EP0835926A2 - Verfahren zur Herstellung eines gecoateten Bleichaktivatorgranulats - Google Patents
Verfahren zur Herstellung eines gecoateten Bleichaktivatorgranulats Download PDFInfo
- Publication number
- EP0835926A2 EP0835926A2 EP97116693A EP97116693A EP0835926A2 EP 0835926 A2 EP0835926 A2 EP 0835926A2 EP 97116693 A EP97116693 A EP 97116693A EP 97116693 A EP97116693 A EP 97116693A EP 0835926 A2 EP0835926 A2 EP 0835926A2
- Authority
- EP
- European Patent Office
- Prior art keywords
- coating
- granules
- activator
- coated
- bleach activator
- 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
- 239000008187 granular material Substances 0.000 title claims abstract description 84
- 239000012190 activator Substances 0.000 title claims abstract description 49
- 239000007844 bleaching agent Substances 0.000 title claims abstract description 28
- 238000004519 manufacturing process Methods 0.000 title claims abstract description 5
- 238000000034 method Methods 0.000 title claims description 39
- 238000000576 coating method Methods 0.000 claims abstract description 89
- 239000011248 coating agent Substances 0.000 claims abstract description 86
- 238000005496 tempering Methods 0.000 claims abstract description 26
- 238000002844 melting Methods 0.000 claims abstract description 20
- 230000008018 melting Effects 0.000 claims abstract description 19
- 239000000126 substance Substances 0.000 claims description 44
- 230000008569 process Effects 0.000 claims description 23
- 239000003599 detergent Substances 0.000 claims description 15
- 229920000642 polymer Polymers 0.000 claims description 9
- 239000000654 additive Substances 0.000 claims description 8
- 229910052751 metal Inorganic materials 0.000 claims description 4
- 239000002184 metal Substances 0.000 claims description 4
- 239000001993 wax Substances 0.000 claims description 4
- 150000001408 amides Chemical class 0.000 claims description 3
- 150000001412 amines Chemical class 0.000 claims description 3
- 239000012459 cleaning agent Substances 0.000 claims description 3
- 150000007524 organic acids Chemical class 0.000 claims description 3
- YIKSCQDJHCMVMK-UHFFFAOYSA-N Oxamide Chemical class NC(=O)C(N)=O YIKSCQDJHCMVMK-UHFFFAOYSA-N 0.000 claims description 2
- 150000008063 acylals Chemical class 0.000 claims description 2
- 150000001244 carboxylic acid anhydrides Chemical class 0.000 claims description 2
- 150000001733 carboxylic acid esters Chemical class 0.000 claims description 2
- 239000008139 complexing agent Substances 0.000 claims description 2
- 235000014113 dietary fatty acids Nutrition 0.000 claims description 2
- 239000000194 fatty acid Substances 0.000 claims description 2
- 229930195729 fatty acid Natural products 0.000 claims description 2
- 150000002576 ketones Chemical class 0.000 claims description 2
- 150000003951 lactams Chemical class 0.000 claims description 2
- 150000002596 lactones Chemical class 0.000 claims description 2
- 150000007522 mineralic acids Chemical class 0.000 claims description 2
- 150000002825 nitriles Chemical class 0.000 claims description 2
- 235000005985 organic acids Nutrition 0.000 claims description 2
- 229920001296 polysiloxane Polymers 0.000 claims description 2
- 235000000346 sugar Nutrition 0.000 claims description 2
- 239000003945 anionic surfactant Substances 0.000 claims 1
- 239000000645 desinfectant Substances 0.000 claims 1
- 150000004665 fatty acids Chemical class 0.000 claims 1
- 150000002191 fatty alcohols Chemical class 0.000 claims 1
- 239000002736 nonionic surfactant Substances 0.000 claims 1
- 229920001515 polyalkylene glycol Polymers 0.000 claims 1
- 125000001453 quaternary ammonium group Chemical group 0.000 claims 1
- 150000008163 sugars Chemical class 0.000 claims 1
- 239000000463 material Substances 0.000 abstract description 6
- KFSLWBXXFJQRDL-UHFFFAOYSA-N Peracetic acid Chemical compound CC(=O)OO KFSLWBXXFJQRDL-UHFFFAOYSA-N 0.000 description 58
- FRPJTGXMTIIFIT-UHFFFAOYSA-N tetraacetylethylenediamine Chemical compound CC(=O)C(N)(C(C)=O)C(N)(C(C)=O)C(C)=O FRPJTGXMTIIFIT-UHFFFAOYSA-N 0.000 description 30
- 239000000047 product Substances 0.000 description 24
- 230000015572 biosynthetic process Effects 0.000 description 22
- 235000021355 Stearic acid Nutrition 0.000 description 18
- QIQXTHQIDYTFRH-UHFFFAOYSA-N octadecanoic acid Chemical compound CCCCCCCCCCCCCCCCCC(O)=O QIQXTHQIDYTFRH-UHFFFAOYSA-N 0.000 description 18
- OQCDKBAXFALNLD-UHFFFAOYSA-N octadecanoic acid Natural products CCCCCCCC(C)CCCCCCCCC(O)=O OQCDKBAXFALNLD-UHFFFAOYSA-N 0.000 description 18
- 239000008117 stearic acid Substances 0.000 description 18
- 238000003860 storage Methods 0.000 description 13
- 239000000203 mixture Substances 0.000 description 12
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 description 11
- 239000000428 dust Substances 0.000 description 10
- 239000012530 fluid Substances 0.000 description 10
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 9
- TWJNQYPJQDRXPH-UHFFFAOYSA-N 2-cyanobenzohydrazide Chemical compound NNC(=O)C1=CC=CC=C1C#N TWJNQYPJQDRXPH-UHFFFAOYSA-N 0.000 description 8
- 102000004190 Enzymes Human genes 0.000 description 8
- 108090000790 Enzymes Proteins 0.000 description 8
- 235000021360 Myristic acid Nutrition 0.000 description 8
- TUNFSRHWOTWDNC-UHFFFAOYSA-N Myristic acid Natural products CCCCCCCCCCCCCC(O)=O TUNFSRHWOTWDNC-UHFFFAOYSA-N 0.000 description 8
- 238000005299 abrasion Methods 0.000 description 8
- 238000004061 bleaching Methods 0.000 description 8
- 238000002156 mixing Methods 0.000 description 7
- 229920002472 Starch Polymers 0.000 description 6
- -1 ether carboxylic acid Chemical class 0.000 description 6
- 150000003839 salts Chemical class 0.000 description 6
- 238000005204 segregation Methods 0.000 description 6
- 239000008107 starch Substances 0.000 description 6
- 235000019698 starch Nutrition 0.000 description 6
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 6
- 230000000052 comparative effect Effects 0.000 description 5
- 230000000694 effects Effects 0.000 description 5
- 238000005469 granulation Methods 0.000 description 5
- 230000003179 granulation Effects 0.000 description 5
- 150000004965 peroxy acids Chemical class 0.000 description 5
- 238000005406 washing Methods 0.000 description 5
- 238000000137 annealing Methods 0.000 description 4
- 150000001735 carboxylic acids Chemical class 0.000 description 4
- 238000006243 chemical reaction Methods 0.000 description 4
- 238000009472 formulation Methods 0.000 description 4
- 230000008092 positive effect Effects 0.000 description 4
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 3
- 239000004480 active ingredient Substances 0.000 description 3
- 229920003086 cellulose ether Polymers 0.000 description 3
- 238000010438 heat treatment Methods 0.000 description 3
- 230000006872 improvement Effects 0.000 description 3
- 239000010410 layer Substances 0.000 description 3
- 239000000155 melt Substances 0.000 description 3
- NLKNQRATVPKPDG-UHFFFAOYSA-M potassium iodide Chemical compound [K+].[I-] NLKNQRATVPKPDG-UHFFFAOYSA-M 0.000 description 3
- 239000000843 powder Substances 0.000 description 3
- 230000009467 reduction Effects 0.000 description 3
- 238000012360 testing method Methods 0.000 description 3
