / or dispersants admixed, cools to room temperature, adds the other components and on The crystalline layered silicate is added at the end of the mixing process.
Bei dem Alkaliträger handelt es sich bevorzugt um Natriumcarbonat, Natriumhydroxid, Kaliumhydroxid und/oder um wasserlösliche Alkalisilkate.The alkali carrier is preferably sodium carbonate, sodium hydroxide, potassium hydroxide and / or around water-soluble alkali silicates.
Bei den Komponenten handelt es sich bevorzugt um Tenside, Bleichmittel, Füllstoffe, Builder, Cobuilder, Phosphate, organische Komplexbildner, Schauminhibitoren, Parfüme und/oder Farbstoffe und/oder gegebenenfalls um weitere Maschinengeschirrspülmittelinhaltsstoffe.The components are preferably surfactants, bleaches, fillers, builders, Cobuilders, phosphates, organic complexing agents, foam inhibitors, perfumes and / or dyes and / or possibly other ingredients for machine dishwashing detergents.
Die Erfindung betrifft auch die Verwendung des erfindungsgemäßen Maschinengeschirrspülmittels zum maschinellen Geschirrspülen.The invention also relates to the use of the dishwasher detergent according to the invention for automatic dishwashing.
Das im erfindungsgemäßen Maschinengeschirrspülmittel enthaltene schichtförmige Silikat,
welches wie zuvor beschrieben der allgemeinen Formel
Weitere, bevorzugt enthaltene Ionen sind solche der dritten und fünften Hauptgruppe des Periodensystems, hierzu zählen vor allem Bor bzw. Phosphor. Dies trifft inbesondere dann zu, wenn als schichtförmiges Silikat ein Dinatriumdisilikat, wie es weiter oben und nachfolgend beschrieben ist, eingesetzt wird.Further, preferably contained ions are those of the third and fifth main group of the periodic table, these include above all boron or phosphorus. This is especially true if a disodium disilicate as layered silicate, as described above and below is used.
Das schichtförmige Silikat kann aber auch ein Natriumkaliumdisilikat sein, in welchem das Natrium- zu Kalium-Verhältnis in einem weiten Bereich variiert werden kann.The layered silicate can also be a sodium potassium disilicate, in which the Sodium to potassium ratio can be varied within a wide range.
Erfindungsgemäß sind ebenfalls schichtförmige Silikate der vorgenannten Formel, die im wesentlichen Alkalimetalle (Li, Na, K) und/oder Wasserstoff enthalten, und bei denen geringe Anteile an den oben erwähnten Erdalkalimetallen (Be, Mg, Ca, Sr, Ba) sowie Elemente der dritten (B, Al, Ga, In, Tl) bzw. fünften Hauptgruppe (P, As, Sb, Bi) des Periodensystem enthalten sind.According to the invention are also layered silicates of the above formula, which are essentially Contain alkali metals (Li, Na, K) and / or hydrogen, and in those low Shares in the above-mentioned alkaline earth metals (Be, Mg, Ca, Sr, Ba) and elements of third (B, Al, Ga, In, Tl) and fifth main group (P, As, Sb, Bi) of the periodic table are.
Für das erfindungsgemäße Maschinengeschirrspülmittel wird das vorgenannte Silikat entweder in einer feingemahlenen Form eingesetzt, d.h. als Pulver mit einem mittleren Teilchendurchmesser von 1 bis 200 Mikrometer, oder in leicht dispergierbarer Form z.B. als Preßgranulat, das beim Einarbeiten in die Geschirreinigerdispersion zu mikroskopisch kleinen Teilchen zerfüllt.For the machine dishwasher detergent according to the invention, the aforementioned silicate is either used in a finely ground form, i.e. as a powder with an average particle diameter from 1 to 200 microns, or in easily dispersible form e.g. as pressed granules, that when working into the dishwashing dispersion into microscopic particles crushed.
Bevorzugt geeignet sind auch leicht dispergierbare Compounds von kristallinem, schichtförmigem Natriumdisilikat mit Polycarboxylaten, wie sie in der DE-OS 197 19 888 beschrieben sind. Bevorzugte Polycarboxylate sind Homo- bzw beliebige Kombinationen von Copolymeren der Monomere Acrylsäure und/oder Maleinsäure und/oder Vinylacetat und/oder Methallylsulfonat. Das bevorzugte Compound von Polycarboxylaten und kristallinem, schichtförmigem Natriumdisilikat besteht dabei zu 50 bis 98 Gew.-% aus besagtem Silikat und 2 bis 50 Gew.-% Polycarboxylat.Easily dispersible compounds of crystalline, layered are also particularly preferred Sodium disilicate with polycarboxylates, as described in DE-OS 197 19 888 are. Preferred polycarboxylates are homo- or any combination of copolymers the monomers acrylic acid and / or maleic acid and / or vinyl acetate and / or methallylsulfonate. The preferred compound of polycarboxylates and crystalline, layered Sodium disilicate consists of 50 to 98% by weight of said silicate and 2 to 50% by weight polycarboxylate.
