EP0826768A1 - Granular components containing benzotriazole for automatic dishwashing compositions, and method of making them - Google Patents
Granular components containing benzotriazole for automatic dishwashing compositions, and method of making them Download PDFInfo
- Publication number
- EP0826768A1 EP0826768A1 EP97113068A EP97113068A EP0826768A1 EP 0826768 A1 EP0826768 A1 EP 0826768A1 EP 97113068 A EP97113068 A EP 97113068A EP 97113068 A EP97113068 A EP 97113068A EP 0826768 A1 EP0826768 A1 EP 0826768A1
- Authority
- EP
- European Patent Office
- Prior art keywords
- group
- component
- solid
- granular
- surfactants
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
- 239000000203 mixture Substances 0.000 title claims abstract description 32
- 238000004851 dishwashing Methods 0.000 title claims description 20
- 238000004519 manufacturing process Methods 0.000 title claims description 5
- QRUDEWIWKLJBPS-UHFFFAOYSA-N benzotriazole Chemical compound C1=CC=C2N[N][N]C2=C1 QRUDEWIWKLJBPS-UHFFFAOYSA-N 0.000 title abstract description 17
- 239000012964 benzotriazole Substances 0.000 title abstract description 16
- 239000007787 solid Substances 0.000 claims abstract description 25
- 239000004094 surface-active agent Substances 0.000 claims abstract description 12
- 239000002245 particle Substances 0.000 claims abstract description 11
- 239000007788 liquid Substances 0.000 claims abstract description 10
- 239000000843 powder Substances 0.000 claims abstract description 10
- 229930195733 hydrocarbon Natural products 0.000 claims abstract description 8
- 150000002430 hydrocarbons Chemical class 0.000 claims abstract description 8
- 238000005507 spraying Methods 0.000 claims abstract description 4
- 239000003495 polar organic solvent Substances 0.000 claims abstract 2
- 239000003599 detergent Substances 0.000 claims description 27
- 238000000034 method Methods 0.000 claims description 24
- 239000000126 substance Substances 0.000 claims description 18
- 238000002844 melting Methods 0.000 claims description 13
- 230000008018 melting Effects 0.000 claims description 13
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 claims description 11
- 229910052709 silver Inorganic materials 0.000 claims description 11
- 239000004332 silver Substances 0.000 claims description 11
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 9
- 125000000217 alkyl group Chemical group 0.000 claims description 9
- 239000007844 bleaching agent Substances 0.000 claims description 9
- 238000005260 corrosion Methods 0.000 claims description 9
- 239000008187 granular material Substances 0.000 claims description 9
- 230000007797 corrosion Effects 0.000 claims description 8
- 150000002191 fatty alcohols Chemical class 0.000 claims description 8
- 239000002736 nonionic surfactant Substances 0.000 claims description 8
- 239000011814 protection agent Substances 0.000 claims description 8
- ZWEHNKRNPOVVGH-UHFFFAOYSA-N 2-Butanone Chemical compound CCC(C)=O ZWEHNKRNPOVVGH-UHFFFAOYSA-N 0.000 claims description 6
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims description 6
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 claims description 6
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 6
- DNIAPMSPPWPWGF-UHFFFAOYSA-N Propylene glycol Chemical compound CC(O)CO DNIAPMSPPWPWGF-UHFFFAOYSA-N 0.000 claims description 6
- 239000003795 chemical substances by application Substances 0.000 claims description 5
- 239000011248 coating agent Substances 0.000 claims description 5
- 238000000576 coating method Methods 0.000 claims description 5
- 238000005469 granulation Methods 0.000 claims description 5
- 230000003179 granulation Effects 0.000 claims description 5
- 239000004615 ingredient Substances 0.000 claims description 5
- -1 Contains defoamers Substances 0.000 claims description 4
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 claims description 4
- 239000013543 active substance Substances 0.000 claims description 4
- 239000000470 constituent Substances 0.000 claims description 4
- 238000001035 drying Methods 0.000 claims description 4
- 238000005470 impregnation Methods 0.000 claims description 4
- 229920001223 polyethylene glycol Polymers 0.000 claims description 4
- 239000002904 solvent Substances 0.000 claims description 4
- 150000002148 esters Chemical class 0.000 claims description 3
- 239000003960 organic solvent Substances 0.000 claims description 3
- 239000003205 fragrance Substances 0.000 claims description 2
- 239000002304 perfume Substances 0.000 claims description 2
- 229920000642 polymer Polymers 0.000 claims description 2
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 claims 2
- 150000001565 benzotriazoles Chemical class 0.000 claims 2
- 238000002360 preparation method Methods 0.000 abstract description 5
- 239000004215 Carbon black (E152) Substances 0.000 abstract 1
- 125000003354 benzotriazolyl group Chemical class N1N=NC2=C1C=CC=C2* 0.000 description 9
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 8
- 102000004190 Enzymes Human genes 0.000 description 7
- 108090000790 Enzymes Proteins 0.000 description 7
- 229940088598 enzyme Drugs 0.000 description 7
- 239000012459 cleaning agent Substances 0.000 description 6
- 150000003839 salts Chemical class 0.000 description 6
- 239000002253 acid Substances 0.000 description 5
- 239000003513 alkali Substances 0.000 description 5
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 4
- UIIMBOGNXHQVGW-UHFFFAOYSA-M Sodium bicarbonate Chemical compound [Na+].OC([O-])=O UIIMBOGNXHQVGW-UHFFFAOYSA-M 0.000 description 4
- 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 4
- 150000007513 acids Chemical class 0.000 description 4
- 150000001298 alcohols Chemical class 0.000 description 4
- 150000001875 compounds Chemical class 0.000 description 4
- 230000001590 oxidative effect Effects 0.000 description 4
- 239000001509 sodium citrate Substances 0.000 description 4
- 235000000346 sugar Nutrition 0.000 description 4
- 102000013142 Amylases Human genes 0.000 description 3
- 108010065511 Amylases Proteins 0.000 description 3
- IAYPIBMASNFSPL-UHFFFAOYSA-N Ethylene oxide Chemical compound C1CO1 IAYPIBMASNFSPL-UHFFFAOYSA-N 0.000 description 3
- 102000004882 Lipase Human genes 0.000 description 3
- 239000004367 Lipase Substances 0.000 description 3
- 108090001060 Lipase Proteins 0.000 description 3
- 229910019142 PO4 Inorganic materials 0.000 description 3
- 239000005662 Paraffin oil Substances 0.000 description 3
- 108091005804 Peptidases Proteins 0.000 description 3
- 239000004365 Protease Substances 0.000 description 3
- 235000019418 amylase Nutrition 0.000 description 3
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 3
- 150000004649 carbonic acid derivatives Chemical class 0.000 description 3
- 239000002270 dispersing agent Substances 0.000 description 3
- 150000004665 fatty acids Chemical class 0.000 description 3
- 239000003112 inhibitor Substances 0.000 description 3
- 235000019421 lipase Nutrition 0.000 description 3
- 229910052751 metal Inorganic materials 0.000 description 3
- 239000002184 metal Substances 0.000 description 3
- 238000002156 mixing Methods 0.000 description 3
- 229910052760 oxygen Inorganic materials 0.000 description 3
- 239000001301 oxygen Substances 0.000 description 3
- 235000021317 phosphate Nutrition 0.000 description 3
- 239000000047 product Substances 0.000 description 3
- 238000003860 storage Methods 0.000 description 3
- 108010084185 Cellulases Proteins 0.000 description 2
- 102000005575 Cellulases Human genes 0.000 description 2
- 244000060011 Cocos nucifera Species 0.000 description 2
- 235000013162 Cocos nucifera Nutrition 0.000 description 2
- QUSNBJAOOMFDIB-UHFFFAOYSA-N Ethylamine Chemical compound CCN QUSNBJAOOMFDIB-UHFFFAOYSA-N 0.000 description 2
- QIGBRXMKCJKVMJ-UHFFFAOYSA-N Hydroquinone Chemical compound OC1=CC=C(O)C=C1 QIGBRXMKCJKVMJ-UHFFFAOYSA-N 0.000 description 2
- BAVYZALUXZFZLV-UHFFFAOYSA-N Methylamine Chemical compound NC BAVYZALUXZFZLV-UHFFFAOYSA-N 0.000 description 2
- 102000035195 Peptidases Human genes 0.000 description 2
- 239000012190 activator Substances 0.000 description 2
- 229910052783 alkali metal Inorganic materials 0.000 description 2
- 229910052910 alkali metal silicate Inorganic materials 0.000 description 2
- 125000002947 alkylene group Chemical group 0.000 description 2
- 229910021529 ammonia Inorganic materials 0.000 description 2
- 229940025131 amylases Drugs 0.000 description 2
- GGNQRNBDZQJCCN-UHFFFAOYSA-N benzene-1,2,4-triol Chemical compound OC1=CC=C(O)C(O)=C1 GGNQRNBDZQJCCN-UHFFFAOYSA-N 0.000 description 2
- 239000000969 carrier Substances 0.000 description 2
- YCIMNLLNPGFGHC-UHFFFAOYSA-N catechol Chemical compound OC1=CC=CC=C1O YCIMNLLNPGFGHC-UHFFFAOYSA-N 0.000 description 2
- 238000006243 chemical reaction Methods 0.000 description 2
- 239000007795 chemical reaction product Substances 0.000 description 2
- 238000001816 cooling Methods 0.000 description 2
- 229920001577 copolymer Polymers 0.000 description 2
- 235000014113 dietary fatty acids Nutrition 0.000 description 2
- 239000000194 fatty acid Substances 0.000 description 2
- 229930195729 fatty acid Natural products 0.000 description 2
- LNTHITQWFMADLM-UHFFFAOYSA-N gallic acid Chemical compound OC(=O)C1=CC(O)=C(O)C(O)=C1 LNTHITQWFMADLM-UHFFFAOYSA-N 0.000 description 2
- 229920001519 homopolymer Polymers 0.000 description 2
- 238000010348 incorporation Methods 0.000 description 2
- 150000002923 oximes Chemical class 0.000 description 2
- 150000003013 phosphoric acid derivatives Chemical class 0.000 description 2
- WQGWDDDVZFFDIG-UHFFFAOYSA-N pyrogallol Chemical compound OC1=CC=CC(O)=C1O WQGWDDDVZFFDIG-UHFFFAOYSA-N 0.000 description 2
- 150000004760 silicates Chemical class 0.000 description 2
- 229910000030 sodium bicarbonate Inorganic materials 0.000 description 2
- 235000017557 sodium bicarbonate Nutrition 0.000 description 2
- 229910000029 sodium carbonate Inorganic materials 0.000 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 description 2
