EP0835926A2 - Method of production of a coated bleach activator granule - Google Patents
Method of production of a coated bleach activator granule 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
Bleichaktivatoren sind wichtige Bestandteile in Waschmitteln, Fleckensalzen und Maschinengeschirrspülmitteln. Sie ermöglichen eine bleichende Wirkung bereits bei relativ niedrigen Temperaturen, indem sie mit Wasserstoffperoxid - meist Perborate oder Percarbonate - unter Freisetzung einer organischen Peroxicarbonsäure reagieren.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.
Das erzielbare Bleichergebnis wird bestimmt durch Art und Reaktivität der gebildeten Peroxicarbonsäure, die Struktur der zu perhydrolisierenden Bindung sowie die Wasserlöslichkeit des Bleichaktivators. Da es sich meist um einen reaktiven Ester oder ein Amid handelt, ist es in vielen Fällen notwendig, ihn für das vorgesehene Einsatzgebiet in granulierter Form einzusetzen, um eine Hydrolyse in Gegenwart alkalischer Waschmittelbestandteile zu verhindern und eine ausreichende Lagerstabilität zu gewährleisten.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.
Zur Granulierung dieser Substanzen sind in der Vergangenheit zahlreiche Hilfsstoffe und Verfahren vorgeschlagen worden. In EP-A-0 037 026 wird ein Verfahren zur Herstellung eines leicht löslichen Aktivatorgranulates aus 90 bis 98 % Aktivator mit 10 bis 2 % Celluloseether, Stärke oder Stärkeether beschrieben. Granulate bestehend aus Bleichaktivator, filmbildenden Polymeren und Zusätzen einer organischen C3-C6-Carbon-, Hydroxycarbon- oder Ethercarbonsäure werden in WO 90/01535 angeführt. Aus EP-A-0 468 824 sind Granulate aus Bleichaktivator und einem filmbildenden Polymer, das bei pH 10 besser löslich ist als bei pH 7, bekannt. DE-OS-44 39 039 beschreibt ein Verfahren zur Herstellung eines Aktivatorgranulats durch Vermischen eines trockenen Bleichaktivators mit einem trockenen, anorganischen, hydratwasserhaltigen Bindematerial, Verpressen dieser Mischung zu größeren Agglomeraten und Zerkleinern dieser Agglomerate auf die gewünschte Korngröße. Ein wasserfreies Herstellverfahren durch Kompaktierung des Bleichaktivators ohne Einsatz von Wasser mit mindestens einem mit Wasser quellbaren Hilfsstoff ist aus EP-A-0 075 818 bekannt.Numerous auxiliaries and processes have been proposed in the past for granulating these substances. 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.
Nachteilig bei diesen Aktivatorgranulaten ist, daß die Eigenschaften des Granulates im wesentlichen durch das Bindemittel und das verwendete Granulierverfahren festgelegt sind und oft neben den in der Literatur beschriebenen Vorteilen auch gewisse Nachteile, z.B. nicht optimale Wirkstofffreisetzung, geringe Abriebfestigkeit, hoher Staubanteil, ungenügende Lagerstabilität, Entmischung im Pulver oder Farbschädigung des Gewebes beim Einsatz in Wasch- und Reinigungsmitteln aufweisen.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.
Um an Granulaten definierte Eigenschaften einzustellen, wird oftmals nachträglich zum Granulierschritt ein Coatingschritt durchgeführt. Gängige Verfahren sind das Coating in Mischern (mechanisch induzierte Wirbelschicht) oder das Umhüllen in Wirbelschichtapparaturen (pneumatisch induzierte Wirbelschicht).In order to adjust the properties defined on granules, it is often added later a coating step is carried out for the granulating step. These are common procedures Coating in mixers (mechanically induced fluidized bed) or wrapping in Fluid bed apparatus (pneumatically induced fluid bed).
So wird in WO-92/13798 für einen Bleichaktivator ein Coating mit einer wasserlöslichen oberhalb 30°C schmelzenden organischen Säure und in WO-94/03305 ein Coating mit einem wasserlöslichen sauren Polymer zur Reduzierung der Farbschädigung der Wäsche beschrieben.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.
Aus WO-94/26862 ist das Coating eines Granulates, bestehend aus Bleichaktivator und wasser- und oder alkalilöslichem Polymer, mit einer zwischen 30°C und 100°C schmelzenden organischen Verbindung zur Reduzierung der Entmischung im pulverförmigen Endprodukt bekannt. Dabei wird das Aktivatorgranulat in einem Lödige-Pflugscharmischer vorgelegt, ohne Verwendung des Zerhackers bei Raumtemperatur mit 160 bis 180 U/min umgewälzt und dann mit der heißen Schmelze besprüht. Nachteil dieses Verfahrens ist eine sehr schlechte Coatingqualität, die zwar eine Reduzierung der Entmischung im pulverförmigen Endprodukt bewirkt, jedoch keinen Einfluß auf die anderen Granulateigenschaften, wie z.B. Wirkstofffreisetzung, Abriebfestigkeit, Staubanteil oder Lagerstabilität hat. Der positive Effekt auf das Entmischungsverhalten ist vermutlich auf ein tröpfchenförmiges Erstarren der Coatingsubstanz auf der Granulatoberfläche zurückzuführen, wodurch ein Verhaken des Granulatkorns im Schüttgut bewirkt wird.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.
Aufgabe der vorliegenden Erfindung war die Entwicklung eines Coatingverfahrens für Aktivatorgranulate, das ein gezieltes Einstellen der Granulateigenschaften in einem weiten Bereich bei gleichzeitig optimaler Ausnutzung des Coatingmaterials ermöglicht.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.