- TUNFSRHWOTWDNC-HKGQFRNVSA-N tetradecanoic acid Chemical compound CCCCCCCCCCCCC[14C](O)=O TUNFSRHWOTWDNC-HKGQFRNVSA-N 0.000 description 3
- BVKZGUZCCUSVTD-UHFFFAOYSA-M Bicarbonate Chemical class OC([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-M 0.000 description 2
- SCKXCAADGDQQCS-UHFFFAOYSA-N Performic acid Chemical compound OOC=O SCKXCAADGDQQCS-UHFFFAOYSA-N 0.000 description 2
- 240000003834 Triticum spelta Species 0.000 description 2
- 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 2
- 239000003513 alkali Substances 0.000 description 2
- 239000002585 base Substances 0.000 description 2
- 230000008901 benefit Effects 0.000 description 2
- 239000013590 bulk material Substances 0.000 description 2
- 235000013877 carbamide Nutrition 0.000 description 2
- BVKZGUZCCUSVTD-UHFFFAOYSA-N carbonic acid Chemical class OC(O)=O BVKZGUZCCUSVTD-UHFFFAOYSA-N 0.000 description 2
- 150000004649 carbonic acid derivatives Chemical class 0.000 description 2
- 239000007795 chemical reaction product Substances 0.000 description 2
- 150000001875 compounds Chemical class 0.000 description 2
- 238000001816 cooling Methods 0.000 description 2
- VTIIJXUACCWYHX-UHFFFAOYSA-L disodium;carboxylatooxy carbonate Chemical compound [Na+].[Na+].[O-]C(=O)OOC([O-])=O VTIIJXUACCWYHX-UHFFFAOYSA-L 0.000 description 2
- 239000012153 distilled water Substances 0.000 description 2
- 150000002148 esters Chemical class 0.000 description 2
- 239000004615 ingredient Substances 0.000 description 2
- 239000002245 particle Substances 0.000 description 2
- 229920000036 polyvinylpyrrolidone Polymers 0.000 description 2
- 239000001267 polyvinylpyrrolidone Substances 0.000 description 2
- 235000013855 polyvinylpyrrolidone Nutrition 0.000 description 2
- 230000009257 reactivity Effects 0.000 description 2
- 150000004760 silicates Chemical class 0.000 description 2
- 229940045872 sodium percarbonate Drugs 0.000 description 2
- AKHNMLFCWUSKQB-UHFFFAOYSA-L sodium thiosulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=S AKHNMLFCWUSKQB-UHFFFAOYSA-L 0.000 description 2
- 235000019345 sodium thiosulphate Nutrition 0.000 description 2
- 238000007711 solidification Methods 0.000 description 2
- 230000008023 solidification Effects 0.000 description 2
- 150000003467 sulfuric acid derivatives Chemical class 0.000 description 2
- 238000004448 titration Methods 0.000 description 2
- KYVZSRPVPDAAKQ-UHFFFAOYSA-N 2-benzoyloxybenzenesulfonic acid Chemical compound OS(=O)(=O)C1=CC=CC=C1OC(=O)C1=CC=CC=C1 KYVZSRPVPDAAKQ-UHFFFAOYSA-N 0.000 description 1
- XSVSPKKXQGNHMD-UHFFFAOYSA-N 5-bromo-3-methyl-1,2-thiazole Chemical compound CC=1C=C(Br)SN=1 XSVSPKKXQGNHMD-UHFFFAOYSA-N 0.000 description 1
- LSNNMFCWUKXFEE-UHFFFAOYSA-M Bisulfite Chemical compound OS([O-])=O LSNNMFCWUKXFEE-UHFFFAOYSA-M 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- 239000004215 Carbon black (E152) Substances 0.000 description 1
- 206010013710 Drug interaction Diseases 0.000 description 1
- 229910019142 PO4 Inorganic materials 0.000 description 1
- ABLZXFCXXLZCGV-UHFFFAOYSA-N Phosphorous acid Chemical class OP(O)=O ABLZXFCXXLZCGV-UHFFFAOYSA-N 0.000 description 1
- 229920000388 Polyphosphate Polymers 0.000 description 1
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Chemical compound NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 description 1
- 230000002378 acidificating effect Effects 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- 230000004913 activation Effects 0.000 description 1
- 230000000996 additive effect Effects 0.000 description 1
- 150000001447 alkali salts Chemical class 0.000 description 1
- 150000008051 alkyl sulfates Chemical class 0.000 description 1
- QGZKDVFQNNGYKY-UHFFFAOYSA-O ammonium group Chemical group [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 description 1
- 125000000129 anionic group Chemical group 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 235000012216 bentonite Nutrition 0.000 description 1
- 239000011230 binding agent Substances 0.000 description 1
- 239000004202 carbamide Substances 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 125000004432 carbon atom Chemical group C* 0.000 description 1
- 150000003857 carboxamides Chemical class 0.000 description 1
- 230000015556 catabolic process Effects 0.000 description 1
- 239000003054 catalyst Substances 0.000 description 1
- 239000001913 cellulose Substances 0.000 description 1
- 229920002678 cellulose Polymers 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 239000011362 coarse particle Substances 0.000 description 1
- 229920001577 copolymer Polymers 0.000 description 1
- 230000007423 decrease Effects 0.000 description 1
- 230000003247 decreasing effect Effects 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000006731 degradation reaction Methods 0.000 description 1
- 230000003111 delayed effect Effects 0.000 description 1
- 238000004851 dishwashing Methods 0.000 description 1
- 238000004090 dissolution Methods 0.000 description 1
- 239000003814 drug Substances 0.000 description 1
- 229940079593 drug Drugs 0.000 description 1
- 239000000975 dye Substances 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 239000004744 fabric Substances 0.000 description 1
- 238000011049 filling Methods 0.000 description 1
- 239000010419 fine particle Substances 0.000 description 1
- 230000009969 flowable effect Effects 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 150000002334 glycols Chemical class 0.000 description 1
- 229920000578 graft copolymer Polymers 0.000 description 1
- 239000003979 granulating agent Substances 0.000 description 1
- 239000008240 homogeneous mixture Substances 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 230000007062 hydrolysis Effects 0.000 description 1
- 238000006460 hydrolysis reaction Methods 0.000 description 1
- 230000003993 interaction Effects 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 238000012423 maintenance Methods 0.000 description 1
- 150000004682 monohydrates Chemical class 0.000 description 1
- 239000012170 montan wax Substances 0.000 description 1
- 125000002560 nitrile group Chemical group 0.000 description 1
- 230000003287 optical effect Effects 0.000 description 1
- 238000005457 optimization Methods 0.000 description 1
- 150000002894 organic compounds Chemical class 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 239000012188 paraffin wax Substances 0.000 description 1
- 235000019809 paraffin wax Nutrition 0.000 description 1
- 239000002304 perfume Substances 0.000 description 1
- 235000019271 petrolatum Nutrition 0.000 description 1
- 235000021317 phosphate Nutrition 0.000 description 1
- 150000003009 phosphonic acids Chemical class 0.000 description 1
- 150000003013 phosphoric acid derivatives Chemical class 0.000 description 1
- 229920001223 polyethylene glycol Polymers 0.000 description 1
- 229920000098 polyolefin Polymers 0.000 description 1
- 239000001205 polyphosphate Substances 0.000 description 1
- 235000011176 polyphosphates Nutrition 0.000 description 1
- 229920002451 polyvinyl alcohol Polymers 0.000 description 1
- 235000019422 polyvinyl alcohol Nutrition 0.000 description 1
- 229910052700 potassium Inorganic materials 0.000 description 1
- 238000003825 pressing Methods 0.000 description 1