Die übrigen Geschirrspülkomponenten, die teilweise bereits weiter oben genannt wurden, wie Füllstoffe, Alkaliträger, Tenside, Builder, Bleichmittel, rheologische Additive und Dispergiermittel, Schauminhibitoren sowie gegebenfalls Parfüme und Farbstoffe und andere, können Stoffe sein, die für diese Zwecke bereits hinreichend bekannt sind. The other dishwasher components, some of which have already been mentioned above, such as Fillers, alkali carriers, surfactants, builders, bleaches, rheological additives and dispersants, Foam inhibitors and possibly perfumes and dyes and others can Substances that are already well known for these purposes.
Als Füllstoff kann z.B. Natriumsulfat eingesetzt werden.As a filler e.g. Sodium sulfate can be used.
Als Alkaliträger seien die Oxide, Hydroxide, Carbonate und Silikate der Alkalimetalle, bevorzugt Natriumcarbonat und/oder Natriumhydroxid und/oder Kaliumhydroxid oder wasserlösliche Alkalisilikate genannt.Oxides, hydroxides, carbonates and silicates of the alkali metals are preferred as alkali carriers Sodium carbonate and / or sodium hydroxide and / or potassium hydroxide or water soluble Called alkali silicates.
Als Tenside sind chlorstabile Blockpolymerisate langkettiger aliphatischer Alkohole mit Ethylenoxid- oder Propylenoxidgruppen oder modifizierte Fettalkoholpolyglykolether oder Mono- und Di-alkylsulfate oder Alkansulfonate oder Aminoxide oder Fettsäuremethylpolyglykolester geeignet.Chlorine-stable block polymers of long-chain aliphatic alcohols are also included as surfactants Ethylene oxide or propylene oxide groups or modified fatty alcohol polyglycol ethers or Mono- and di-alkyl sulfates or alkanesulfonates or amine oxides or fatty acid methyl polyglycol esters suitable.
Als Builder können monomere, dimere, oligomere oder polymere Alkaliphosphate, vorzugsweise Pentaalkalitriphosphat, wasserfrei und/anhydratisiert und/oder Hexahydrat eingesetzt werden.As builders, monomeric, dimeric, oligomeric or polymeric alkali phosphates, preferably Pentaalkali nitrate phosphate, anhydrous and / anhydrated and / or hexahydrate used become.
Desweiteren kommen als erfindungsgemäßer Bestandteil organische Komplexbildner, wie Mono-, Di-, Tri-, Oligo- und/oder Polycarbonsäuren, Hydroxycarbonsäuren, Aminocarbonsäuren und Phosphonsäuren, vorzugsweise in Form ihrer wasserlöslichen Salze in Frage. Bevorzugte Oligocarbonsäuren sind Citronen-, Wein-, Maleinsäure usw. Diese werden bevorzugt zusammen mit dem kristallinen, schichtförmigen Silikat als Preßgranulat eingesetzt.Organic complexing agents such as Mono-, di-, tri-, oligo- and / or polycarboxylic acids, hydroxycarboxylic acids, aminocarboxylic acids and phosphonic acids, preferably in the form of their water-soluble salts. Preferred Oligocarboxylic acids are citric, tartaric, maleic, etc. These are preferred used together with the crystalline, layered silicate as press granulate.
Als bevorzugte Bleichmittel kommen Aktivchlorträger, wie Natriumdichlorisocyanurat oder Natriumhypochlorit-Lösung (Chlorbleichlauge) und Aktivsauerstoffträger, wie Wasserstoffperoxid, Alkalimetallperoxide, Erdalkalimetallperoxide, Alkaliperborat, -persulfat, -percarbonat, -perphosphat sowie Peroxycarbonsäuren und deren Salze wie Dodecanperoxidicarbonsäure oder Magnesiumperoxiphthalat in Betracht.Active chlorine carriers such as sodium dichloroisocyanurate or come as preferred bleaching agents Sodium hypochlorite solution (chlorine bleach) and active oxygen carriers, such as hydrogen peroxide, Alkali metal peroxides, alkaline earth metal peroxides, alkali perborate, persulfate, percarbonate, -perphosphate and peroxycarboxylic acids and their salts such as dodecane peroxidicarboxylic acid or magnesium peroxiphthalate.