- 235000019832 sodium triphosphate Nutrition 0.000 description 2
- 150000008163 sugars Chemical class 0.000 description 2
- 108010075550 termamyl Proteins 0.000 description 2
- HRXKRNGNAMMEHJ-UHFFFAOYSA-K trisodium citrate Chemical compound [Na+].[Na+].[Na+].[O-]C(=O)CC(O)(CC([O-])=O)C([O-])=O HRXKRNGNAMMEHJ-UHFFFAOYSA-K 0.000 description 2
- 229940038773 trisodium citrate Drugs 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 2
- 239000010457 zeolite Substances 0.000 description 2
- XEGAKAFEBOXGPV-UHFFFAOYSA-N 2,3,3a,4-tetrahydro-1h-benzotriazole Chemical class C1C=CC=C2NNNC12 XEGAKAFEBOXGPV-UHFFFAOYSA-N 0.000 description 1
- 240000002234 Allium sativum Species 0.000 description 1
- 235000019489 Almond oil Nutrition 0.000 description 1
- 239000004382 Amylase Substances 0.000 description 1
- 101000740449 Bacillus subtilis (strain 168) Biotin/lipoyl attachment protein Proteins 0.000 description 1
- BVKZGUZCCUSVTD-UHFFFAOYSA-M Bicarbonate Chemical compound OC([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-M 0.000 description 1
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical group [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- 229910052684 Cerium Inorganic materials 0.000 description 1
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 1
- KRKNYBCHXYNGOX-UHFFFAOYSA-K Citrate Chemical compound [O-]C(=O)CC(O)(CC([O-])=O)C([O-])=O KRKNYBCHXYNGOX-UHFFFAOYSA-K 0.000 description 1
- WQZGKKKJIJFFOK-GASJEMHNSA-N Glucose Natural products OC[C@H]1OC(O)[C@H](O)[C@@H](O)[C@@H]1O WQZGKKKJIJFFOK-GASJEMHNSA-N 0.000 description 1
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 description 1
- BPQQTUXANYXVAA-UHFFFAOYSA-N Orthosilicate Chemical compound [O-][Si]([O-])([O-])[O-] BPQQTUXANYXVAA-UHFFFAOYSA-N 0.000 description 1
- 229920002257 Plurafac® Polymers 0.000 description 1
- 239000002202 Polyethylene glycol Substances 0.000 description 1
- GOOHAUXETOMSMM-UHFFFAOYSA-N Propylene oxide Chemical compound CC1CO1 GOOHAUXETOMSMM-UHFFFAOYSA-N 0.000 description 1
- 102100037486 Reverse transcriptase/ribonuclease H Human genes 0.000 description 1
- UAOKXEHOENRFMP-ZJIFWQFVSA-N [(2r,3r,4s,5r)-2,3,4,5-tetraacetyloxy-6-oxohexyl] acetate Chemical compound CC(=O)OC[C@@H](OC(C)=O)[C@@H](OC(C)=O)[C@H](OC(C)=O)[C@@H](OC(C)=O)C=O UAOKXEHOENRFMP-ZJIFWQFVSA-N 0.000 description 1
- 238000005299 abrasion Methods 0.000 description 1
- 229910000288 alkali metal carbonate Inorganic materials 0.000 description 1
- 150000008041 alkali metal carbonates Chemical class 0.000 description 1
- 150000008044 alkali metal hydroxides Chemical class 0.000 description 1
- 150000001340 alkali metals Chemical class 0.000 description 1
- 239000008168 almond oil Substances 0.000 description 1
- 150000008064 anhydrides Chemical class 0.000 description 1
- 125000003118 aryl group Chemical group 0.000 description 1
- 238000010923 batch production Methods 0.000 description 1
- 108010064866 biozym Proteins 0.000 description 1
- 238000004061 bleaching Methods 0.000 description 1
- 125000000484 butyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 239000011575 calcium Substances 0.000 description 1
- 229910052791 calcium Inorganic materials 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 125000004432 carbon atom Chemical group C* 0.000 description 1
- 239000000460 chlorine Substances 0.000 description 1
- 229910052801 chlorine Inorganic materials 0.000 description 1
- 238000004140 cleaning Methods 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 238000002845 discoloration Methods 0.000 description 1
- 238000007580 dry-mixing Methods 0.000 description 1
- 230000003628 erosive effect Effects 0.000 description 1
- 238000006266 etherification reaction Methods 0.000 description 1
- 238000007046 ethoxylation reaction Methods 0.000 description 1
- 239000000835 fiber Substances 0.000 description 1
- 238000009472 formulation Methods 0.000 description 1
- 229940074391 gallic acid Drugs 0.000 description 1
- 235000004515 gallic acid Nutrition 0.000 description 1
- 235000004611 garlic Nutrition 0.000 description 1
- 239000010647 garlic oil Substances 0.000 description 1
- 239000000499 gel Substances 0.000 description 1
- 239000008103 glucose Substances 0.000 description 1
- 238000000227 grinding Methods 0.000 description 1
- 229910052735 hafnium Inorganic materials 0.000 description 1
- 125000005843 halogen group Chemical group 0.000 description 1
- 150000002460 imidazoles Chemical class 0.000 description 1
- 150000003949 imides Chemical class 0.000 description 1
- 150000002484 inorganic compounds Chemical class 0.000 description 1
- 229910010272 inorganic material Inorganic materials 0.000 description 1
- VYFOAVADNIHPTR-UHFFFAOYSA-N isatoic anhydride Chemical compound NC1=CC=CC=C1CO VYFOAVADNIHPTR-UHFFFAOYSA-N 0.000 description 1
- 150000002646 long chain fatty acid esters Chemical class 0.000 description 1
- 150000004668 long chain fatty acids Chemical class 0.000 description 1
- 239000011777 magnesium Substances 0.000 description 1
- 229910052749 magnesium Inorganic materials 0.000 description 1
- 229910052748 manganese Inorganic materials 0.000 description 1
- 239000000155 melt Substances 0.000 description 1
- 108010003855 mesentericopeptidase Proteins 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- 108010020132 microbial serine proteinases Proteins 0.000 description 1
- QJGQUHMNIGDVPM-UHFFFAOYSA-N nitrogen group Chemical group [N] QJGQUHMNIGDVPM-UHFFFAOYSA-N 0.000 description 1
- 238000006384 oligomerization reaction Methods 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 239000012188 paraffin wax Substances 0.000 description 1
- 239000006072 paste Substances 0.000 description 1
- 150000002989 phenols Chemical class 0.000 description 1
- QCDYQQDYXPDABM-UHFFFAOYSA-N phloroglucinol Chemical compound OC1=CC(O)=CC(O)=C1 QCDYQQDYXPDABM-UHFFFAOYSA-N 0.000 description 1
- 229960001553 phloroglucinol Drugs 0.000 description 1
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 description 1
- 239000010452 phosphate Substances 0.000 description 1
- 150000003014 phosphoric acid esters Chemical class 0.000 description 1
- 230000000704 physical effect Effects 0.000 description 1
- 229920001451 polypropylene glycol Polymers 0.000 description 1
- 230000008092 positive effect Effects 0.000 description 1
- 238000003825 pressing Methods 0.000 description 1
- 235000019419 proteases Nutrition 0.000 description 1
- 229940079877 pyrogallol Drugs 0.000 description 1
- 238000006722 reduction reaction Methods 0.000 description 1
- 238000006268 reductive amination reaction Methods 0.000 description 1
- 150000003334 secondary amides Chemical class 0.000 description 1
- 238000005204 segregation Methods 0.000 description 1
- 235000017550 sodium carbonate Nutrition 0.000 description 1
- 229960001922 sodium perborate Drugs 0.000 description 1
- 229910000031 sodium sesquicarbonate Inorganic materials 0.000 description 1
- 235000018341 sodium sesquicarbonate 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
- YKLJGMBLPUQQOI-UHFFFAOYSA-M sodium;oxidooxy(oxo)borane Chemical compound [Na+].[O-]OB=O YKLJGMBLPUQQOI-UHFFFAOYSA-M 0.000 description 1
- 239000007921 spray Substances 0.000 description 1
- 125000001424 substituent group Chemical group 0.000 description 1
- 239000003826 tablet Substances 0.000 description 1
- 229910052719 titanium Inorganic materials 0.000 description 1
- UNXRWKVEANCORM-UHFFFAOYSA-I triphosphate(5-) Chemical compound [O-]P([O-])(=O)OP([O-])(=O)OP([O-])([O-])=O UNXRWKVEANCORM-UHFFFAOYSA-I 0.000 description 1
- WCTAGTRAWPDFQO-UHFFFAOYSA-K trisodium;hydrogen carbonate;carbonate Chemical compound [Na+].[Na+].[Na+].OC([O-])=O.[O-]C([O-])=O WCTAGTRAWPDFQO-UHFFFAOYSA-K 0.000 description 1
- 229910052720 vanadium Inorganic materials 0.000 description 1
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 description 1
- 229920002554 vinyl polymer Polymers 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
- 238000004383 yellowing Methods 0.000 description 1
- 150000003752 zinc compounds Chemical class 0.000 description 1
- 229910052726 zirconium Inorganic materials 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
- C11D11/00—Special methods for preparing compositions containing mixtures of detergents
- C11D11/0082—Special methods for preparing compositions containing mixtures of detergents one or more of the detergent ingredients being in a liquefied state, e.g. slurry, paste or melt, and the process resulting in solid detergent particles such as granules, powders or beads
- C11D11/0088—Special methods for preparing compositions containing mixtures of detergents one or more of the detergent ingredients being in a liquefied state, e.g. slurry, paste or melt, and the process resulting in solid detergent particles such as granules, powders or beads the liquefied ingredients being sprayed or adsorbed onto solid particles
-
- C—CHEMISTRY; METALLURGY
- C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
- C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
- C11D17/00—Detergent materials or soaps characterised by their shape or physical properties
- C11D17/06—Powder; Flakes; Free-flowing mixtures; Sheets
-
- 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
- C11D3/0005—Other compounding ingredients characterised by their effect
- C11D3/0073—Anticorrosion compositions
-
- 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
- C11D3/18—Hydrocarbons
-
- C—CHEMISTRY; METALLURGY
- C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
- C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
- C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
- C11D3/16—Organic compounds
- C11D3/26—Organic compounds containing nitrogen
- C11D3/28—Heterocyclic compounds containing nitrogen in the ring
Definitions
- the application relates to granular components containing benzotriazole for the Use in MGSM and process for its production
- Granular cleaning agents for MGSM are known because they are easy to dose pourable and pourable, stable in storage and visually appealing to the consumer are.