- 239000011241 protective layer Substances 0.000 description 1
- 238000012216 screening Methods 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 239000007921 spray Substances 0.000 description 1
- 238000001694 spray drying Methods 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 150000003460 sulfonic acids Chemical class 0.000 description 1
- 239000004094 surface-active agent Substances 0.000 description 1
- 150000004685 tetrahydrates Chemical class 0.000 description 1
- 239000010409 thin film Substances 0.000 description 1
- 150000003672 ureas Chemical class 0.000 description 1
- 239000010457 zeolite Substances 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
- C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
- 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
-
- C—CHEMISTRY; METALLURGY
- C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
- C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
- C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
- C11D3/39—Organic or inorganic per-compounds
- C11D3/3902—Organic or inorganic per-compounds combined with specific additives
- C11D3/3905—Bleach activators or bleach catalysts
- C11D3/3935—Bleach activators or bleach catalysts granulated, coated or protected
-
- 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
- C11D17/0039—Coated compositions or coated components in the compositions, (micro)capsules
-
- C—CHEMISTRY; METALLURGY
- C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
- C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
- C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
- C11D3/39—Organic or inorganic per-compounds
- C11D3/3902—Organic or inorganic per-compounds combined with specific additives
- C11D3/3905—Bleach activators or bleach catalysts
- C11D3/3907—Organic compounds
Definitions
- Bleach activators are important components in detergents, stain salts and Dishwasher detergents. They already enable a bleaching effect relatively low temperatures by using hydrogen peroxide - mostly perborates or percarbonates - with the release of an organic peroxycarboxylic acid react.
- the achievable bleaching result is determined by the type and reactivity of the Peroxycarboxylic acid formed, the structure of the bond to be hydrolyzed as well as the water solubility of the bleach activator. Since it's mostly one reactive ester or an amide, in many cases it is necessary to use it for that intended use in granular form to hydrolysis in To prevent the presence of alkaline detergent ingredients and a to ensure sufficient storage stability.
- EP-A-0 037 026 describes a process for producing easily soluble activator granules from 90 to 98% activator with 10 to 2% cellulose ether, starch or starch ether.
- Granules consisting of bleach activator, film-forming polymers and additives of an organic C 3 -C 6 carbon-, hydroxycarbon- or ether carboxylic acid are listed in WO 90/01535.
- EP-A-0 468 824 discloses granules of bleach activator and a film-forming polymer which is more soluble at pH 10 than at pH 7.
- DE-OS-44 39 039 describes a process for producing an activator granulate by mixing a dry bleach activator with a dry, inorganic, hydrate-containing binding material, compressing this mixture to larger agglomerates and comminuting these agglomerates to the desired particle size.
- a water-free manufacturing process by compacting the bleach activator without using water with at least one water-swellable auxiliary is known from EP-A-0 075 818.
- a disadvantage of these activator granules is that the properties of the granules essentially by the binder and the granulation process used are fixed and often in addition to the advantages described in the literature certain disadvantages, e.g. not optimal release of active ingredient, low abrasion resistance, high dust content, insufficient storage stability, segregation in powder or Color damage to the fabric when used in detergents and cleaning agents exhibit.
- WO-92/13798 describes a coating with a bleach activator water-soluble organic acid melting above 30 ° C and in WO-94/03305 a coating with a water-soluble acidic polymer for reduction the color damage of the laundry described.
- WO-94/26862 describes the coating of a granulate consisting of a bleach activator and water and or alkali soluble polymer, with a between 30 ° C and 100 ° C. melting organic compound to reduce segregation in the powdered end product known.
- the activator granulate is in one Lödige ploughshare mixer submitted without using the chopper Room temperature circulated at 160 to 180 rpm and then with the hot Sprayed melt.
- the disadvantage of this method is a very bad one Coating quality, which is a reduction in the segregation in powder
- the end product has no effect on the other granule properties, such as. Active ingredient release, abrasion resistance, dust content or storage stability.
- the positive effect on the segregation behavior is probably on one droplet-like solidification of the coating substance on the granulate surface attributable, which causes the granules to get caught in the bulk material becomes.
- the object of the present invention was to develop a coating process for activator granules, which is a targeted adjustment of the granule properties in a wide range with optimal use of the coating material enables.
- This task was solved by tempering during and / or after the coating.
- the invention thus relates to a method for producing a coated Bleach activator granules, wherein a bleach activator base granules with a Coating substance wrapped and tempered simultaneously or subsequently.
- activators can be used as basic granules, those in granulated Form have a melting point of above 100 ° C.
- Activator substances are tetraacetylethylenediamine (TAED), tetraacetylglucoluril (TAGU), diacetyldioxohexahydrotriazine (DADHT), acyloxybenzenesulfonates (e.g. Nonanyloxybenzenesulfonate [NOBS], benzoyloxybenzenesulfonate [BOBS]), acylated Sugar (e.g.
- PAG pentaacetyl glucose
- activators are N-acylated amines, amides, lactams, activated Carboxylic acid esters, carboxylic anhydrides, lactones, acylals, carboxamides, Acyl lactams, acylated ureas and oxamides, but also in particular Nitriles, which in addition to the nitrile group also a quaternized ammonium group can contain.
- Mixtures of different bleach activators can also Basic granules are available.
- These basic granules can contain the usual granulation aids, which should have a melting point of over 100 ° C.
- Film-forming polymers are suitable here, for example: cellulose ether, starch, starch ether, homo-, co-, graft copolymers of unsaturated carboxylic acids and / or sulfonic acid and salts thereof; Organic substances, e.g. cellulose, crosslinked polyvinylpyrrolidone or inorganic substances, e.g.
- the Bleach activator base granules contain other additives that Properties such as storage stability and bleach activation capacity improve.
- additives include inorganic acids, organic Acids such as mono- or polyvalent carboxylic acids, hydroxycarboxylic acids and / or ether carboxylic acids and their salts, complexing agents, metal complexes and ketones.
- the aforementioned additives can be used as individual substances or as Mixtures are used.