Weiterhin können Bleichaktivatoren oder -katalysatoren eingesetzt werden. Ein üblicher Bleichaktivator ist Tetraacetylethylendiamin. Übliche Bleichkatalysatoren sind Komplexe des Mangans mit speziellen Liganden z.B. Derivate des 1,4,7-Triaminocyclononans.Bleach activators or catalysts can also be used. A common one Bleach activator is tetraacetylethylene diamine. Common bleaching catalysts are complexes of Manganese with special ligands e.g. Derivatives of 1,4,7-triaminocyclononane.
Bevorzugte rheologische Additive und Dispergierhilfsmittel sind Carboxymethylcellulose, Polycarboxylate, Phosphonate oder synthetische Tone. Preferred rheological additives and dispersing agents are carboxymethyl cellulose, Polycarboxylates, phosphonates or synthetic clays.
Erfindungsgemäß einsetzbare Tone sind natürlich vorkommende aktivierte und zum Teil modifizierte Tonmineralien wie Bentone-Typen der Fa. Rheox oder auch synthetische Tonminerale wie die Laponite-Typen der Fa. Laporte oder synthetischer Hectorit der Type SKS-21 der Fa. Hoechst und synthetischer Saponit der Type SKS-20 der Fa. Hoechst. Weitere, geeignete Tone sind dem Fachmann bekannt und den Herstellerkatalogen zu entnehmen.Clays which can be used according to the invention are naturally occurring activated and partly modified Clay minerals such as Bentone grades from Rheox or synthetic clay minerals such as the Laponite grades from Laporte or synthetic hectorite from the SKS-21 type Hoechst and synthetic saponite type SKS-20 from Hoechst. More suitable Clays are known to the person skilled in the art and can be found in the manufacturer's catalogs.
Bei der Dispergierung können gelöste Alkalisilikate bzw. Mono-, Oligo- und Polyphosphate unterstützend wirken.Dissolved alkali silicates or mono-, oligo- and polyphosphates can be used in the dispersion act supportive.
Als Dispersionsträger (flüssige Komponente) können monomeres, oligomeres oder polymeres Ethylenglykol oder Cooligo-/Copolymere von Propylenoxid und Ethylenoxid und/oder Wasser eingesetzt werden.Monomeric, oligomeric or polymeric can be used as the dispersion carrier (liquid component) Ethylene glycol or cooligo / copolymers of propylene oxide and ethylene oxide and / or water be used.
Schaum in Geschirrspülmaschinen, meistens hervorgerufen durch schaumproduzierende Tenside oder einweißhaltige Speiserückstände bewirkt eine Verringerung der Reinigungsleistung. Deshalb ist es notwendig, den Geschirreinigungsmitteln einen Schaumdrücker oder Schaumdämpfer zuzusetzen, beispielsweise chlorstabile Phosphorsäureester, wie etwa Triisobutylphosphat (Entschäumer TIP der Clariant GmbH), oder bekannte Silikone wie die SP-Typen der Fa. Wacker Chemie GmbH.Foam in dishwashers, mostly caused by foam-producing surfactants or food residues containing protein causes a reduction in cleaning performance. Therefore, it is necessary to use a foam presser or foam damper to clean the dishes to add, for example chlorine-stable phosphoric acid esters, such as triisobutyl phosphate (Defoamer TIP from Clariant GmbH), or well-known silicones like the SP types from Wacker Chemie GmbH.
Die vorgenannten Komponenten können im erfindungsgemäßen Maschinengeschirrspülmittel einzeln oder in Gemischen neben den kristallinen schichtförmigen Silikaten, insbesondere Natriumdisilikaten (z.B. Type SKS-6 der Clariant GmbH) enthalten sein.The aforementioned components can be used in the dishwasher detergent according to the invention individually or in mixtures in addition to the crystalline layered silicates, in particular Sodium disilicates (e.g. type SKS-6 from Clariant GmbH) may be included.
Die Konsistenz der erfindungsgemäßen Mischungen kann je nach Feststoffanteil niedrigviskos/flüssig bis pastös/gallertig eingestellt werden.Depending on the solids content, the consistency of the mixtures according to the invention can be of low viscosity / liquid until pasty / gelatinous.
Erfindungsgemäße Maschinengeschirrspülmittel können sowohl Phosphat enthalten als auch phosphatfrei sein. Machine dishwashing detergents according to the invention can contain phosphate as well be phosphate free.