- Benzotriazole is a corrosion protection component that in active oxygen Cleaners is widely used today.
- the chemical stability in these systems is only given to a limited extent, since benzotriazole is easily oxidized is broken down. This is especially the case with longer storage, e.g. yellow colored and unpleasant smelling oxidation products that discolor the Cleaner, the loss of corrosion protection and the lack of Acceptance of the product by the consumer.
- WO 95/1416 (Procter & Gamble) describes a bleaching composition which is suitable for automatic dishwashing, the one Contains oxygen bleach, paraffin oil and a benzotriazole component, the entire component is intended for use in detergents.
- the Components can be powder, granules, pastes, liquids, gels, Tablets are present, with granular preparation forms being preferred. Densities of at least 650 g / l or usually at least 700 g / l and preferably between 800 and 1200 g / l and particle sizes which are distributed in such a way that no more than 5% of the particles are larger than 1.4 mm in diameter and not more than 5% of the particles are less than 0.15 mm in diameter prefers.
- a preferred process for making the connection involves premixing paraffin oil and a dispersant, where this premix is sprayed onto the rest of the composition.
- the dispersant is advantageously nonionic surfactant.
- one Method of spraying paraffin oil and dispersant on the Bleach, with the associated reduction in dissolving speed of the bleaching agent in water, the so-called "coating”, is preferred, the coated bleach particles thereafter in a dry mixing process with the rest the composition is mixed.
- The is also described Compact the bleach before mixing it with the rest of the ingredients the composition mixed dry. There is no instruction how Benzotriazole homogeneously in a free-flowing dishwasher detergent component should be incorporated.
- the task was to provide a free-flowing, storage-stable, homogeneous granulate to make, which contains benzotriazole and as silver protection for the machine dishwashing is suitable.
- the one contained in the granulate Benzotriazole should be protected against oxidative attack.
- the present invention relates to a granular, free-flowing Component containing one at a temperature above 50 ° C meltable solid (I) from the group organic redox-active Substances, preferably from the group of benzotriazoles and one of the Melting temperature fixed inventory component (II) selected from the group of in Dishwasher detergents usual builder components and one or more others Components from the group of hydrocarbons or their mixtures and one or more further constituents from the group comprising the polar contains organic solvents and the surfactants, the ratio between solid (I) and solid (II) between 1 to 100 and 2 to 1, preferred between 1 to 70 and 3 to 2 and particularly preferably between 1 to 50 and 2 to 3 and the component has a particle size between 0.01 and 2 Millimeters, preferably 0.05 and 1.8 millimeters and particularly preferred between 0.1 and 1.6 millimeters.
- Water-soluble and water-insoluble builders can be used. There are water-soluble builders preferred as they are usually less on dishes and hard surfaces tend to form insoluble residues. Usual builders present may be the low molecular weight polycarboxylic acids and their salts, the homopolymeric and copolymeric polycarboxylic acids and their salts, the Carbonates, phosphates and silicates. Water-insoluble builders include Zeolites, which can also be used, as well as mixtures of the aforementioned builder substances. For the components according to the invention are preferably trisodium citrate and / or soda and / or bicarbonate and / or Alkali tripolyphosphates and / or disilicate and / or metasilicate used.
- the granular components according to the invention contain between 0.001 % By weight and 50% by weight, preferably between 0.05 and 20% by weight and particularly preferably between 0.5 and 10% by weight of benzotriazole compounds.
- benzotriazole compounds all chemical Derivatives of the benzotriazole skeleton.
- Derivatives of benzotriazole, in the sense of present invention, above all, those on the aromatic ring are whole or partially substituted compounds, with suitable substituents can be linear or branched alkyl chains with 1 to 20 carbon atoms. But OH, SH, vinyl or halogen groups are also conceivable.
- the ratio between Solid (I) and solid (II) between 1 to 100 and 2 to 1, preferably between 1 to 70 and 3 to 2 and particularly preferably between 1 to 50 and 2 to 3.
- An important parameter for the present means is the particle size of the Component that is between 0.01 and 2 millimeters, preferably 0.05 and 1.8 Millimeters and particularly preferably between 0.1 and 1.6 millimeters should.
- Another object of the invention is the use of these granular trickle-shaped component as a silver protection agent in automatic dishwashing detergents.
- Another object of the invention is a method for manufacturing granular free-flowing components, which is characterized in that the solid (I) melting above 50 ° C. in liquid form sprayed onto the solid (II) at elevated temperature.
- coarse-grained solid (I) preferably coarse-grained sodium citrate and / or coarse-grain soda and / or coarse-grained sodium bicarbonate is combined in one commercial mixer, preferably a ploughshare mixer, if possible low energy input and in a way that reduces the abrasion of the grain minimized, for example without the use of a knife ring, inside short time, preferably between 1 and 5 minutes, particularly preferably 3 Minutes at a spray temperature of above 100 ° C, preferably above 105 ° C particularly preferably between 110 and 120 ° C with the organic Brushed solid (II) in liquid form, and optionally cooled or let cool.
- the melt of the organic solid (I) can be used in this process will.
- the Substance (I) in the form of a solution in an organic solvent (III) is preferred in polar organic liquids, particularly preferably in concentrations of more than 30% by weight.
- This solvent (III) is preferred selected from the group consisting of methanol, ethanol, isopropanol, Ethylene glycol, propylene glycol, acetone, methyl ethyl ketone, polyethylene glycols and polypropylene glycols.
- the solvent is the group of surfactants, the nonionic surfactants being particularly preferred. Most notably preferred in the sense of the invention are the surfactants from the group of Alkyl polyglycosides, the fatty alcohol ethoxylates or propoxylates and their esters.
- a final spraying of the after has a particularly positive effect Granular components with hydrocarbons produced by the above method or a mixture of hydrocarbons with a melting point between 30 ° C and 120 ° C, preferably between 30 and 80 ° C, particularly preferably between 45 ° C and 65 ° C at elevated temperature.
- Prefers are used above all in the sense of the present invention macrocrystalline paraffins with melting points between 40 ° C and 60 ° C, microcrystalline paraffins with melting points between 60 ° C and 75 ° C and Mixtures between macro and micro crystalline paraffins with melting points from e.g. between 45 ° C and 65 ° C. But also other hydrocarbons and Mixtures of hydrocarbons can be used.
- dishwashing detergent containing granular component, preferably in amounts between 1 and 40% by weight based on the entire mixture, the dishwashing detergent also others Components common in dishwashing detergents, such as builder substances, sheet metal detergents, Surfactants, corrosion protection agents, polymers, other silver protection agents, May contain defoamers, perfumes and fragrances and others.
- Water-soluble and water-insoluble builders especially for binding calcium and magnesium be used.
- Water-soluble builders are preferred because they are based on Dishes and hard surfaces tend to be less insoluble To form residues.
- Usual builders that are within the scope of the invention 10 and 90% by weight, based on the total preparation, can be present, are the low molecular weight polycarboxylic acids and their salts, the homopolymeric and copolymeric polycarboxylic acids and their salts, the Carbonates, phosphates and silicates.
- Water-insoluble builders include Zeolites, which can also be used, as well as mixtures of the aforementioned builder substances.
- For the cleaning agents according to the invention are preferred trisodium citrate and / or pentasodium tripolyphosphate and silicate builders from the class of disilicates used.
- Alkali carriers can be present as further constituents.
- Alkali carbonates, especially sodium carbonate, sodium hydrogen carbonate or Sodium sesquicarbonate can be used.
- bleach activators are compounds that contain one or more N or O-acyl groups, like substances from the class of anhydrides, contain Esters, the imides and the acylated imidazoles or oximes.
- examples are Tetraacetylethylenediamine TAED, Tetraacetylmethylenediamine TAMD and Tetraacetylhexylenediamine TAHD, but also pentaacetylglucose PAG, 1,5-diacetyl-2,2-dioxo-hexahydro-1,3,5-triazine DADHT and isatoic anhydride ISA.
- bleach activator proportions between 1 and 5% by weight based on the entire preparation.
- Enzymes between 0 and 5% by weight of the cleaning agent Enzymes based on the entire preparation are added to the To increase the performance of the cleaning agents or under milder conditions To ensure cleaning performance of the same quality.
- the most common Enzymes used include lipases, amylases, cellulases and proteases.
- Preferred proteases are e.g. B. BLAP®140 from Biozym, Optimase®-M-440 and Opticlean®-M-250 from Solvay Enzymes; Maxacal®CX and Maxapem® or Esperase® from Gist Brocades or Savinase® from Novo.
- Celluzym® 0.7 T and. are particularly suitable cellulases and lipases Lipolase® 30 T from Novo Nordisk. Special use as amylases find Termamyl® 60 T, and Termamyl® 90 T and Duramyl® from Novo, Amylase-LT® from Solvay Enzymes or Maxamyl® P5000 from Gist Brocades but also other enzymes can be used.
- Surfactants can also be added to the dishwashing detergent according to the invention , in particular the nonionic surfactants, such as alkyl polyglycosides, ethoxylated fatty alcohols and glucamides are preferred.
- Alkyl polyglycosides are surfactants caused by the reaction of sugars and Alcohols according to the relevant procedures of preparative organic Chemistry can be obtained, depending on the type of manufacture to one Mixture of monoalkylated, oligomeric or polymeric sugar comes.
- Preferred Alkyl polyglycosides can be alkyl polyglucosides, with particular preference the alcohol is a long chain fatty alcohol or a mixture of long chain Is fatty alcohols and the degree of oligomerization of the sugars is between 1 and 10.