- These basic granules are produced by mixing the dry Bleach activator with the dry granulating agent, pressing this mixture to larger agglomerates and crushing these agglomerates to the desired one Grain size.
- the ratio of bleach activator to granulation aid is usually 50:50 to 98: 2, preferably 70:30 to 96: 4% by weight.
- the amount of the additive depends in particular on its type. So acidifying additives and organic catalysts to increase the performance of peracid in amounts of 0 up to 20 wt .-%, in particular in amounts of 1 to 10 wt .-%, based on the Total weight, added, however, metal complexes in concentrations in ppm Area.
- C 8 -C 31 fatty acids for example: lauric, myristic, stearic acid); C 8 -C 31 fatty alcohols; Polyalkenyl glycols (eg polyethylene glycols with a molecular weight of 1,000 to 50,000 g / mol); Nonionics (e.g.
- C 8 -C 31 fatty alcohol polyalkoxylates with 1 to 100 moles of EO C 8 -C 31 fatty alcohol polyalkoxylates with 1 to 100 moles of EO
- Anionics for example alkanesulfonates, alkylbenzenesulfonates, ⁇ -olefinsulfonates, alkyl sulfates, alkyl ether sulfates with C 8 -C 31 -hydrocarbon radicals
- Polymers eg polyvinyl alcohols
- Waxes for example: montan waxes, paraffin waxes, ester waxes, polyolefin waxes
- Silicones for example: montan waxes, paraffin waxes, ester waxes, polyolefin waxes.
- softening or melting substances in dissolved or suspended form are present, e.g .: polymers (e.g. homo-, co- or plug copolymers unsaturated carboxylic acids and / or sulfonic acids and their alkali salts, Cellulose ether, starch, starch ether, polyvinylpyrrolidone); Organic substances (e.g. mono- or polyvalent carboxylic acids, hydroxycarboxylic acids or Ether carboxylic acids with 3 to 8 carbon atoms and their salts); Dyes; Inorganic substances (e.g. silicates, carbonates, bicarbonates, sulfates, Phosphates, phosphonates).
- polymers e.g. homo-, co- or plug copolymers unsaturated carboxylic acids and / or sulfonic acids and their alkali salts, Cellulose ether, starch, starch ether, polyvinylpyrrolidone
- Organic substances e.g. mono- or polyvalent
- the content of the coating substance is 1 to 30% by weight, preferably 5 to 15% by weight on coated activator granules.
- Mixers mechanically induced Fluidized bed
- fluidized bed apparatus pneumatically induced fluidized bed
- mixers e.g. Ploughshare mixer (continuous and in batches)
- ring-layer mixer or Schugi mixer possible.
- the Tempering can be done using a mixer in a granule preheater and / or in the mixer directly and / or in a downstream of the mixer Fluidized bed.
- Granulate coolers can be used to cool the coated granulate or fluid bed coolers can be used.
- the tempering takes place via the hot gas used for whirling up. That after The granulate coated by the fluidized bed process can be similar to the Mixer process cooled via a granulate cooler or a fluid bed cooler will. Both in the mixer process and in the fluidized bed process can the coating substance via a single-substance or a two-substance nozzle device be sprayed on.
- the tempering consists of a heat treatment at a temperature of 30 to 100 ° C, but equal to or below the melting or softening temperature of the respective shell substance. It is preferred to work at a temperature that is scarce is below the melting or softening temperature.
- the grain size of the coated bleach activator granules is from 0.1 to 2.0 mm, preferably from 0.2 to 1.0 mm and particularly preferably from 0.3 to 0.8 mm.
- the exact temperature during tempering or the temperature difference to The melting point of the coating substance depends on the amount of coating Annealing time and the desired for the coated bleach activator granulate Properties and must be determined for the respective system in preliminary tests.
- the time for the annealing is approximately 1 to 180, preferably 3 to 60, particularly preferably 5 to 30 minutes.
- the advantage of the new method over the prior art is that that the liquid coating agent does not solidify too quickly and thus the possibility has to run as a thin film on the granulate surface.
- the individual droplets solidify too quickly on the cold granulate surface a.
- the surface is only covered with fine individual droplets and still has large coating defects.
- the desired coating effect is thus achieved insufficiently or a significantly higher amount of coating substance is required to achieve a desired coating effect. The latter but reduces the content of activator substance, which is often undesirable.
- the granules obtained in this way can be used directly in washing and Suitable detergents. They are ideal for use in heavy-duty detergents, Stain salts, machine dishwashing detergents, powdered all-purpose cleaners and denture cleaners.
- the invention Granules mostly used in combination with a hydrogen peroxide source. Examples include perborate monohydrate, perborate tetrahydrate and percarbonates as well as hydrogen peroxide adducts with urea or amine oxides.
- detergent ingredients such as organic or inorganic builders and Co-builders, surfactants, enzymes, washing additives, optical brighteners and perfume.
- Example 1 Coating in a Schugi mixer with a downstream fluid bed Tempering and cooling
- TAED 4303 (Hoechst AG) was continuously with a throughput of 480 kg / h metered into a Schugi mixer (Flexomix 160, Hosokawa Schugi) and sprayed with a melt of myristic acid at a temperature of 75 ° C.
- the coated Material fell directly into a downstream fluid bed (Hosokawa Schugi) and was there in a first chamber for 5 to 10 minutes at fluidized bed temperatures of annealed at approx. 54 ° C and then in a second chamber at fluidized bed temperatures cooled from approx. 35 ° C.
- TAED 4303 was used for comparison purposes (prior art) continuously with a throughput of 480 kg / h in the Schugi mixer dosed, sprayed with a 75 ° C melt of myristic acid and then directly in the downstream fluid bed at fluidized bed temperatures of approx. 35 ° C chilled.
- the coating quality of the products was determined by determining the speed of the Peracetic acid formation assessed at a temperature of 20 ° C. The slower that Peracetic acid formation is the better the degree of coating achieved.
- Peracetic acid formation rate of the TAED granules coated in a Schugi mixer with a downstream fluidized bed products 1 and 4: comparative examples
- Basic granulate (BG, not coated) 75 95 100 2nd BG + 10% myristic acid, annealed 11 21 55 3rd BG + 15% myristic acid, annealed 9 18th 54 4th BG + 15% myristic acid, chilled 39 59 83
- the coating quality can be expressed by the delay in the formation of peracetic acid, improve significantly (Comparison of products 3 and 4).
- Example 2 Coating according to the fluidized bed process with downstream Tempering
- 500 - 600 g TAED 4303 were in the fluidized bed (fluidized bed apparatus Strea 1, from Aeromatic) and with a melt of approx. 80 ° C Sprayed stearic acid. In one case, this was used for comparison purposes Fluidized bed operated at low temperatures and after finishing the Spray again after cooling for about 5 minutes (prior art). In the other The coated granulate fell again according to the method of the invention presented and tempered in the fluidized bed. This became the fluidized bed gradually heated to temperatures of about 65 to 70 ° C and this Product temperature for about 5 to 8 min. kept constant. Then that was annealed product gradually cooled again.