Die Herstellung sollte bevorzugt nach folgendem Verfahren erfolgen:
In einem vorgelegten wäßrigen Medium oder einem anderen Dispersionsträger werden zuerst
Alkaliträger, wie z.B. Natriumcarbonat und/oder Natriumhydroxid und/oder Natriumwasserglas,
aufgelöst, dann rheologische Additive und/oder Dispergiermittel (bevorzugt Polycarboxylate
und/oder Phosphonsäuren) zugemischt, auf Raumtemperatur abgekühlt und die weiteren
Komponenten (etwa Bleichmittel, Tensid und Builder (Phosphat)) zugefügt. Am Ende
des Mischvorgangs wird das kristalline schichtförmige Silikat zugesetzt.The production should preferably be carried out according to the following procedure:
In a submitted aqueous medium or another dispersion carrier, alkali carriers, such as sodium carbonate and / or sodium hydroxide and / or sodium water glass, are first dissolved, then rheological additives and / or dispersants (preferably polycarboxylates and / or phosphonic acids) are mixed in, cooled to room temperature and the others Components (such as bleach, surfactant and builder (phosphate)) added. At the end of the mixing process, the crystalline layered silicate is added.
Die Untermischung erfolgt bevorzugt unter Einwirkung von starken Scherkräften z.B. mit üblichen Dispensoren, High-Shear-Mixern der Fa. Haake&Kunkel (Ultraturrax(TM)) oder Impeller-, Propeller- bzw. Turbinenrührern.The mixing is preferably carried out under the action of strong shear forces e.g. With usual dispensers, high-shear mixers from Haake & Kunkel (Ultraturrax (TM)) or Impeller, propeller or turbine stirrers.
Die Maschinengeschirrspülmittel gemäß der Erfindung zeichnen sich durch ein gutes Reinigungsvermögen auch bei kritischen Anschmutzungen wie angebrannten eiweißhaltigen Speiserückständen aus. Des Weiteren zeigen sie eine hohe Chlor- oder Aktivsauerstoffstabilität.The machine dishwashing detergents according to the invention are notable for good cleaning properties even with critical soiling such as burnt-on protein-containing food residues out. Furthermore, they show a high chlorine or active oxygen stability.
Die Schädigung von Gläsern und dekorierten Porzellantellern durch Ablagerungen und durch Korosion ist viel bis sehr geringer als bei handelsüblichen Geschirrreinigern, die dem Stand der Technik entsprechen. Dies ist aus den nachfolgenden Beispielen leicht ersehbar.The damage to glasses and decorated porcelain plates by deposits and by Corrosion is much to very low than with standard dishwashers that stand correspond to the technology. This can easily be seen from the examples below.
Die erfindungsgemäßen Maschinengeschirrspülmittel werden vorzugsweise in Haushaltsgeschirrspülmaschinen eingesetzt, können aber auch in Gewerbegeschirrspülern verwendet werden.The dishwasher detergents according to the invention are preferably used in household dishwashers used, but can also be used in commercial dishwashers.
Folgende Beispiele sollen die vorteilhaften Eigenschaften des erfindungsgemäßen Maschinengeschirrspülmittels unter Beweis stellen. Als Vergleich gelten marktübliche Geschirreiniger-Gels auf Phosphatbasis und eine Versuchsmischung ohne Zusatz von (erfindungsgemäßem) kristallinem schichtförmigem Silikat.The following examples are intended to illustrate the advantageous properties of the dishwasher detergent according to the invention prove. Standard tableware cleaner gels are used as a comparison based on phosphate and a test mixture without adding (according to the invention) crystalline layered silicate.
Der pH-Wert der Reinigungsflotten wurde nach Abfiltrieren der Schmutzbelastung unmittelbar danach mit Hilfe einer Glaselektrode ermittelt. The pH value of the cleaning liquors became immediately after filtering off the contamination then determined using a glass electrode.