- alkoxylated alcohols as Reaction products of alkylene oxide, preferably ethylene oxide, with alcohols, preferred in the sense of the present invention, the longer-chain alcohols. In usually arise from n moles of ethylene oxide and one mole of alcohol, depending a complex mixture of addition products from the reaction conditions different degrees of ethoxylation. Another embodiment exists when using mixtures of the alkylene oxides preferred the mixture of Ethylene oxide and propylene oxide. You can also, if desired, by a final etherification with short-chain alkyl groups, such as the Butyl group, to the substance class of "closed" alcohol ethoxylates arrive, which can also be used in the sense of the invention. All are particularly preferred for the purposes of the present invention highly ethoxylated fatty alcohols or mixtures thereof end-capped fatty alcohol ethoxylates.
- Fatty acid polyhydroxylamides are acylated reaction products of the reductive amination of a sugar (glucose) with ammonia, whereby long-chain fatty acids, long-chain fatty acid esters or long-chain fatty acid chlorides are generally used as acylating agents.
- Secondary amides are formed when reducing with methylamine or ethylamine instead of with ammonia, such as. B. in S ⁇ FW-Journal, 119, (1993), 794-808.
- Carbon chain lengths of C 8 to C 12 in the fatty acid residue are preferably used.
- Dishwashing agents according to the invention can be used to protect the items to be washed or the machine contain other corrosion inhibitors, especially Silver protection agent in the field of automatic dishwashing a special one Have meaning as z. B. in DE 43 25 922, DE 41 28 672 or DE 43 38 724 are described.
- active chlorine-containing agents which corrode the Can significantly reduce the silver surface.
- oxygen and nitrogenous organic redox-active compounds such as di- and trihydric phenols, e.g. B. Hydroquinone, pyrocatechol, hydroxyhydroquinone, gallic acid, phloroglucin, Pyrogallol or derivatives of these classes of compounds.
- salt and complex inorganic compounds such as salts of the metals Mn, Ti, Zr, Hf, V, Co and Ce are often used. Zinc compounds can also be used to prevent corrosion on the wash ware.
- composition of the component according to the invention is a composition of the component according to the invention:
- This component was in amounts up to 6 wt .-%, based on the finished Means in one or more subsequent mixing steps with other Recipe ingredients for a dishwashing detergent for the machine Dishwashing mixed.
- Table (I) shows the compositions of the granules used.
- Surfactants e.g. Dehydol® LS4 (nonionic surfactant: coconut alcohol-4EO), Dehypon® LS54 (Nonionic surfactant: coconut alcohol-5EO4PO), Plurafac® LF 403 (nonionic surfactant C11-C13, 4EO-3PO),
- Polyethylene glycols Different molecular weights were used, e.g. B. 1500.
- Paraffins Macrocrystalline paraffins with melting points were preferred between 40 ° C and 60 ° C and microcrystalline paraffins with melting points between 60 ° C and 75 ° C, as well as mixtures of macrocrystalline and microcrystalline Paraffins with melting points between 45 ° C and 65 ° C used.
- Components I-VII had a particle size between 0.1 and 1.6 millimeters.
- Components I to VII were with percarbonate / TAED or perborate / TAED and the usual detergent components (citrate / phosphate, alkali carrier, enzymes) mixed up.
- the powder mixture is spread on crystallizing dishes and stored open for four days at 30 ° C and 80% relative humidity. Find oxidative processes and decomposition of the benzotriazole take place, that's it Powder colored yellow and has an unpleasant smell of garlic or Almond oil.
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Abstract
Description
Die Anmeldung betrifft benzotriazolhaltige, granulare Komponenten für den Einsatz in MGSM und Verfahren zu dessen HerstellungThe application relates to granular components containing benzotriazole for the Use in MGSM and process for its production
Granulare Reinigungsnsmittel für MGSM sind bekannt, weil sie gut dosierbar schütt- und rieselfähig, lagerstabil und optisch ansprechend für den Verbraucher sind.Granular cleaning agents for MGSM are known because they are easy to dose pourable and pourable, stable in storage and visually appealing to the consumer are.
Benzotriazol ist eine Korrosionsschutzkomponente, die in aktivsauerstoffhaltigen Reinigern heute weit verbreitet ist. Die chemische Stabilität in diesen Systemen ist aber nur bedingt gegeben, da Benzotriazol von Oxidationsmitteln leicht abgebaut wird. Dabei entstehen vor allem bei längerer Lagerung z.B. gelb gefärbte und unangenehm riechende Oxidationsprodukte, die zur Verfärbung des Reinigers, dem Verlust der Korrosionsschutzwirkung und zur mangelnden Akzeptanz des Produktes beim Verbraucher führen.Benzotriazole is a corrosion protection component that in active oxygen Cleaners is widely used today. The chemical stability in these systems is only given to a limited extent, since benzotriazole is easily oxidized is broken down. This is especially the case with longer storage, e.g. yellow colored and unpleasant smelling oxidation products that discolor the Cleaner, the loss of corrosion protection and the lack of Acceptance of the product by the consumer.
Aus der britischen Patentschrift GB 1 400 444 (Unilever) sind Granulate bekannt,
die einen organischen extrudierbaren Feststoff gleichmäßig dispergiert enthalten,
der ausgewählt ist aus der Gruppe der Korrosionsinhibitoren, wie der
Benzotriazole, der Bismethylenbenzotriazole, der ethoxylierten Phosphatester,
der Oxime und der Hydroxamate und die zur Einarbeitung in
Waschmittelpulverzusammensetzung geeignet sind. Wichtig dabei ist, daß der
extrudierbare Feststoff so gewählt ist, daß das Granulat in 20°C warmen Wasser
innerhalb 10 Minuten, bevorzugt innerhalb 2 Minuten aufgelöst wird. Das
beschriebene Verfahren beansprucht alle 
Die WO 95/1416 (Procter & Gamble) beschreibt eine Bleichzusammensetzung, die für das maschinelle Geschirrspülen geeignet ist, die eine Sauerstoffbleichmittel, Paraffinöl und eine Benzotriazolkomponente enthält, wobei die Gesamtkomponente zum Einsatz in Waschmitteln gedacht ist. Die Komponenten können als Pulver, Granulate, Pasten, Flüssigkeiten, Gele, Tabletten vorliegen, wobei granulare Zubereitungsformen bevorzugt sind. Dichten von mindestens 650 g/l oder üblicherweise mindestens 700 g/l und bevorzugt zwischen 800 und 1200 g/l sowie Teilchengrößen, die so verteilt sind, daß nicht mehr als 5% der Partikel größer als 1,4 mm im Durchmesser und nicht mehr als 5% der Partikel weniger als 0,15 mm im Durchmesser betragen, sind bevorzugt. In der Anmeldung werden mehrere Verfahren beschrieben, diese Granulate zu erhalten. Ein bevorzugter Prozeß zur Herstellung der Verbindung beinhaltet das Vormischen von Paraffinöl und einem Dispersionsmittel, wobei dieses Vorgemisch auf den Rest der Zusammensetzung aufgesprüht wird. Das Dispersionsmittel ist vorteilhafterweise nichtionisches Tensid. Aber auch eine Methode des Aufsprühens von Paraffinöl und Dispersionsmittel auf das Bleichmittel, mit der damit verbundenen Reduzierung der Lösegeschwindigkeit des Bleichmittels in Wasser, dem sogenannten "coaten", ist bevorzugt, wobei die gecoateten Bleichpartikel danach in einem Trockenmischprozess mit dem Rest der Zusammensetzung vermengt wird. Ebenfalls beschrieben ist die Kompaktierung des Bleichmittels bevor man es mit den restlichen Inhaltsstoffen der Zusammensetzung trocken vermischt. Es gibt keine Anweisung wie Benzotriazol homogen in eine gut rieselfähige Geschirrspülmittelkomponente eingearbeitet werden soll. WO 95/1416 (Procter & Gamble) describes a bleaching composition which is suitable for automatic dishwashing, the one Contains oxygen bleach, paraffin oil and a benzotriazole component, the entire component is intended for use in detergents. The Components can be powder, granules, pastes, liquids, gels, Tablets are present, with granular preparation forms being preferred. Densities of at least 650 g / l or usually at least 700 g / l and preferably between 800 and 1200 g / l and particle sizes which are distributed in such a way that no more than 5% of the particles are larger than 1.4 mm in diameter and not more than 5% of the particles are less than 0.15 mm in diameter prefers. Several procedures are described in the application, these To obtain granules. A preferred process for making the connection involves premixing paraffin oil and a dispersant, where this premix is sprayed onto the rest of the composition. The The dispersant is advantageously nonionic surfactant. But also one Method of spraying paraffin oil and dispersant on the Bleach, with the associated reduction in dissolving speed of the bleaching agent in water, the so-called "coating", is preferred, the coated bleach particles thereafter in a dry mixing process with the rest the composition is mixed. The is also described Compact the bleach before mixing it with the rest of the ingredients the composition mixed dry. There is no instruction how Benzotriazole homogeneously in a free-flowing dishwasher detergent component should be incorporated.
Die Patentschrift US 4 321 166 (Procter & Gamble) beschreibt builderfreie, flüssige Waschmittelsysteme, die als Korrosionsinhibitor eine Mischung aus aromatischen Triazolen und oligomeren olefinischen Fettsäuren enthalten. Das Antikorrosionsmittel soll hierbei die Verfärbung der metallenen Waschkörbe in automatischen Waschmaschinen und die Verfärbung von Fasern, die in Kontakt mit den Waschkörben kommen, verhindern. In der Schrift ist kein Hinweis darauf gegeben, wie organische redoxaktive Substanzen homogen in Bleichmittelkomponenten eingearbeitet werden können, und wie Silberschutz durch diese Komponenten erreicht werden kann.The US Pat. No. 4,321,166 (Procter & Gamble) describes builder-free, liquid detergent systems that act as a corrosion inhibitor aromatic triazoles and oligomeric olefinic fatty acids. The Anti-corrosion agents are said to discolor the metal wash baskets in automatic washing machines and the discoloration of fibers in contact prevent coming with the wash baskets. There is no reference to this in the scriptures given how organic redox-active substances homogeneous in Bleach components can be incorporated, and like silver protection can be achieved through these components.