- TAED granules peracetic acid formed [%] 5 min 10 min 20 min 5 Basic granulate (BG) 75 95 100 6 BG + 10% stearic acid, annealed 10th 21 50 7 BG + 20% stearic acid, annealed 12th 22 52 8th BG + 10% stearic acid, untempered 70 85 98 9 BG + 20% stearic acid, untempered 40 60 84 10th BG + 30% stearic acid, untempered 20th 35 60
- the coating quality can be expressed by the delay in the formation of peracetic acid, improve significantly (Comparison of products 6 and 8 or products 7 and 9).
- tempering The influence of tempering on the coating quality is also evident in the Storage stability of TAED granules in detergent formulations.
- the storage stability was tested in prefabricated folding boxes (height: 6.5 cm; width 3.2 cm; depth 2.2 cm) at 38 ° C and 80% relative humidity (RH) over a period of 28 days.
- Each folding box was filled with a homogeneous mixture of 8.0 g of test detergent WMP, 1.5 g of sodium percarbonate and 0.5 g of the TAED granules to be tested and then sealed at the top with scotch tape. All samples were mixed and filled on the same day.
- the filled and labeled folding boxes were then placed at a sufficient distance from each other in the climate cabinet and stored at 38 ° C / 80% rh.
- the samples were removed from the climate chamber, and the entire sample was introduced at 20 ° C. into 1 l of distilled water with stirring using a magnetic stirrer (250 to 280 rpm) and 1 g of sodium percarbonate were added.
- the amount of peracetic acid formed was further determined analogously to the information in Example 1.
- the TAED content of the sample was then calculated from the maximum value of peracetic acid found.
- the degree of TAED maintenance represents the percentage TAED content of the sample after storage in relation to the TAED content of the unstored sample.
- Example 3 Coating using the fluidized bed process with simultaneous Tempering
- TAED 4303 was continuously fed at 40 kg / h via a flexible dosing screw the fluidized bed apparatus (technical fluidized bed apparatus) metered in and with 20% coated with myristic acid.
- the residence time in the fluidized bed was approximately 30 Minutes.
- the product discharged through a rotary valve was removed using a dosing screw on a screening machine, on which the coarse fraction of greater than 1.0 mm and the fine fraction of less than 0.2 mm separated were.
- the bulk was then crushed in a mill and then together with the fine portion via a flexible dosing screw in the Fluidized bed apparatus returned.
- the Fluid bed temperature increased from initially 46 ° C to finally 54 ° C.
- the coating quality was checked by determining the rate of formation of peracetic acid at a temperature of 20 ° C and the dust content of less than 0.2 mm of the coated TAED granules.
- the slower the formation of peracetic acid the better the degree of coating achieved.
- the lower the dust content the better the dedusting achieved by the coating and the higher the abrasion resistance.
- Peracetic acid formation rate of TAED granules coated in a fluidized bed process with simultaneous tempering (product 11: comparative example) Product no.
- Fluid bed temperature decreases the coating quality expressed by the delay of peracid formation, and you get a better dedusting and higher abrasion resistance, expressed by the decreasing proportion of dust ⁇ 0.2 mm of the coated granulate.
- Example 4 Coating in a ploughshare mixer with simultaneous tempering
- 1.2 kg of TAED granules according to EP-A-0 037 026 were in a batch ploughshare mixer (M5R, Fa. Lödige) and mixed with a The speed of the mixing tools is approx. 150 rpm with 210 g at 80 ° C Sprayed stearic acid melt.
- the mixer content was during the Coating step heated to a temperature of 50 ° C over a heating jacket.
- the coating and annealing time was approx. 10 minutes.
- WO-94/26826 1.2 kg TAED granules according to EP-A-0 037 026 in one Batch ploughshare mixer submitted and at room temperature with thorough mixing with a speed of the mixing tools of approx. 150 U / min with 210 g of an 80 ° C sprayed hot stearic acid melt.
- the coating quality was checked by determining the rate of formation of peracetic acid at a temperature of 20 ° C.
- Peracetic acid formation rate of TAED granules coated in a ploughshare mixer with tempering during the coating step products 16 and 18; comparative examples
- the coating can have a positive effect Achieve segregation behavior in the powder (product 18), but the improvement many other properties, here for example the delay of the Peracetic acid formation is only by tempering, i.e. by the invention Process possible (product 17).
- the positive effect on the segregation behavior caused by the coating without Annealing is probably due to the droplet-like solidification of the The coating substance can be attributed to the surface of the granules, causing them to get caught of the granules in the bulk material is effected. However, this is not a positive effect many other properties connected.
- Example 5 Coating in a ploughshare mixer with simultaneous tempering
- TAED 4303 was in continuous with throughputs from 100 to 300 kg / h dosed the ploughshare mixer (KT-160, Drais).
- the Mixer content via a heating jacket at temperatures in the range of 44 to 52 ° C tempered.
- the residence time in the mixer was 8 to 12 minutes.
- a melt of stearic acid with a temperature of 80 ° C in the front Part of the mixer (closer to the product entry) injected.
- the coating amount was 7%.
- the mixer was at a speed of 90 rpm and the mixing tools operated without using the chopper knife.
- the degree of filling in the mixer was like this set that the product just covered the mixing shaft.
- the coated Material was continuously withdrawn from the mixer and directly through a sieve (0.2 to 1.0 mm) to separate fine and coarse particles.
- the coating quality was checked by determining the rate of formation of peracetic acid at a temperature of 20 ° C.
- Peracetic acid formation rate of TAED granules coated in a ploughshare mixer with simultaneous tempering product 19: comparative example
- Prod.No. TAED granules T mix [° C] Peracetic acid [%] 5 min 10 min 20 min 19th Basic granulate --- 75 95 100 20th BG + 7% stearic acid 44 72 95 99 21 BG + 7% stearic acid 48 70 90 98 22 BG + 7% stearic acid 52 60 80 94
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Abstract
Description
Zur Vermeidung der Wechselwirkung zwischen dem Bleichsystem und dem Enzymsystem ist eine zeitlich geringfügig verzögerte Reaktion und Wirkstofffreisetzung des Bleichsystems bei gleichzeitig schneller Enzymwirkung vorteilhaft. Auf diese Weise können die Enzyme in den ersten Minuten des Waschprozesses ihre Waschkraft voll entfalten ohne durch das Bleichsystem geschädigt zu werden. Erst nachdem die Enzyme ihre Arbeit verrichtet haben wird dann durch Reaktion des Bleichaktivators mit der Wasserstoffperoxidquelle der Bleichprozeß in Gang gesetzt. Durch geeignetes Coating des Bleichaktivators kann die Reaktivität, d.h. die Auflösegeschwindigkeit bzw. die Geschwindigkeit der Persäurebildung gezielt auf das Enzymsystem abgestimmt werden. Bei dem Verfahren ist eine gezielte Einstellung der Persäurebildungsgeschwindigkeit bei gleichzeitig minimaler Menge Coatingsubstanz und daher maximalem Aktivatorgehalt möglich.
Durch Coating eines Granulates mit erweichenden oder schmelzenden Substanzen kann die Abriebfestigkeit eines Aktivatorgranulates erhöht werden. Dabei ist die Erhöhung der Abriebfestigkeit umso größer, je besser die Granulatoberfläche mit der Coatingsubstanz umhüllt ist. Durch das erfindungsgemäße Coating-Verfahren kann mit minimaler Coatingmenge ein optimales Verlaufen der Coating-Substanz auf der Granulatoberfläche und damit eine optimale Verbesserung der Abriebfestigkeit bewirkt werden.