- 22,20 Gew%
- Natriumtripolyphosphat, teilhydratisiert
- 9,00 Gew%
- Natriumhypochlorit-Lösung (Chlorbleichlauge, 15 % Aktivchlor)
- 0,10 Gew%
- Verdickungsmittel
- 0,04 Gew%
- Silikonentschäumer
- 49,50 Gew%
- Natriumsilikat (Wasserglas, 45,5 Gew%, Siliciumdioxid zu Dinatriumoxid Verhältnis 2,0)
- 1,50 Gew%
- Natriumalkansulfonat (®Hostapur SAS 60 der Clariant GmbH)
- 0,80 Gew%
- Natriumpolyacrylat
- 0,60 Gew%
- Phosphonat (43 % Wirksubstanz)
- 3,96 Gew%
- Natriumcarbonat
- 12,30 Gew%
- Wasser
- 22.20% by weight
- Sodium tripolyphosphate, partially hydrated
- 9.00% by weight
- Sodium hypochlorite solution (chlorine bleach, 15% active chlorine)
- 0.10% by weight
- Thickener
- 0.04% by weight
- Silicone defoamer
- 49.50% by weight
- Sodium silicate (water glass, 45.5% by weight, silicon dioxide to disodium oxide ratio 2.0)
- 1.50% by weight
- Sodium alkane sulfonate (®Hostapur SAS 60 from Clariant GmbH)
- 0.80% by weight
- Sodium polyacrylate
- 0.60% by weight
- Phosphonate (43% active substance)
- 3.96% by weight
- sodium
- 12.30% by weight
- water
- 1,0 Gew%
- kristallines schichtförmiges Natriumdisilikat (SKS-6 der Clariant GmbH)
- 25,0 Gew%
- Natriumtripolyphosphat-Granulat
- 9,0 Gew%
- Natriumhypochlorit-Lösung
- 0,2 Gew%
- Entschäumer
- 1,5 Gew%
- Natriumalkylsulfat
- 1,1 Gew%
- Natriumpolyacrylat
- 0,3 Gew%
- Phosphonsäure (60 % Wirksubstanz)
- 0,5 Gew%
- Natriumhydroxid
- 6,0 Gew%
- Natriumcarbonat
- 46,5 Gew%
- Natriumwasserglas (wie bei D)
- 8,9 Gew%
- Wasser
- 1.0% by weight
- crystalline layered sodium disilicate (SKS-6 from Clariant GmbH)
- 25.0% by weight
- Sodium tripolyphosphate granules
- 9.0% by weight
- Sodium hypochlorite solution
- 0.2% by weight
- Defoamer
- 1.5% by weight
- Sodium alkyl sulfate
- 1.1% by weight
- Sodium polyacrylate
- 0.3% by weight
- Phosphonic acid (60% active substance)
- 0.5% by weight
- Sodium hydroxide
- 6.0% by weight
- sodium
- 46.5% by weight
- Sodium water glass (like D)
- 8.9% by weight
- water
- 5,5 Gew%
- kristallines schichtförmiges Natriumdisilikat (SKS-6 der Clariant GmbH)
- 22,2 Gew%
- Natriumtripolyphosphat, wasserfrei
- 9,0 Gew%
- Natriumhypochlorit-Lösung
- 0,4 Gew%
- Entschäumer (®Entschäumer TIP der Clariant GmbH)
- 49,50 Gew%
- Natriumsilikat (Wasserglas, 45,5 Gew%, Siliciumdioxid zu Dinatriumoxid Verhältnis 2,0)
- 1,0 Gew%
- Natriumalkansulfonat
- 2,0 Gew%
- Natriumpolyacrylat
- 0,6 Gew%
- Phosphonsäure (50 % Wirksubstanz)
- 1,0 Gew%
- Natriumhydroxid
- 4,0 Gew%
- Natriumcarbonat
- 17,3 Gew%
- Wasser
- 5.5% by weight
- crystalline layered sodium disilicate (SKS-6 from Clariant GmbH)
- 22.2% by weight
- Sodium tripolyphosphate, anhydrous
- 9.0% by weight
- Sodium hypochlorite solution
- 0.4% by weight
- Defoamer (® defoamer TIP from Clariant GmbH)
- 49.50% by weight
- Sodium silicate (water glass, 45.5% by weight, silicon dioxide to disodium oxide ratio 2.0)
- 1.0% by weight
- Sodium alkane sulfonate
- 2.0% by weight
- Sodium polyacrylate
- 0.6% by weight
- Phosphonic acid (50% active substance)
- 1.0% by weight
- Sodium hydroxide
- 4.0% by weight
- sodium
- 17.3% by weight
- water
- 17,5 Gew%
- kristallines schichtförmiges Natriumdisilikat /Copolymer-Compound auf Basis Acrylsäure/Maleinsäure (SKS-6 HD der Clariant GmbH)
- 20,0 Gew%
- Natriumtripolyphosphat, wasserfrei
- 10,0 Gew%
- Natriumpercarbonat
- 1,4 Gew%
- Fettsäurepolyglykolester
- 0,6 Gew%
- Entschäumer
- 49,50 Gew%
- Natriumsilikat (Wasserglas, 45,5 Gew%, Siliciumdioxid zu Dinatriumoxid Verhältnis 2,0)
- 0,2 Gew%
- Verdickungsmittel Bentonit
- 18,3 Gew%
- Wasser
- 17.5% by weight
- crystalline layered sodium disilicate / copolymer compound based on acrylic acid / maleic acid (SKS-6 HD from Clariant GmbH)
- 20.0% by weight
- Sodium tripolyphosphate, anhydrous