Keine der oben genannten Patentschriften zeigt aber, wie eine Benzotriazol enthaltende granulare gut rieselförmige Komponente herstellbar ist. Das Problem liegt u.a. darin, daß Benzotriazol enthaltende Mischungen, die nach den üblichen Methoden der Granulation, wie zum Beispiel der Verwendung von Flüssigkeiten zum Kornaufbau, hergestellt werden, schlecht zu verarbeiten sind, da das Gemisch zum Verbacken neigt und daher schlecht rieselfähig ist. Die physikalische Eigenschaft der Rieselfähigkeit der Komponente sollte über einen langen Zeitraum stabil gehalten werden. Aber auch die chemische Stabilität von Benzotriazol enthaltenden Komponenten kann mit den Erkenntnissen der obigen Schriften nicht gelöst werden. Diese Eigenschaft wird um so wichtiger vor dem Hintergrund der Einarbeitung dieser Komponenten in Maschinengeschirrspülmittel. Hier sind die Eigenschaften der physikalischen und chemischen Stabilität der granularen Komponenten besonders wünschenswert. Besonders Benzotriazol soll bei Anwesenheit von oxidativ wirksamen Komponenten stabil bleiben, damit es noch als Silberschutzmittel wirksam sein kann.However, none of the above-mentioned patents shows how a benzotriazole containing granular well poured component can be produced. The problem lies among other things in that mixtures containing benzotriazole, according to the usual Methods of granulation, such as the use of liquids to build grain, are difficult to process, because that Mixture tends to cake and is therefore difficult to pour. The The physical property of the pourability of the component should have one be kept stable for a long period of time. But also the chemical stability of Components containing benzotriazole can use the knowledge of the above Fonts cannot be resolved. This property becomes all the more important before Background to the incorporation of these components in Dishwasher detergent. Here are the characteristics of the physical and chemical stability of the granular components is particularly desirable. Benzotriazole in particular is said to be oxidatively active in the presence of Components remain stable so that it can still be effective as a silver protection agent can.
Aufgabe war ein gut rieselfähiges, lagerstabiles, homogenes Granulat verfügbar zu machen, welches Benzotriazol enthält und als Silberschutz für das maschinelle Geschirrspülen geeignet ist. Das im Granulat enthaltende Benzotriazol sollte gegen oxidativen Angriff geschützt werden. The task was to provide a free-flowing, storage-stable, homogeneous granulate to make, which contains benzotriazole and as silver protection for the machine dishwashing is suitable. The one contained in the granulate Benzotriazole should be protected against oxidative attack.
Gegenstand der vorliegenden Erfindung ist eine granulare rieselförmige Komponente beinhaltend einen bei einer Temperatur oberhalb 50 °C schmelzbaren Feststoff (I) aus der Gruppe organischen redoxaktiven Substanzen, bevorzugt aus der Gruppe der Benzotriazole und einen bei dessen Schmelztemperatur festen Bestandsanteil (II) ausgewählt aus der Gruppe der in Geschirrspülmitteln üblichen Builderkomponenten und eine oder mehrere weitere Bestandteile aus der Gruppe der Kohlenwasserstoffe bzw. deren Gemische und ein oder mehrere weitere Bestandteile aus der Gruppe umfassend die polaren organischen Lösungsmittel und die Tenside enthält, wobei das Verhältnis zwischen Feststoff (I) und Feststoff (II) zwischen 1 zu 100 und 2 zu 1, bevorzugt zwischen 1 zu 70 und 3 zu 2 und besonders bevorzugt zwischen 1 zu 50 und 2 zu 3 liegt und die Komponente eine Teilchengröße zwischen 0,01 und 2 Millimetern, bevorzugt 0,05 und 1,8 Millimetern und besonders bevorzugt zwischen 0,1 und 1,6 Millimetern aufweist.The present invention relates to a granular, free-flowing Component containing one at a temperature above 50 ° C meltable solid (I) from the group organic redox-active Substances, preferably from the group of benzotriazoles and one of the Melting temperature fixed inventory component (II) selected from the group of in Dishwasher detergents usual builder components and one or more others Components from the group of hydrocarbons or their mixtures and one or more further constituents from the group comprising the polar contains organic solvents and the surfactants, the ratio between solid (I) and solid (II) between 1 to 100 and 2 to 1, preferred between 1 to 70 and 3 to 2 and particularly preferably between 1 to 50 and 2 to 3 and the component has a particle size between 0.01 and 2 Millimeters, preferably 0.05 and 1.8 millimeters and particularly preferred between 0.1 and 1.6 millimeters.
In den erfindungsgemäßen Komponenten können wasserlösliche und wasserunlösliche Builder eingesetzt werden. Dabei sind wasserlösliche Builder bevorzugt, da sie auf Geschirr und harten Oberflächen in der Regel weniger dazu tendieren unlösliche Rückstände zu bilden. Übliche Builder, die zugegen sein können, sind die niedermolekularen Polycarbonsäuren und ihre Salze, die homopolymeren und copolymeren Polycarbonsäuren und ihre Salze, die Carbonate, Phosphate und Silikate. Zu wasserunlöslichen Buildern zählen die Zeolithe, die ebenfalls verwendet werden können, ebenso wie Mischungen der vorgenannten Buildersubstanzen. Für die erfindungsgemäßen Komponenten werden bevorzugt Trinatriumcitrat und/oder Soda und/oder Bicarbonat und/oder Alkalitripolyphosphate und/oder Disilikat und/oder Metasilkat eingesetzt.Water-soluble and water-insoluble builders can be used. There are water-soluble builders preferred as they are usually less on dishes and hard surfaces tend to form insoluble residues. Usual builders present may be the low molecular weight polycarboxylic acids and their salts, the homopolymeric and copolymeric polycarboxylic acids and their salts, the Carbonates, phosphates and silicates. Water-insoluble builders include Zeolites, which can also be used, as well as mixtures of the aforementioned builder substances. For the components according to the invention are preferably trisodium citrate and / or soda and / or bicarbonate and / or Alkali tripolyphosphates and / or disilicate and / or metasilicate used.
Die erfindungsgemäßen granularen Komponenten beinhalten zwischen 0,001 Gew.-% und 50 Gew.-% bevorzugt zwischen 0,05 und 20 Gew.-% und besonders bevorzugt zwischen 0,5 und 10 Gew.-% Benzotriazolverbindungen. Der Fachmann versteht unter Benzotriazolverbindungen alle chemischen Derivate des Benzotriazolgerüstes. Derivate des Benzotriazols, im Sinne der vorliegenden Erfindung, sind vor allen Dingen die am aromatischen Ring ganz oder teilweise substituierten Verbindungen, wobei geeignete Substituenten lineare oder verzweigte Alkylketten mit 1 bis 20 Kohlenstoffatomen sein können. Aber auch OH, SH, Vinyl- oder Halogengruppen sind denkbar. Besonders die in der britischen Patentschrift GB 1 065 995 genannten Benzotriazolderivate sind geeignet, aber auch die in der britischen Patentschrift GB 1 226 100 beschriebenen 4, 5, 6, 7, Tetrahydrobenzotriazole können Verwendung finden. Ebenfalls geeignet sind Derivate des Bisbenzotriazols, wie sie unter anderem in der britischen Schrift GB 1 180 437 beschrieben sind.The granular components according to the invention contain between 0.001 % By weight and 50% by weight, preferably between 0.05 and 20% by weight and particularly preferably between 0.5 and 10% by weight of benzotriazole compounds. The expert understands by benzotriazole compounds all chemical Derivatives of the benzotriazole skeleton. Derivatives of benzotriazole, in the sense of present invention, above all, those on the aromatic ring are whole or partially substituted compounds, with suitable substituents can be linear or branched alkyl chains with 1 to 20 carbon atoms. But OH, SH, vinyl or halogen groups are also conceivable. Especially the one in British Patent GB 1,065,995 called benzotriazole derivatives suitable, but also that in British Patent GB 1 226 100 4, 5, 6, 7, tetrahydrobenzotriazoles described can be used. Derivatives of bisbenzotriazole, as described, inter alia, in the British document GB 1 180 437 are described.
Bevorzugt im Sinne der Erfindung sind Mittel, bei denen das Verhältnis zwischen Feststoff (I) und Feststoff (II) zwischen 1 zu 100 und 2 zu 1, bevorzugt zwischen 1 zu 70 und 3 zu 2 und besonders bevorzugt zwischen 1 zu 50 und 2 zu 3 liegt.For the purposes of the invention, means are preferred in which the ratio between Solid (I) and solid (II) between 1 to 100 and 2 to 1, preferably between 1 to 70 and 3 to 2 and particularly preferably between 1 to 50 and 2 to 3.
Ein wichtiger Parameter für die vorliegenden Mittel ist die Teilchengröße der Komponente, die zwischen 0,01 und 2 Millimetern, bevorzugt 0,05 und 1,8 Millimetern und besonders bevorzugt zwischen 0,1 und 1,6 Millimetern liegen sollte.An important parameter for the present means is the particle size of the Component that is between 0.01 and 2 millimeters, preferably 0.05 and 1.8 Millimeters and particularly preferably between 0.1 and 1.6 millimeters should.
Ein weiterer Gegenstand der Erfindung ist die Verwendung dieser granularen rieselförmigen Komponente als Silberschutzmittel in maschinellen Geschirrspülmitteln.Another object of the invention is the use of these granular trickle-shaped component as a silver protection agent in automatic dishwashing detergents.
Ein weiterer Gegenstand der Erfindung ist ein Verfahren zur Herstellung granularer rieselförmiger Komponenten, das dadurch gekennzeichnet ist, daß man den oberhalb 50 °C schmelzenden Feststoff (I) in flüssiger Form bei erhöhter Temperatur auf den Feststoff (II) aufsprüht.Another object of the invention is a method for manufacturing granular free-flowing components, which is characterized in that the solid (I) melting above 50 ° C. in liquid form sprayed onto the solid (II) at elevated temperature.