Durch das erfindungsgemäße Coating-Verfahren, bei dem durch geeignete Temperierung während und/oder nach dem Umhüllungsschritt ein zu schnelles Erstarren der erweichenden oder schmelzenden Coatingsubstanz verhindert wird, ist auch ein optimales Entstauben eines Granulates bei minimaler Coatingmenge möglich, da die Coatingsubstanz über einen längeren Zeitraum fließ- und bindefähig bleibt und damit in der Lage ist, mehr Staubpartikel zu binden. Beim Coating gemäß dem Stand der Technik muß dagegen im ungünstigen Fall sogar mit einer Erhöhung des Staubanteils infolge teilweiser direkter Sprühtrocknung gerechnet werden.
Bei Lagerung eines Wasch- und Reinigungsmittels kann es an der Grenze zwischen Aktivatorkorn und direkt benachbartem Korn der Wasserstoffperoxidquelle zu einer Reaktion mit anschließendem Aktivsauerstoffverlust und damit zu unkontrolliertem Abbau des Bleichsystems kommen. Durch ein optimales Coating, wie es nur durch das erfindungsgemäße Coatingverfahren möglich ist, wird an der Korngröße eine vollständige Schutzschicht aufgebaut, die dann eine Reaktion des Aktivatorkorns mit dem Korn der Wasserstoffperoxidquelle während der Lagerung unterbindet. Bei Verwendung wasserlöslicher und/oder niedrig schmelzender Coatingsubstanzen kann trotzdem im Waschprozeß die erforderliche Bleichleistung erzielt werden.
100 % gesetzt und auf dieser Basis schließlich die nach 5, 10 und 20 Minuten gebildete Peressigsäuremenge in Prozent als Maß für die Geschwindigkeit der Peressigsäurebildung bestimmt.
Peressigsäurebildungsgeschwindigkeit der im Schugi-Mischer mit nachgeschaltetem Fließbett gecoateten TAED-Granulate (Produkte 1 und 4: Vergleichsbeispiele) | ||||
Produkt-Nr. | TAED-Granulat | gebildete Peressigsäure [%] | ||
5 min | 10 min | 20 min | ||
1 | Basisgranulat (BG, nicht gecoatet) | 75 | 95 | 100 |
2 | BG+10 % Myristinsäure, getempert | 11 | 21 | 55 |
3 | BG+ 15 % Myristinsäure, getempert | 9 | 18 | 54 |
4 | BG+ 15 % Myristinsäure, gekühlt | 39 | 59 | 83 |
Peressigsäurebildungsgeschwindigkeit von im Wirbelschichtverfahren mit anschließender Temperung gecoateten TAED-Granulaten (Produkte 5, 8 bis 10: Vergleichsbeispiele) | ||||
Produkt-Nr. | TAED-Granulat | gebildete Peressigsäure [%] | ||
5 min | 10 min | 20 min | ||
5 | Basisgranulat (BG) | 75 | 95 | 100 |
6 | BG+ 10 % Stearinsäure, getempert | 10 | 21 | 50 |
7 | BG+ 20 % Stearinsäure, getempert | 12 | 22 | 52 |
8 | BG+ 10 % Stearinsäure, ungetempert | 70 | 85 | 98 |
9 | BG+ 20 % Stearinsäure, ungetempert | 40 | 60 | 84 |
10 | BG+ 30 % Stearinsäure, ungetempert | 20 | 35 | 60 |
Lagerstabilität in Waschmittelformulierungen von im Wirbelschichtverfahren mit anschließender Temperung gecoateten TAED-Granulaten | ||||||||
Produkt Nr. | TAED-Granulat | TAED-Erhaltungsgrad nach Lagerung [%] | ||||||
0d | 3d | 6d | 9d | 15d | 23d | 28d | ||
5 | Basisgranulat (BG) | 100 | 24 | 14 | 12 | 10 | 9 | 8 |
6 | BG+ 10 % Stearinsäure, getempert | 100 | 88 | 61 | 56 | 47 | 45 | 45 |
8 | BG+ 10 % Stearinsäure, ungetempert | 100 | 52 | 24 | 20 | 18 | 16 | 15 |
Peressigsäurebildungsgeschwindigkeit von im Wirbelschichtverfahren mit gleichzeitiger Temperung gecoateten TAED-Granulaten (Produkt 11: Vergleichsbeispiel) | ||||||
Produkt-Nr. | TAED-Granulat | TWirbelbett [°C] | Peressigsäure [%] Staubanteil | |||
5 min | 10 min | 20 min | [%] | |||
11 | Basisgranulat (BG) | --- | 75 | 95 | 100 | --- |
12 | BG+ 20 % Myristinsäure | 46 | 66 | 81 | 94 | 30 |
13 | BG+ 20 % Myristinsäure | 49 | 48 | 68 | 87 | 15 |
14 | BG+ 20 % Myristinsäure | 52 | 38 | 60 | 86 | 10 |
15 | BG+ 20 % Myristinsäure | 54 | 20 | 36 | 62 | 5 |
Peressigsäurebildungsgeschwindigkeit von im Pflugscharmischer mit Temperung während des Coatingschrittes gecoateten TAED-Granulaten (Produkte 16 und 18; Vergleichsbeispiele) | ||||
Produkt-Nr. | TAED-Granulat | Peressigsäure [%] | ||
5 min | 10 min | 20 min | ||
16 | Basisgranulat | 81 | 96 | 100 |
17 | BG+ 15 % Stearinsäure, getempert (50°C) | 44 | 61 | 79 |
18 | BG+ 15 % Stearinsäure, ungetempert | 75 | 90 | 98 |
Peressigsäurebildungsgeschwindigkeit von im Pflugscharmischer mit gleichzeitiger Temperung gecoateten TAED-Granulaten (Produkt 19: Vergleichsbeispiel) | |||||
Prod.-Nr. | TAED-Granulat | TMischgut [°C] | Peressigsäure [%] | ||
5 min | 10 min | 20 min | |||
19 | Basisgranulat | --- | 75 | 95 | 100 |
20 | BG+ 7 % Stearinsäure | 44 | 72 | 95 | 99 |
21 | BG+ 7 % Stearinsäure | 48 | 70 | 90 | 98 |
22 | BG+ 7 % Stearinsäure | 52 | 60 | 80 | 94 |
Claims (13)
- Verfahren zur Herstellung eines gecoateten Bleichaktivatorgranulats, dadurch gekennzeichnet, daß man ein Bleichaktivatorbasisgranulat mit einer Coatingsubstanz umhüllt und gleichzeitig oder anschließend tempert.
- Verfahren nach Anspruch 1, dadurch gekennzeichnet, daß das Aktivatorbasisgranulat einen Schmelzpunkt von über 100°C aufweist.
- Verfahren nach Anspruch 1 oder 2, dadurch gekennzeichnet, daß die Coatingsubstanz einen Erweichungs- oder Schmelzpunkt im Bereich von 30 bis 100°C hat.