- 10.0% by weight
- Sodium percarbonate
- 1.4% by weight
- Fatty acid polyglycol esters
- 0.6% by weight
- Defoamer
- 49.50% by weight
- Sodium silicate (water glass, 45.5% by weight, silicon dioxide to disodium oxide ratio 2.0)
- 0.2% by weight
- Bentonite thickener
- 18.3% by weight
- water
- 10,0 Gew%
- kristallines schichtförmiges Natriumdisilikat
- 10,0 Gew%
- Natriumperborat-Monohydrat
- 0,1 Gew%
- Silikonentschäumer
- 0,9 Gew%
- Natriumalkansulfonat
- 5,0 Gew%
- Natriumcarbonat
- 15,0 Gew%
- Natriumtripolyphosphat, teilhydratisiert
- 15,0 Gew%
- Natriumtripolyphosphat-Hexahydrat
- 1,5 Gew%
- Bentonit
- 42,5 Gew%
- Wasser
- 10.0% by weight
- crystalline layered sodium disilicate
- 10.0% by weight
- Sodium perborate monohydrate
- 0.1% by weight
- Silicone defoamer
- 0.9% by weight
- Sodium alkane sulfonate
- 5.0% by weight
- sodium
- 15.0% by weight
- Sodium tripolyphosphate, partially hydrated
- 15.0% by weight
- Sodium tripolyphosphate hexahydrate
- 1.5% by weight
- Bentonite
- 42.5% by weight
- water
- 30,0 Gew%
- kristallines schichtförmiges Natriumdisilikat -Granulat
- 4,0 Gew%
- Natriumcarbonat
- 1,0 Gew%
- Natriumhydroxid
- 0,5 Gew%
- Phosphonsäure, 50 %ig
- 1,0 Gew%
- Natriumcopolymer (Sokalan CP5, BASF)
- 1,5 Gew%
- Blockpolymerisat (Genapol 2909, Clariant GmbH)
- 1,5 Gew%
- Protease-Enzym
- 1,5 Gew%
- Amylase-Enzym
- 10,0 Gew%
- Natriumperborat-Monohydrat
- 49,0 Gew%
- Wasser
- 30.0% by weight
- crystalline layered sodium disilicate granules
- 4.0% by weight
- sodium
- 1.0% by weight
- Sodium hydroxide
- 0.5% by weight
- Phosphonic acid, 50%
- 1.0% by weight
- Sodium copolymer (Sokalan CP5, BASF)
- 1.5% by weight
- Block polymer (Genapol 2909, Clariant GmbH)
- 1.5% by weight
- Protease enzyme
- 1.5% by weight
- Amylase enzyme
- 10.0% by weight
- Sodium perborate monohydrate
- 49.0% by weight
- water
An Gläsern und dekorierten Porzellantellern verschiedener Provenienz, Zusammensetzung und Form wurde die erfindungsgemäßen Mischungen D bis H im Vergleich zu den Handelsprodukten B und C auf irreversible Schädigung geprüft. Porzellanteller und -tassen sowie Edelstahlbestecke dienten als Ballast zur Auffüllung der vorgeschriebenen Spülgutmenge von 12 Maßgedecken. Das Prüfverfahren erfolgt nach DIN V ENV 12875-1: April 1998, Mechanische Geschirrspülmaschinenbeständigkeit von Haushaltswaren, Teil 1. Die Dosierung der Testreiniger weicht von der Vornorm ab, es wurden jeweils 40 g flüssige Testmischung im Reinigungsgang und 3 ml Klarspüler im Klarspülgang der Prüf-Geschirrspülmaschine dosiert.On glasses and decorated porcelain plates of various origins, composition The mixtures D to H according to the invention became shaped and shaped in comparison to the commercial products B and C checked for irreversible damage. Porcelain plates and cups as well Stainless steel cutlery served as ballast for filling the prescribed amount of wash ware 12 place settings. The test is carried out according to DIN V ENV 12875-1: April 1998, mechanical Dishwasher resistance of household goods, part 1. The dosage of Test cleaner deviates from the pre-standard, there were 40 g of liquid test mixture in each Cleaning cycle and 3 ml of rinse aid dosed in the final rinse cycle of the test dishwasher.
Nach 125 Spülgängen wird das Geschirr mit Hilfe untengenannter Punktebewertungstabelle
visuell bei Tageslicht und in einer sogen.
Man bestimmt die Anzahl von Spülgängen nach denen erstmalig eine sichtbare Trübung auftritt.
Der arithmetische Mittelwert, gebildet aus der Summe der Bewertungen und Anzahl der Gläser, ergibt die Note für den eingetretenen Schaden.The arithmetic mean, formed from the sum of the ratings and the number of glasses, gives the grade for the damage occurred.