Dabei kann kontinuierlich oder im Batch-Verfahren gearbeitet werden. Der grobkörnige Feststoff (I), bevorzugt grobkörniges Natriumcitrat und/oder grobkörnige Soda und/oder grobkörniges Natriumbicarbonat wird in einem handelsüblichen Mischer, bevorzugt einem Pflugscharmischer, unter möglichst geringem Energieeintrag und auf eine Weise, die den Abrieb des Kornes minimiert, beispielsweise ohne den Einsatz eines Messerkranzes, innerhalb kurzer Zeit, bevorzugt zwischen 1 und 5 Minuten, besonders bevorzugt 3 Minuten bei einer Düstemperatur von oberhalb 100 °C, bevorzugt oberhalb 105 °C besonders bevorzugt zwischen 110 und 120 °C mit dem organischen Feststoff (II) in flüssiger Form bedüst, und gegebenenfalls abgekühlt oder auch abkühlen gelassen. Darüberhinaus können noch weitere bei der Waschmittelgranulation übliche Schritte, wie etwa Coaten, Imprägnieren, Zumischen von Fließverbesserern, Trocknen, Ertrudieren, u.ä. zur Einstellung der Pulvereigenschaften durchgeführt werden. Besonders geeignet ist dabei die Zumischung von Fließverbesserern.This can be done continuously or in a batch process. Of the coarse-grained solid (I), preferably coarse-grained sodium citrate and / or coarse-grain soda and / or coarse-grained sodium bicarbonate is combined in one commercial mixer, preferably a ploughshare mixer, if possible low energy input and in a way that reduces the abrasion of the grain minimized, for example without the use of a knife ring, inside short time, preferably between 1 and 5 minutes, particularly preferably 3 Minutes at a spray temperature of above 100 ° C, preferably above 105 ° C particularly preferably between 110 and 120 ° C with the organic Brushed solid (II) in liquid form, and optionally cooled or let cool. In addition, more can be used for detergent granulation usual steps, such as coating, impregnation, mixing in Flow improvers, drying, eroding, etc. for setting the powder properties be performed. The is particularly suitable Admixture of flow improvers.
In diesem Verfahren kann die Schmelze des organischen Feststoffs (I) eingesetzt werden. In einer bevorzugten Ausführungsform der Erfindung wird allerdings der Stoff (I) in Form einer Lösung in einem organischen Lösungsmittel (III), bevorzugt in polaren organischen Flüssigkeiten, besonders bevorzugt in Konzentrationen von mehr als 30 Gew.% eingesetzt. Dieses Lösungsmittel (III) wird bevorzugt ausgewählt aus der Gruppe bestehend aus Methanol, Ethanol, Isopropanol, Ethylenglycol, Propylenglykol, Aceton, Methylethylketon, Polyethylenglycolen und Polypropylenglycolen.The melt of the organic solid (I) can be used in this process will. In a preferred embodiment of the invention, however, the Substance (I) in the form of a solution in an organic solvent (III) is preferred in polar organic liquids, particularly preferably in concentrations of more than 30% by weight. This solvent (III) is preferred selected from the group consisting of methanol, ethanol, isopropanol, Ethylene glycol, propylene glycol, acetone, methyl ethyl ketone, polyethylene glycols and polypropylene glycols.
Ebenfalls bevorzugt als Lösungsmittel ist aber auch die Gruppe der Tenside, wobei die nichtionischen Tenside besonders bevorzugt werden. Ganz besonders bevorzugt im Sinne der Erfindung sind die Tenside aus der Gruppe der Alkylpolyglycoside, der Fettalkoholethoxylate bzw. -propoxylate und deren Ester.Also preferred as the solvent is the group of surfactants, the nonionic surfactants being particularly preferred. Most notably preferred in the sense of the invention are the surfactants from the group of Alkyl polyglycosides, the fatty alcohol ethoxylates or propoxylates and their esters.
Einen besonders positiven Effekt hat ein abschließendes Besprühen der nach obigem Verfahren hergestellten granularen Komponenten mit Kohlenwasserstoffen oder einem Gemisch aus Kohlenwasserstoffen mit einem Schmelzpunkt zwischen 30°C und 120°C, bevorzugt zwischen 30 und 80°C, besonders bevorzugt zwischen 45°C und 65°C bei erhöhter Temperatur. Bevorzugt verwendet werden im Sinne der vorliegenden Erfindung vor allem makrokristalline Paraffine mit Schmelzpunkten zwischen 40°C und 60°C, mikrokristalline Paraffine mit Schmelzpunkten zwischen 60°C und 75°C und Gemische zwischen makro- und mikrokristallinen Paraffinen mit Schmelzpunkten von z.B. zwischen 45°C und 65°C. Aber auch andere Kohlenwasserstoffe und Gemische von Kohlenwasserstoffen können eingesetzt werden.A final spraying of the after has a particularly positive effect Granular components with hydrocarbons produced by the above method or a mixture of hydrocarbons with a melting point between 30 ° C and 120 ° C, preferably between 30 and 80 ° C, particularly preferably between 45 ° C and 65 ° C at elevated temperature. Prefers are used above all in the sense of the present invention macrocrystalline paraffins with melting points between 40 ° C and 60 ° C, microcrystalline paraffins with melting points between 60 ° C and 75 ° C and Mixtures between macro and micro crystalline paraffins with melting points from e.g. between 45 ° C and 65 ° C. But also other hydrocarbons and Mixtures of hydrocarbons can be used.
Nach einem möglichen Abkühlungsschritt kann noch mit weiterem Feststoff (II) aus der Gruppe der Buildersubstanzen versetzt werden, wodurch eine gut rieselfähige granulare Komponente entsteht, die sich sehr gut in Geschirrspülmittel einarbeiten läßt und lagerstabile Reinigungsmittel mit gutem Silberschutz ergibt. Darüberhinaus können noch weitere bei der Waschmittelgranulation übliche Schritte, wie etwa Coaten, Imprägnieren, Zumischen von Fließverbesserern, Trocknen, Extrudieren, u.ä. zur Einstellung der Pulvereigenschaften durchgeführt werden.After a possible cooling step, another solid (II) from the group of builder substances, which makes a good free-flowing granular component is created, which is very good in Lets incorporate dishwashing detergent and storage-stable cleaning agents with good Silver protection results. In addition, more can be found at Detergent granulation usual steps, such as coating, impregnation, Admixing flow improvers, drying, extruding, etc. for adjustment the powder properties.
Ein weiterer Gegenstand der Erfindung ist ein Geschirrspülmittel, enthaltend eine granulare Komponente, bevorzugt in Mengen zwischen 1 und 40 Gew.-% bezogen auf die gesamte Mischung, wobei das Geschirrspülmittel auch weitere in Geschirrspülmitteln übliche Komponenten, wie Buildersubstanzen, Blechmittel, Tenside, Korrosionsschutzmittel, Polymere, andere Silberschutzmittel, Entschäumer, Parfum- und Duftstoffe und andere enthalten kann.Another object of the invention is a dishwashing detergent containing granular component, preferably in amounts between 1 and 40% by weight based on the entire mixture, the dishwashing detergent also others Components common in dishwashing detergents, such as builder substances, sheet metal detergents, Surfactants, corrosion protection agents, polymers, other silver protection agents, May contain defoamers, perfumes and fragrances and others.
In den erfindungsgemäßen Reinigungsmitteln können wasserlösliche und wasserunlösliche Builder vor allem zum Binden von Calcium und Magnesium eingesetzt werden. Dabei sind wasserlösliche Builder bevorzugt, da sie auf Geschirr und harten Oberflächen in der Regel weniger dazu tendieren unlösliche Rückstände zu bilden. Übliche Builder, die im Rahmen der Erfindung zwischen 10 und 90 Gew.-% bezogen auf die gesamte Zubereitung zugegen sein können, sind die niedermolekularen Polycarbonsäuren und ihre Salze, die homopolymeren und copolymeren Polycarbonsäuren und ihre Salze, die Carbonate, Phosphate und Silikate. Zu wasserunlöslichen Buildern zählen die Zeolithe, die ebenfalls verwendet werden können, ebenso wie Mischungen der vorgenannten Buildersubstanzen. Für die erfindungsgemäßen Reinigungsmittel werden bevorzugt Trinatriumcitrat und/oder Pentanatriumtripolyphosphat und silikatische Builder aus der Klasse der Disilikate eingesetzt.Water-soluble and water-insoluble builders especially for binding calcium and magnesium be used. Water-soluble builders are preferred because they are based on Dishes and hard surfaces tend to be less insoluble To form residues. Usual builders that are within the scope of the invention 10 and 90% by weight, based on the total preparation, can be present, are the low molecular weight polycarboxylic acids and their salts, the homopolymeric and copolymeric polycarboxylic acids and their salts, the Carbonates, phosphates and silicates. Water-insoluble builders include Zeolites, which can also be used, as well as mixtures of the aforementioned builder substances. For the cleaning agents according to the invention are preferred trisodium citrate and / or pentasodium tripolyphosphate and silicate builders from the class of disilicates used.
Als weitere Bestandteile können Alkaliträger zugegen sein. Als Alkaliträger gelten Alkalimetallhydroxide, Alkalimetallcarbonate, Alkalimetallhydrogencarbonate, Alkalimetallsesquicarbonate, Alkalisilikate, Alkalimetasilikate, und Mischungen der vorgenannten Stoffe, wobei im Sinne dieser Erfindung bevorzugt die Alkalicarbonate, insbesondere Natriumcarbonat, Natriumhydrogencarbonat oder Natriumsesquicarbonat eingesetzt werden.Alkali carriers can be present as further constituents. Are considered to be alkali carriers Alkali metal hydroxides, alkali metal carbonates, alkali metal hydrogen carbonates, Alkali metal sesquicarbonates, alkali silicates, alkali metal silicates, and mixtures the abovementioned substances, the preferred being in the sense of this invention Alkali carbonates, especially sodium carbonate, sodium hydrogen carbonate or Sodium sesquicarbonate can be used.
Bekannte Bleichaktivatoren sind Verbindungen, die eine oder mehrere N- bzw. O-Acylgruppen enthalten, wie Substanzen aus der Klasse der Anhydride, der Ester, der Imide und der acylierten Imidazole oder Oxime. Beispiele sind Tetraacetylethylendiamin TAED, Tetraacetylmethylendiamin TAMD und Tetraacetylhexylendiamin TAHD, aber auch Pentaacetylglucose PAG, 1,5-Diacetyl-2,2-dioxo-hexahydro-1,3,5-triazin DADHT und Isatosäureanhydrid ISA. Für die vorliegende Erfindung haben sich Bleichaktivatorenanteile zwischen 1 und 5 Gew.-% bezogen auf die gesamte Zubereitung bewährt.Known bleach activators are compounds that contain one or more N or O-acyl groups, like substances from the class of anhydrides, contain Esters, the imides and the acylated imidazoles or oximes. examples are Tetraacetylethylenediamine TAED, Tetraacetylmethylenediamine TAMD and Tetraacetylhexylenediamine TAHD, but also pentaacetylglucose PAG, 1,5-diacetyl-2,2-dioxo-hexahydro-1,3,5-triazine DADHT and isatoic anhydride ISA. For the present invention, bleach activator proportions between 1 and 5% by weight based on the entire preparation.