- Verfahren nach einem oder mehreren der Ansprüche 1 bis 3, dadurch gekennzeichnet, daß die Temperung während oder nach dem Coatingschritt bei Temperaturen in der Nähe des Erweichungs- oder Schmelzpunktes der Coatingsubstanz erfolgt.
- Verfahren nach einem oder mehreren der Ansprüche 1 bis 4, dadurch gekennzeichnet, daß als Bleichaktivatoren N-acylierte Amine, Amide, Lactame, Acyloxybenzolsulfonate, acylierte Zucker, aktivierte Carbonsäureester, Carbonsäureanhydride, Lactone, Acylale, Oxamide und/oder Nitrile, die eine quaternäre Ammoniumgruppe enthalten können, verwendet werden.
- Verfahren nach einem oder mehreren der Ansprüche 1 bis 5, dadurch gekennzeichnet, daß als Coatingsubstanzen Fettsäuren, Fettalkohole, Polyalkylenglykole, nichtionische Tenside, anionische Tenside, Polymere, Wachse und/oder Silikone verwendet werden.
- Verfahren nach einem oder mehreren der Ansprüche 1 bis 6, dadurch gekennzeichnet, daß die Coatingsubstanz Polymere, organische Substanzen und/oder anorganische Substanzen in gelöster oder suspendierter Form enthält.
- Verfahren nach einem oder mehreren der Ansprüche 1 bis 7, dadurch gekennzeichnet, daß der Gehalt an Coatingsubstanz 1 bis 30 Gew.-% bevorzugt 5 bis 15 Gew.-% beträgt, bezogen auf das gecoatete Aktivatorgranulat.
- Verfahren nach einem oder mehreren der Ansprüche 1 bis 8, dadurch gekennzeichnet, daß das Aufbringen der Coatingsubstanz in einem Mischer oder in einem Wirbelschichtapparat erfolgt.
- Verfahren nach einem oder mehreren der Ansprüche 1 bis 9, dadurch gekennzeichnet, daß die Korngröße des gecoateten Bleichaktivatorgranulats 0.1 bis 2.0 mm, bevorzugt von 0.2 bis 1.0 mm und besonders bevorzugt von 0.3 bis 0.8 mm beträgt.
- Verfahren nach einem oder mehreren der Ansprüche 1 bis 10, dadurch gekennzeichnet, daß das Aktivatorbasisgranulat bis zu 20 Gew.-% bezogen auf das Gewicht des Aktivatorbasisgranulats eines oder mehrerer Zusätze ausgewählt aus der Gruppe bestehend aus anorganischen Säuren, organischen Säuren, Komplexbildnern, Ketonen und Metallkomplexen enthält.
- Gecoatete Bleichaktivatorgranulate, hergestellt nach dem Verfahren gemäß einem oder mehreren der Ansprüche 1 bis 11.
- Wasch-, Reinigungs-, Blech- und Desinfektionmittel, enthaltend ein gecoatetes Bleichaktivatorgranulat, hergestellt nach dem Verfahren gemäß einem oder mehreren der Ansprüche 1 bis 11.
Applications Claiming Priority (2)
Application Number | Priority Date | Filing Date | Title |
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DE19641708A DE19641708A1 (de) | 1996-10-10 | 1996-10-10 | Verfahren zur Herstellung eines gecoateten Bleichaktivatorgranulats |
DE19641708 | 1996-10-10 |
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EP0835926A2 true EP0835926A2 (de) | 1998-04-15 |
EP0835926A3 EP0835926A3 (de) | 1999-01-07 |
EP0835926B1 EP0835926B1 (de) | 2007-01-24 |
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EP97116693A Expired - Lifetime EP0835926B1 (de) | 1996-10-10 | 1997-09-25 | Verfahren zur Herstellung eines gecoateten Bleichaktivatorgranulats |
Country Status (13)
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US (3) | US6107266A (de) |
EP (1) | EP0835926B1 (de) |
JP (1) | JP4897988B2 (de) |
KR (1) | KR100507515B1 (de) |
AR (1) | AR008887A1 (de) |
BR (1) | BR9704995A (de) |
CA (1) | CA2216193C (de) |
CZ (1) | CZ294306B6 (de) |
DE (2) | DE19641708A1 (de) |
ES (1) | ES2276414T3 (de) |
HU (1) | HUP9701617A3 (de) |
PL (1) | PL188368B1 (de) |
TW (1) | TW418252B (de) |
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Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
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CN110114450B (zh) | 2016-10-18 | 2020-07-03 | 斯特里莱克斯有限责任公司 | 环境湿气可活化的表面处理粉末 |
Citations (6)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
EP0037026A1 (de) * | 1980-03-28 | 1981-10-07 | Henkel Kommanditgesellschaft auf Aktien | Verfahren zur Herstellung eines lagerstabilen, leichtlöslichen Granulates mit einem Gehalt an Bleichaktivatoren |
US5200236A (en) * | 1989-11-15 | 1993-04-06 | Lever Brothers Company, Division Of Conopco, Inc. | Method for wax encapsulating particles |
US5230822A (en) * | 1989-11-15 | 1993-07-27 | Lever Brothers Company, Division Of Conopco, Inc. | Wax-encapsulated particles |
WO1994026862A1 (de) * | 1993-05-17 | 1994-11-24 | Henkel Kommanditgesellschaft Auf Aktien | Bleich- und desinfektionsmittel |
US5480577A (en) * | 1994-06-07 | 1996-01-02 | Lever Brothers Company, Division Of Conopco, Inc. | Encapsulates containing surfactant for improved release and dissolution rates |
EP0737739A2 (de) * | 1995-04-13 | 1996-10-16 | The Procter & Gamble Company | Verfahren zur Herstellung eines Waschmittelteilchens |
Family Cites Families (23)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
AT339246B (de) * | 1974-08-14 | 1977-10-10 | Henkel & Cie Gmbh | Als bestandteil von pulverformigen wasch- und bleichmitteln geeignetes bleichhilfsmittel |
ATE12517T1 (de) * | 1980-12-09 | 1985-04-15 | Unilever Nv | Bleichmittelaktivatorgranulate. |
DE3128336A1 (de) * | 1981-07-17 | 1983-01-27 | Henkel KGaA, 4000 Düsseldorf | "verfahren zur herstellung umhuellter koerniger bleichaktivatoren" |
DE3268039D1 (en) * | 1981-09-28 | 1986-01-30 | Basf Ag | Granular bleach activator |
US4486327A (en) * | 1983-12-22 | 1984-12-04 | The Procter & Gamble Company | Bodies containing stabilized bleach activators |
US4678594A (en) * | 1985-07-19 | 1987-07-07 | Colgate-Palmolive Company | Method of encapsulating a bleach and activator therefor in a binder |
CA1302835C (en) * | 1987-03-17 | 1992-06-09 | Frederick Edward Hardy | Bleaching compositions |
US4889651A (en) * | 1988-01-21 | 1989-12-26 | Colgate-Palmolive Company | Acetylated sugar ethers as bleach activators and detergency boosters |