Ein Vergleich von erfindungsgemäßen Maschinengeschirrspülmittel mit Handelsprodukten nach dem Stand der Technik bzw. dem Testprodukt nach dem Stand der Technik hinsichtlich der Benotungen nach den Methoden 1 und 2 zeigt, daß die erfindungsgemäßen Produkte wesentlich geringere Schädigung durch Ablagerungen und durch Korrosion ergeben.A comparison of dishwasher detergents according to the invention with commercial products according to the prior art or the test product according to the prior art with regard to The marks according to methods 1 and 2 show that the products according to the invention are essential less damage due to deposits and corrosion.
Die Maschinengeschirrspülmittel A bis I wurden in Anlehnung an DIN-Norm-Entwurf 44990
und der IKW-Methode in drei Haushaltsgeschirrspülmaschinen Miele G 688 SC auf ihre Reinigungswirkung
geprüft. Die erfindungsgemäßen Testprodukte, das Vergleichsprodukt nach
dem Stand der Technik und die Handelsprodukte nach dem Stand der Technik wurden mit
gleicher Dosierung von 40 g Geschirrspülmittel und 3 ml Klarspüler eingesetzt. Die Auswertung
erfolgt nach dem Spülen durch visuelle Abmusterung des Spülgutes. Das Prüfergebnis
wird in Prozent dargestellt (100%= sauber). In folgender Tabelle sind die Ergebnisse der Versuche
und die pH-Werte der Spülflotte zusammengestellt.
Die Ergebnisse zeigen, daß die erfindungsgemäßen Maschinengeschirrspülmittel eine deutliche Steigerung der Reinigungswirkung gegenüber solchen aus dem Stand der Technik aufweisen.The results show that the machine dishwashing detergents according to the invention clearly Have an increase in the cleaning effect compared to those from the prior art.
Claims (29)
- 2,5 bis 50 Gew.-%
- kristallines schichtförmiges Natriumdisilikat
- 0 bis 20 Gew.-%
- Tensid
- 0 bis 40 Gew.-%
- Natriumtripolyphosphat
- 0 bis 20 Gew.-%
- Bleichmittel
- 0,1 bis 15 Gew.-%
- rheologisches Additiv und /oder Dispergiermittel
- 50 bis 80 Gew.-%
- Dispersionsträger
- 2.5 to 50% by weight
- crystalline layered sodium disilicate
- 0 to 20% by weight
- Surfactant
- 0 to 40% by weight
- Sodium tripolyphosphate
- 0 to 20% by weight
- Bleach
- 0.1 to 15% by weight
- rheological additive and / or dispersant
- 50 to 80% by weight
- Dispersion carrier
- 5 bis 30 Gew.-%
- kristallines schichtförmiges Natriumdisilikat
- 0 bis 20 Gew.-%
- Tensid
- 15 bis 30 Gew.-%
- Natriumtripolyphosphat
- 5 bis 15 Gew.-%
- Bleichmittel
- 0,1 bis 10 Gew.-%
- rheologisches Additiv und /oder Dispergiermittel
- 50 bis 70 Gew.-%
- Dispersionsträger
- 5 to 30% by weight
- crystalline layered sodium disilicate
- 0 to 20% by weight
- Surfactant
- 15 to 30% by weight
- Sodium tripolyphosphate
- 5 to 15% by weight
- Bleach
- 0.1 to 10% by weight
- rheological additive and / or dispersant
- 50 to 70% by weight
- Dispersion carrier
- 5 bis 30 Gew.-%
- kristallines schichtförmiges Natriumdisilikat
- 5 bis 15 Gew.-%
- Bleichmittel
- 0 bis 20 Gew.-%
- Tensid
- 0,1 bis 10 Gew.-%
- rheologisches Additiv und /oder Dispergiermittel
- 30 bis 70 Gew.-%
- Dispersionsträger
- 5 to 30% by weight
- crystalline layered sodium disilicate
- 5 to 15% by weight
- Bleach
- 0 to 20% by weight
- Surfactant
- 0.1 to 10% by weight
- rheological additive and / or dispersant
- 30 to 70% by weight
- Dispersion carrier
- 10 bis 40 Gew.-%
- kristallines schichtförmiges Natriumdisilikat
- 0 bis 20 Gew.-%
- Tensid
- 15 bis 30 Gew.-%
- Natriumtripolyphosphat
- 0,1 bis 15 Gew.-%
- rheologisches Additiv und /oder Dispergiermittel
- 30 bis 70 Gew.-%
- Dispersionsträger
- 10 to 40% by weight
- crystalline layered sodium disilicate
- 0 to 20% by weight
- Surfactant
- 15 to 30% by weight
- Sodium tripolyphosphate
- 0.1 to 15% by weight
- rheological additive and / or dispersant
- 30 to 70% by weight
- Dispersion carrier
- 10 bis 50 Gew.-%
- kristallines schichtförmiges Natriumdisilikat
- 0 bis 20 Gew.-%
- Tensid
- 0,1 bis 15 Gew.-%