Erfindungsgemäß können dem Reinigungsmittel zwischen 0 und 5 Gew.-% Enzyme bezogen auf die gesamte Zubereitung zugesetzt werden, um die Leistung der Reinigungsmittel zu steigern oder unter milderen Bedingungen die Reinigungsleistung in gleicher Qualität zu gewährleisten. Zu den am häufigsten verwendeteten Enzymen gehören Lipasen, Amylasen, Cellulasen und Proteasen. Bevorzugte Proteasen sind z. B. BLAP®140 der Fa. Biozym, Optimase®-M-440 und Opticlean®-M-250 der Fa. Solvay Enzymes; Maxacal®CX und Maxapem® oder Esperase® der Fa. Gist Brocades oder auch Savinase® der Fa. Novo. According to the invention, between 0 and 5% by weight of the cleaning agent Enzymes based on the entire preparation are added to the To increase the performance of the cleaning agents or under milder conditions To ensure cleaning performance of the same quality. The most common Enzymes used include lipases, amylases, cellulases and proteases. Preferred proteases are e.g. B. BLAP®140 from Biozym, Optimase®-M-440 and Opticlean®-M-250 from Solvay Enzymes; Maxacal®CX and Maxapem® or Esperase® from Gist Brocades or Savinase® from Novo.
Besonders geeignete Cellulasen und Lipasen sind Celluzym® 0,7 T und Lipolase® 30 T der Fa. Novo Nordisk. Besondere Verwendung als Amylasen finden Termamyl® 60 T, und Termamyl® 90 T und Duramyl® der Fa. Novo, Amylase-LT® der Fa. Solvay Enzymes oder Maxamyl® P5000 der Fa. Gist Brocades aber auch andere Enzyme können angewendet werden.Celluzym® 0.7 T and. Are particularly suitable cellulases and lipases Lipolase® 30 T from Novo Nordisk. Special use as amylases find Termamyl® 60 T, and Termamyl® 90 T and Duramyl® from Novo, Amylase-LT® from Solvay Enzymes or Maxamyl® P5000 from Gist Brocades but also other enzymes can be used.
Auch Tenside können dem erfindungsgemäßen Geschirrspülmittel zugesetzt werden, wobei besonders die nichtionischen Tenside , wie Alkylpolyglycoside, ethoxylierte Fettalkohole und Glucamide bevorzugt sind.Surfactants can also be added to the dishwashing detergent according to the invention , in particular the nonionic surfactants, such as alkyl polyglycosides, ethoxylated fatty alcohols and glucamides are preferred.
Alkylpolyglycoside sind Tenside, die durch die Reaktion von Zuckern und Alkoholen nach den einschlägigen Verfahren der präparativen organischen Chemie erhalten werden können, wobei es je nach Art der Herstellung zu einem Gemisch monoalkylierter, oligomerer oder polymerer Zucker kommt. Bevorzugte Alkylpolyglykoside können Alkylpolyglucoside sein, wobei besonders bevorzugt der Alkohol ein langkettiger Fettalkohol oder ein Gemisch langkettiger Fettalkohole ist und der Oligomerisierungsgrad der Zucker zwischen 1 und 10 ist.Alkyl polyglycosides are surfactants caused by the reaction of sugars and Alcohols according to the relevant procedures of preparative organic Chemistry can be obtained, depending on the type of manufacture to one Mixture of monoalkylated, oligomeric or polymeric sugar comes. Preferred Alkyl polyglycosides can be alkyl polyglucosides, with particular preference the alcohol is a long chain fatty alcohol or a mixture of long chain Is fatty alcohols and the degree of oligomerization of the sugars is between 1 and 10.
Der Fachmann versteht allgemein unter alkoxylierten Alkoholen die Reaktionsprodukte von Alkylenoxid, bevorzugt Ethylenoxid, mit Alkoholen, bevorzugt im Sinne der vorliegenden Erfindung die längerkettigen Alkohole. In der Regel enstehen aus n Molen Ethylenoxid und einem Mol Alkohol, abhängig von den Reaktionsbedingungen ein komplexes Gemisch von Additionsprodukten unterschiedlichen Ethoxylierungsgrades. Eine weitere Ausführungsform besteht im Einsatz von Gemischen der Alkylenoxide bevozugt des Gemisches von Ethylenoxid und Propylenoxid. Auch kann man gewünschtenfalls durch eine abschließende Veretherung mit kurzkettigen Alkylgruppen, wie bevorzugt der Butylgruppe, zur Substanzklasse der "verschlossenen" Alkoholethoxylaten gelangen, die ebenfalls im Sinne der Erfindung eingesetzt werden kann. Ganz besonders bevorzugt im Sinne der vorliegenden Erfindung sind dabei hochethoxylierte Fettalkohole oder deren Gemische mit endgruppenverschlossenen Fettalkoholethoxylaten.The person skilled in the art generally understands alkoxylated alcohols as Reaction products of alkylene oxide, preferably ethylene oxide, with alcohols, preferred in the sense of the present invention, the longer-chain alcohols. In usually arise from n moles of ethylene oxide and one mole of alcohol, depending a complex mixture of addition products from the reaction conditions different degrees of ethoxylation. Another embodiment exists when using mixtures of the alkylene oxides preferred the mixture of Ethylene oxide and propylene oxide. You can also, if desired, by a final etherification with short-chain alkyl groups, such as the Butyl group, to the substance class of "closed" alcohol ethoxylates arrive, which can also be used in the sense of the invention. All are particularly preferred for the purposes of the present invention highly ethoxylated fatty alcohols or mixtures thereof end-capped fatty alcohol ethoxylates.
Fettsäurepolyhydroxylamide (Glucamide) sind acylierte Reakionsprodukte der reduktiven Aminierung eines Zuckers (Glucose) mit Ammoniak, wobei als Acylierungsmittel in der Regel langkettige Fettsäuren, langkettige Fettsäureester oder langkettige Fettsäurechloride genutzt werden. Dabei entstehen sekundäre Amide, wenn man statt mit Ammoniak mit Methylamin oder Ethylamin reduziert, wie z. B. in SÖFW-Journal, 119, (1993), 794-808 beschrieben wird. Bevorzugt benutzt man Kohlenstoffkettenlängen von C8 bis C12 im Fettsäurerest.Fatty acid polyhydroxylamides (glucamides) are acylated reaction products of the reductive amination of a sugar (glucose) with ammonia, whereby long-chain fatty acids, long-chain fatty acid esters or long-chain fatty acid chlorides are generally used as acylating agents. Secondary amides are formed when reducing with methylamine or ethylamine instead of with ammonia, such as. B. in SÖFW-Journal, 119, (1993), 794-808. Carbon chain lengths of C 8 to C 12 in the fatty acid residue are preferably used.
Erfindungsgemäße Geschirrspülmittel können zum Schutze des Spülgutes oder der Maschine weitere Korrosionsinhibitoren enthalten, wobei besonders Silberschutzmittel im Bereich des maschinellen Geschirrspülens eine besondere Bedeutung haben, wie sie z. B. in der DE 43 25 922, der DE 41 28 672 oder der DE 43 38 724 beschrieben sind. Man findet in Reiniger-formulierungen darüberhinaus häufig aktivchlorhaltige Mittel, die das Korrodieren der Silberoberfläche deutlich vermindern können. In chlorfreien Reinigern werden gemäß der obigen Schriften besonders sauerstoff- und stickstoffhaltige organische redoxaktive Verbindungen, wie zwei- und dreiwertige Phenole, z. B. Hydrochinon, Brenzkatechin, Hydroxyhydrochinon, Gallussäure, Phloroglucin, Pyrogallol bzw. Derivate dieser Verbindungsklassen. Auch salz- und komplexartige anorganische Verbindungen, wie Salze der Metalle Mn, Ti, Zr, Hf, V, Co und Ce finden häufig Verwendung. Ebenfalls können Zinkverbindungen zur Verhinderung der Korrosion am Spülgut eingesetzt werden. Dishwashing agents according to the invention can be used to protect the items to be washed or the machine contain other corrosion inhibitors, especially Silver protection agent in the field of automatic dishwashing a special one Have meaning as z. B. in DE 43 25 922, DE 41 28 672 or DE 43 38 724 are described. One finds in cleaner formulations In addition, active chlorine-containing agents which corrode the Can significantly reduce the silver surface. In chlorine-free cleaners according to the above writings especially oxygen and nitrogenous organic redox-active compounds, such as di- and trihydric phenols, e.g. B. Hydroquinone, pyrocatechol, hydroxyhydroquinone, gallic acid, phloroglucin, Pyrogallol or derivatives of these classes of compounds. Also salt and complex inorganic compounds, such as salts of the metals Mn, Ti, Zr, Hf, V, Co and Ce are often used. Zinc compounds can also be used to prevent corrosion on the wash ware.
27.9 kg grobkörnige Soda wurde in einem Lödige-Pflugscharmischer vorgelegt, ohne den Einsatz des Messerkranzes innerhalb 3 Minuten bei einer Schmelztemperatur von 110 und 120 °C mit 2.1 kg Benzotriazol bedüst, wobei nach dem Abkühlen auf Raumtemperatur eine gut rieselfähige granulare Komponente entstand.27.9 kg of coarse-grained soda was placed in a Lödige ploughshare mixer, without using the knife ring within 3 minutes at one Melting temperature of 110 and 120 ° C sprayed with 2.1 kg of benzotriazole, whereby after cooling to room temperature, a free-flowing granular Component was created.