DE3826092A1 (de) * | 1988-08-01 | 1990-02-08 | Henkel Kgaa | Granulares, bleichaktivatoren enthaltendes bleichhilfsmittel mit verbesserten eigenschaften |
DE3843195A1 (de) * | 1988-12-22 | 1990-06-28 | Hoechst Ag | Verfahren zur herstellung eines lagerstabilen, leicht loeslichen bleichaktivator-granulats |
GB8925621D0 (en) * | 1989-11-13 | 1990-01-04 | Unilever Plc | Process for preparing particulate detergent additive bodies and use thereof in detergent compositions |
DK17290D0 (de) * | 1990-01-22 | 1990-01-22 | Novo Nordisk As | |
GB9016504D0 (en) * | 1990-07-27 | 1990-09-12 | Warwick Int Ltd | Granular bleach activator compositions |
DE4024759A1 (de) * | 1990-08-03 | 1992-02-06 | Henkel Kgaa | Bleichaktivatoren in granulatform |
DE69030443T2 (de) * | 1990-12-28 | 1997-11-13 | Ausimont Spa | Verfahren zur Erhöhung der Bleichwirksamkeit von anorganischen Persalzen |
GB9102507D0 (en) * | 1991-02-06 | 1991-03-27 | Procter & Gamble | Peroxyacid bleach precursor compositions |
US5458801A (en) * | 1991-09-27 | 1995-10-17 | Kao Corporation | Process for producing granular bleach activator composition and granular bleach activator composition |
WO1994003305A1 (en) | 1992-08-04 | 1994-02-17 | The Morgan Crucible Company Plc | Gold-nickel-vanadium brazing materials |
US5298061A (en) * | 1993-05-14 | 1994-03-29 | Olin Corporation | Gel-free paint containing zinc pyrithione, cuprous oxide, and amine treated rosin |
US5534196A (en) * | 1993-12-23 | 1996-07-09 | The Procter & Gamble Co. | Process for making lactam bleach activator containing particles |
DE4439039A1 (de) * | 1994-11-02 | 1996-05-09 | Hoechst Ag | Granulierte Bleichaktivatoren und ihre Herstellung |
DE19641708A1 (de) * | 1996-10-10 | 1998-04-16 | Clariant Gmbh | Verfahren zur Herstellung eines gecoateten Bleichaktivatorgranulats |
DE19740671A1 (de) * | 1997-09-16 | 1999-03-18 | Clariant Gmbh | Bleichaktivator-Granulate |
-
1996
- 1996-10-10 DE DE19641708A patent/DE19641708A1/de not_active Withdrawn
-
1997
- 1997-09-22 CA CA002216193A patent/CA2216193C/en not_active Expired - Fee Related
- 1997-09-25 DE DE59712800T patent/DE59712800D1/de not_active Expired - Lifetime
- 1997-09-25 ES ES97116693T patent/ES2276414T3/es not_active Expired - Lifetime
- 1997-09-25 EP EP97116693A patent/EP0835926B1/de not_active Expired - Lifetime
- 1997-10-07 US US08/939,170 patent/US6107266A/en not_active Expired - Lifetime
- 1997-10-08 AR ARP970104657A patent/AR008887A1/es unknown
- 1997-10-08 TW TW086114779A patent/TW418252B/zh not_active IP Right Cessation
- 1997-10-08 KR KR1019970051487A patent/KR100507515B1/ko not_active IP Right Cessation
- 1997-10-08 HU HU9701617A patent/HUP9701617A3/hu unknown
- 1997-10-09 CZ CZ19973198A patent/CZ294306B6/cs not_active IP Right Cessation
- 1997-10-09 BR BR9704995A patent/BR9704995A/pt not_active Application Discontinuation
- 1997-10-09 PL PL97322521A patent/PL188368B1/pl not_active IP Right Cessation
- 1997-10-09 JP JP27750497A patent/JP4897988B2/ja not_active Expired - Fee Related
-
2000
- 2000-07-21 US US09/621,492 patent/US6645927B1/en not_active Expired - Fee Related
-
2003
- 2003-05-12 US US10/436,472 patent/US20030207784A1/en not_active Abandoned
Patent Citations (7)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
EP0037026A1 (de) * | 1980-03-28 | 1981-10-07 | Henkel Kommanditgesellschaft auf Aktien | Verfahren zur Herstellung eines lagerstabilen, leichtlöslichen Granulates mit einem Gehalt an Bleichaktivatoren |
US5200236A (en) * | 1989-11-15 | 1993-04-06 | Lever Brothers Company, Division Of Conopco, Inc. | Method for wax encapsulating particles |
US5230822A (en) * | 1989-11-15 | 1993-07-27 | Lever Brothers Company, Division Of Conopco, Inc. | Wax-encapsulated particles |
WO1994026862A1 (de) * | 1993-05-17 | 1994-11-24 | Henkel Kommanditgesellschaft Auf Aktien | Bleich- und desinfektionsmittel |
DE4316481A1 (de) * | 1993-05-17 | 1994-11-24 | Henkel Kgaa | Bleich- und Desinfektionsmittel |
US5480577A (en) * | 1994-06-07 | 1996-01-02 | Lever Brothers Company, Division Of Conopco, Inc. | Encapsulates containing surfactant for improved release and dissolution rates |
EP0737739A2 (de) * | 1995-04-13 | 1996-10-16 | The Procter & Gamble Company | Verfahren zur Herstellung eines Waschmittelteilchens |
Cited By (4)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US6498133B2 (en) | 2000-11-17 | 2002-12-24 | Clariant Gmbh | Particulate bleach activators based on acetonitriles |
WO2010115582A1 (de) * | 2009-04-11 | 2010-10-14 | Clariant International Ltd | Bleichmittelgranulate mit aktivcoating |
EP2640819B1 (de) | 2010-11-19 | 2018-07-04 | Reckitt Benckiser Finish B.V. | Gefärbte beschichtete bleichstoffe |
WO2017102473A1 (de) * | 2015-12-18 | 2017-06-22 | Henkel Ag & Co. Kgaa | Partikuläres mittel zur verstärkung der bleichwirkung |
Also Published As
Publication number | Publication date |
---|---|
ES2276414T3 (es) | 2007-06-16 |
BR9704995A (pt) | 1998-11-03 |
PL322521A1 (en) | 1998-04-14 |
TW418252B (en) | 2001-01-11 |
DE19641708A1 (de) | 1998-04-16 |
DE59712800D1 (de) | 2007-03-15 |
CA2216193A1 (en) | 1998-04-10 |
EP0835926A3 (de) | 1999-01-07 |
PL188368B1 (pl) | 2005-01-31 |
JPH10152697A (ja) | 1998-06-09 |
US20030207784A1 (en) | 2003-11-06 |
JP4897988B2 (ja) | 2012-03-14 |
AR008887A1 (es) | 2000-02-23 |
CZ319897A3 (cs) | 1998-04-15 |
EP0835926B1 (de) | 2007-01-24 |
HU9701617D0 (en) | 1997-11-28 |
CA2216193C (en) | 2006-07-04 |
HUP9701617A3 (en) | 2000-03-28 |
KR100507515B1 (ko) | 2005-11-14 |
HUP9701617A2 (hu) | 1998-07-28 |
KR19980032630A (ko) | 1998-07-25 |
US6645927B1 (en) | 2003-11-11 |
CZ294306B6 (cs) | 2004-11-10 |
US6107266A (en) | 2000-08-22 |
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