- rheologisches Additiv und /oder Dispergiermittel
- 30 bis 70 Gew.-%
- Dispersionsträger
- 10 to 50% by weight
- crystalline layered sodium disilicate
- 0 to 20% by weight
- Surfactant
- 0.1 to 15% by weight
- rheological additive and / or dispersant
- 30 to 70% by weight
- Dispersion carrier
Applications Claiming Priority (2)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
DE19854960A DE19854960A1 (en) | 1998-11-29 | 1998-11-29 | Dishwasher detergent |
DE19854960 | 1998-11-29 |
Publications (2)
Publication Number | Publication Date |
---|---|
EP1004655A2 true EP1004655A2 (en) | 2000-05-31 |
EP1004655A3 EP1004655A3 (en) | 2002-09-25 |
Family
ID=7889341
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
EP99120429A Ceased EP1004655A3 (en) | 1998-11-29 | 1999-10-14 | Automatic dishwashing composition |
Country Status (4)
Country | Link |
---|---|
US (1) | US6539954B1 (en) |
EP (1) | EP1004655A3 (en) |
CA (1) | CA2291419C (en) |
DE (1) | DE19854960A1 (en) |
Cited By (5)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
EP1162255A2 (en) * | 2000-06-07 | 2001-12-12 | Kao Corporation | Liquid detergent composition |
EP1205537A2 (en) * | 2000-11-14 | 2002-05-15 | Clariant GmbH | Builder composition |
WO2010078979A1 (en) * | 2009-01-09 | 2010-07-15 | Henkel Ag & Co. Kgaa | Color-protecting dishwasher detergent |
DE102007006253B4 (en) * | 2007-02-08 | 2013-08-29 | Comtag Ag | Cleaning agent for the sole of an iron |
WO2015070976A1 (en) * | 2013-11-15 | 2015-05-21 | Weylchem Wiesbaden Gmbh | Dishwashing composition and use thereof |
Families Citing this family (7)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
DE19943551A1 (en) * | 1999-09-11 | 2001-03-15 | Clariant Gmbh | Poorly soluble alkali silicate |
DE10061897A1 (en) * | 2000-12-12 | 2002-06-13 | Clariant Gmbh | Washing or cleaning composition, useful for fabrics or hard surfaces, contains microdisperse, hydrophilic silicate particles that improve soil removal and prevent resoiling |
US20060269441A1 (en) * | 2005-05-25 | 2006-11-30 | Ochomogo Maria G | Nanosilica-based food contact sanitizer |
US20100311633A1 (en) * | 2007-02-15 | 2010-12-09 | Ecolab Usa Inc. | Detergent composition for removing fish soil |
US8093200B2 (en) | 2007-02-15 | 2012-01-10 | Ecolab Usa Inc. | Fast dissolving solid detergent |
DE102008039411A1 (en) * | 2008-08-12 | 2010-02-18 | Alfred Kärcher Gmbh & Co. Kg | Care products, in particular for hot water high pressure cleaners |
US8426349B2 (en) * | 2009-05-26 | 2013-04-23 | Delaval Holding Ab | Chlorinated alkaline pipeline cleaner with methane sulfonic acid |
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-
1998
- 1998-11-29 DE DE19854960A patent/DE19854960A1/en not_active Withdrawn
-
1999
- 1999-10-14 EP EP99120429A patent/EP1004655A3/en not_active Ceased
- 1999-11-24 US US09/448,246 patent/US6539954B1/en not_active Expired - Fee Related
- 1999-11-25 CA CA002291419A patent/CA2291419C/en not_active Expired - Fee Related
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EP1162255A2 (en) * | 2000-06-07 | 2001-12-12 | Kao Corporation | Liquid detergent composition |
EP1162255A3 (en) * | 2000-06-07 | 2002-01-02 | Kao Corporation | Liquid detergent composition |
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DE102007006253B4 (en) * | 2007-02-08 | 2013-08-29 | Comtag Ag | Cleaning agent for the sole of an iron |
WO2010078979A1 (en) * | 2009-01-09 | 2010-07-15 | Henkel Ag & Co. Kgaa | Color-protecting dishwasher detergent |
WO2015070976A1 (en) * | 2013-11-15 | 2015-05-21 | Weylchem Wiesbaden Gmbh | Dishwashing composition and use thereof |
Also Published As
Publication number | Publication date |
---|---|
CA2291419A1 (en) | 2000-05-29 |
CA2291419C (en) | 2003-06-10 |
DE19854960A1 (en) | 2000-05-31 |
US6539954B1 (en) | 2003-04-01 |
EP1004655A3 (en) | 2002-09-25 |
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