Diese Komponente wurde in Mengen bis zu 6 Gew.-%, bezogen auf das fertige Mittel in einem oder mehreren nachfolgenden Mischschritten mit weiteren Rezepturbestandteilen zu einem Geschirrspülmittel für das maschinelle Geschirrspülen vermischt. Dies bestand z. B aus 25 g Natriumcitrat, 25 g Natriumcarbonat, 10 g Natriumperborat, 4 g Tetraethylendiamintetraessigsäure, 3,5 g Enzymen (wie Amylase, Protease und Lipase) und 2 g nichtionischen Tensiden (wie Alkylpolyglycosiden und ethoxylierten Fettalkoholen).This component was in amounts up to 6 wt .-%, based on the finished Means in one or more subsequent mixing steps with other Recipe ingredients for a dishwashing detergent for the machine Dishwashing mixed. This consisted e.g. B from 25 g sodium citrate, 25 g Sodium carbonate, 10 g sodium perborate, 4 g tetraethylenediaminetetraacetic acid, 3.5 g of enzymes (such as amylase, protease and lipase) and 2 g of nonionic Surfactants (such as alkyl polyglycosides and ethoxylated fatty alcohols).
Die erfindungsgemäßen Komponenten lassen sich sehr gut in Geschirrspülmittel
einarbeiten und ergeben lagerstabile Reinigungsmittel mit gutem Silberschutz. In
Tabelle (I) sind die Zusammensetzungen der verwendeten Granulate
angegeben.
Tenside: z.B. Dehydol® LS4 (Niotensid: Kokosalkohol-4EO), Dehypon® LS54 (Niotensid: Kokosalkohol-5EO4PO), Plurafac® LF 403 (Niotensid C11-C13, 4EO-3PO),Surfactants: e.g. Dehydol® LS4 (nonionic surfactant: coconut alcohol-4EO), Dehypon® LS54 (Nonionic surfactant: coconut alcohol-5EO4PO), Plurafac® LF 403 (nonionic surfactant C11-C13, 4EO-3PO),
Polyethylenglycole: Es wurden verschiedene Molekulargewichte eingesetzt, z. B. 1500.Polyethylene glycols: Different molecular weights were used, e.g. B. 1500.
Paraffine: Es wurden bevorzugt makrokristalline Paraffine mit Schmelzpunkten zwischen 40 °C und 60 °C und mikrokristalline Paraffine mit Schmelzpunkten zwischen 60 °C und 75 °C, sowie Gemische aus makrokristallinen und mikrokristallinen Paraffinen mit Schmelzpunktewn zwischen 45 °C und 65 °C eingesetzt.Paraffins: Macrocrystalline paraffins with melting points were preferred between 40 ° C and 60 ° C and microcrystalline paraffins with melting points between 60 ° C and 75 ° C, as well as mixtures of macrocrystalline and microcrystalline Paraffins with melting points between 45 ° C and 65 ° C used.
Die Komponenten I - VII hatten eine Teilchengröße zwischen 0,1 und 1,6 Millimetern.Components I-VII had a particle size between 0.1 and 1.6 millimeters.
Die Komponenten I bis VII wurden mit Percarbonat/TAED bzw. Perborat/TAED und den üblichen Reinigerbestandteilen (Citrat/Phosphat, Alkaliträger, Enzyme) aufgemischt. Das Pulvergemisch wird auf Kristallisierschalen ausgebreitet und vier Tage offen bei 30°C und 80% relativer Luftfeuchteigkeit gelagert. Finden dabei oxidative Prozesse und Zersetzung des Benzotriazols statt, so ist das Pulver gelb gefärbt und hat einen unangenehmen Geruch nach Knoblauch bzw. Mandelöl.Components I to VII were with percarbonate / TAED or perborate / TAED and the usual detergent components (citrate / phosphate, alkali carrier, enzymes) mixed up. The powder mixture is spread on crystallizing dishes and stored open for four days at 30 ° C and 80% relative humidity. Find oxidative processes and decomposition of the benzotriazole take place, that's it Powder colored yellow and has an unpleasant smell of garlic or Almond oil.
Die Mischungen wurden von mehreren Fachleuten auf dem Gebiet des
maschinellen Geschirrspülens visuell und olfaktorisch untersucht. Die Ergebnisse
des Lagertests sind in Tabelle (II) zusammengefaßt.
Claims (13)
wobei das Verhältnis zwischen Feststoff (I) und Feststoff (II) zwischen 1 zu 100 und 2 zu 1, bevorzugt zwischen 1 zu 70 und 3 zu 2 und besonders bevorzugt zwischen 1 zu 50 und 2 zu 3 liegt und die Komponente eine Teilchengröße zwischen 0,01 und 2 Millimetern, bevorzugt 0,05 und 1,8 Millimetern und besonders bevorzugt zwischen 0,1 und 1,6 Millimetern aufweist.
the ratio between solid (I) and solid (II) between 1 to 100 and 2 to 1, preferably between 1 to 70 and 3 to 2 and particularly preferably between 1 to 50 and 2 to 3 and the component has a particle size between 0 , 01 and 2 millimeters, preferably 0.05 and 1.8 millimeters and particularly preferably between 0.1 and 1.6 millimeters.
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| DE19631787 | 1996-08-07 | ||
| DE19631787A DE19631787C2 (en) | 1996-08-07 | 1996-08-07 | Granular component containing benzotriazole for use in machine dishwashing detergents (MGSM) and process for its production |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| EP0826768A1 true EP0826768A1 (en) | 1998-03-04 |
| EP0826768B1 EP0826768B1 (en) | 2001-10-24 |
Family
ID=7801964
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| EP97113068A Expired - Lifetime EP0826768B1 (en) | 1996-08-07 | 1997-07-30 | Granular components for automatic dishwashing compositions, and method of making them |
Country Status (4)
| Country | Link |
|---|---|
| EP (1) | EP0826768B1 (en) |
| AT (1) | ATE207525T1 (en) |
| DE (2) | DE19631787C2 (en) |
| ES (1) | ES2166032T3 (en) |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO1999063044A1 (en) * | 1998-06-03 | 1999-12-09 | Henkel Kommanditgesellschaft Auf Aktien | Production of granulates containing alkylpolyglycoside |
| WO2001072949A1 (en) * | 2000-03-28 | 2001-10-04 | Henkel Kommanditgesellschaft Auf Aktien | Particle-shaped dishwashing machine detergents having a clear rinsing effect |
| DE10313455A1 (en) * | 2003-03-25 | 2004-10-14 | Henkel Kgaa | Detergents and cleaning agents |
Families Citing this family (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE19758262A1 (en) | 1997-12-31 | 1999-07-08 | Henkel Kgaa | Granular component containing alkylaminotriazole for use in machine dishwashing detergents (MGSM) and process for its production |
| DE10049657C2 (en) * | 2000-10-07 | 2003-02-27 | Henkel Kgaa | Machine dishwashing method and machine dishwashing detergent with improved corrosion protection |
| DE102011077098A1 (en) * | 2011-06-07 | 2012-12-13 | Henkel Kgaa | Silver-protecting dishwashing detergent |
| DE102018212206A1 (en) | 2018-07-23 | 2020-01-23 | Henkel Ag & Co. Kgaa | Detergent with silver protection |
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| WO1995010588A1 (en) * | 1993-10-14 | 1995-04-20 | Unilever N.V. | Detergent compositions containing silver anti-tarnishing agents |
| EP0682105A2 (en) * | 1994-04-13 | 1995-11-15 | The Procter & Gamble Company | Bleaching compositions |
| EP0690122A2 (en) * | 1994-06-30 | 1996-01-03 | The Procter & Gamble Company | Detergent compositions |
Family Cites Families (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| GB2285052A (en) * | 1993-12-23 | 1995-06-28 | Procter & Gamble | Detergent composition |
-
1996
- 1996-08-07 DE DE19631787A patent/DE19631787C2/en not_active Expired - Fee Related
-
1997
- 1997-07-30 DE DE59705054T patent/DE59705054D1/en not_active Expired - Fee Related
- 1997-07-30 AT AT97113068T patent/ATE207525T1/en not_active IP Right Cessation
- 1997-07-30 ES ES97113068T patent/ES2166032T3/en not_active Expired - Lifetime
- 1997-07-30 EP EP97113068A patent/EP0826768B1/en not_active Expired - Lifetime
Patent Citations (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP0032236A1 (en) * | 1980-01-12 | 1981-07-22 | Henkel Kommanditgesellschaft auf Aktien | Dishwashing detergent |
| WO1993004153A1 (en) * | 1991-08-13 | 1993-03-04 | The Procter & Gamble Company | Process for making granular automatic dishwashing detergent |
| WO1994026860A1 (en) * | 1993-05-08 | 1994-11-24 | Henkel Kommanditgesellschaft Auf Aktien | Silver-corrosion protection agent (ii) |
| WO1995001416A1 (en) * | 1993-07-01 | 1995-01-12 | The Procter & Gamble Company | Machine dishwashing composition containing oxygen bleach and paraffin oil and benzotriazole compound silver tarnishing inhibitors |
| EP0634478A1 (en) * | 1993-07-16 | 1995-01-18 | The Procter & Gamble Company | Machine dishwashing detergent compositions |
| WO1995010588A1 (en) * | 1993-10-14 | 1995-04-20 | Unilever N.V. | Detergent compositions containing silver anti-tarnishing agents |
| EP0682105A2 (en) * | 1994-04-13 | 1995-11-15 | The Procter & Gamble Company | Bleaching compositions |
| EP0690122A2 (en) * | 1994-06-30 | 1996-01-03 | The Procter & Gamble Company | Detergent compositions |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO1999063044A1 (en) * | 1998-06-03 | 1999-12-09 | Henkel Kommanditgesellschaft Auf Aktien | Production of granulates containing alkylpolyglycoside |
| WO2001072949A1 (en) * | 2000-03-28 | 2001-10-04 | Henkel Kommanditgesellschaft Auf Aktien | Particle-shaped dishwashing machine detergents having a clear rinsing effect |
| DE10313455A1 (en) * | 2003-03-25 | 2004-10-14 | Henkel Kgaa | Detergents and cleaning agents |
Also Published As
| Publication number | Publication date |
|---|---|
| EP0826768B1 (en) | 2001-10-24 |
| ES2166032T3 (en) | 2002-04-01 |
| DE19631787C2 (en) | 2000-06-29 |
| ATE207525T1 (en) | 2001-11-15 |
| DE59705054D1 (en) | 2001-11-29 |
| DE19631787A1 (en) | 1998-02-12 |
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