Die Lösung dieser Aufgabe gelang durch eine Temperung während und/oder nach dem Coaten.This task was solved by tempering during and / or after the coating.
Gegenstand der Erfindung ist somit ein Verfahren zur Herstellung eines gecoateten Bleichaktivatorgranulats, wobei man ein Bleichaktivatorbasisgranulat mit einer Coatingsubstanz umhüllt und gleichzeitig oder anschließend tempert.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.
Als Basisgranulate können alle Aktivatoren verwendet werden, die in granulierter Form einen Schmelzpunkt von oberhalb 100°C aufweisen. Beispiele für Aktivatorsubstanzen sind Tetraacetylethylendiamin (TAED), Tetraacetylglukoluril (TAGU), Diacetyldioxohexahydrotriazin (DADHT), Acyloxybenzolsulfonate (z.B. Nonanyloxybenzolsulfonat [NOBS], Benzoyloxibenzolsulfonat [BOBS]), acylierte Zucker (z.B.: Pentaacetylglucose [PAG]) oder Verbindungen wie sie in EP-A-0 325 100, EP-A-0 492 00 und WO-91/10719 beschrieben sind. Weitere geeignete Aktivatoren sind N-acylierte Amine, Amide, Lactame, aktivierte Carbonsäureester, Carbonsäureanhydride, Lactone, Acylale, Carbonsäureamide, Acyllactame, acylierte Harnstoffe und Oxamide, daneben insbesondere aber auch Nitrile, die neben der Nitrilgruppe auch eine quaternierte Ammoniumgruppe enthalten können. Auch können Mischungen verschiedener Bleichaktivatoren im Basisgranulat vorhanden sein.All activators can be used as basic granules, those in granulated Form have a melting point of above 100 ° C. examples for Activator substances are tetraacetylethylenediamine (TAED), tetraacetylglucoluril (TAGU), diacetyldioxohexahydrotriazine (DADHT), acyloxybenzenesulfonates (e.g. Nonanyloxybenzenesulfonate [NOBS], benzoyloxybenzenesulfonate [BOBS]), acylated Sugar (e.g. pentaacetyl glucose [PAG]) or compounds as described in EP-A-0 325 100, EP-A-0 492 00 and WO-91/10719. Further suitable 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.
Diese Basisgranulate können die üblichen Granulierhilfsmittel enthalten, welche einen Schmelzpunkt von über 100°C haben sollen. In Frage kommen hier filmbildende Polymere, z.B.: Celluloseether, Stärke, Stärkeether, Homo-, Co-, Propfcopolymerisate ungesättigter Carbonsäuren und/oder Sulfonsäure sowie deren Salze; Organische Substanzen, z.B.: Cellulose, vernetztes Polyvinylpyrrolidon oder Anorganische Substanzen, z.B.: Kieselsäure, amorphe Silikate, Zeolithe, Bentonite, Alkalischichtsilikate der Formel MM'SixO2x-1 * y H2O (M, M' = Na, K, H; x = 1.9 - 23; y = 0 - 25), Ortho-, Pyro-, Polyphosphate, Phosphonsäuren und deren Salze, Sulfate, Carbonate, Bicarbonate. Je nach Bedarf können diese Granulierhilfsmittel als Einzelstoffe oder als Gemische eingesetzt werden.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. silica, amorphous silicates, zeolites, bentonites, alkali layer silicates of the formula MM'Si x O 2x-1 * y H 2 O (M, M '= Na, K, H; x = 1.9 - 23; y = 0 - 25), ortho-, pyro-, polyphosphates, phosphonic acids and their salts, sulfates, carbonates, bicarbonates. Depending on requirements, these granulation aids can be used as individual substances or as mixtures.
Neben dem Bleichaktivator und dem Granulierhilfsmittel können die Bleichaktivatorbasisgranulate noch weitere Zusatzstoffe enthalten, die die Eigenschaften wie zum Beispiel Lagerstabilität und Bleichaktivierungsvermögen verbessern. Zu diesen Zusatzstoffen zählen anorganische Säuren, organische Säuren wie etwa ein- oder mehrwertige Carbonsäuren, Hydroxycarbonsäuren und/oder Ethercarbonsäuren sowie deren Salze, Komplexbildner, Metallkomplexe und Ketone.In addition to the bleach activator and the granulation aid, the Bleach activator base granules contain other additives that Properties such as storage stability and bleach activation capacity improve. These 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.
Je nach Bedarf können die vorgenannten Zusatzstoffe als Einzelstoffe oder als Gemische eingesetzt werden.Depending on requirements, the aforementioned additives can be used as individual substances or as Mixtures are used.
Die Herstellung dieser Basisgranulate erfolgt durch Vermischen des trockenen Bleichaktivators mit dem trockenen Granulierhilfsmittel, Verpressen dieser Mischung zu größeren Agglomeraten und Zerkleinern dieser Agglomerate auf die gewünschte Korngröße.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.
Das Verhältnis von Bleichaktivator zu Granulierhilfsmittel beträgt üblicherweise 50:50 bis 98:2, vorzugsweise 70:30 bis 96:4 Gew.-%. Die Menge des Zusatzstoffes richtet sich insbesondere nach seiner Art. So werden acidifizierende Zusätze und organische Katalysatoren zur Leistungssteigerung der Persäure in Mengen von 0 bis 20 Gew.-%, insbesondere in Mengen von 1 bis 10 Gew.-%, bezogen auf das Gesamtgewicht, zugesetzt, Metallkomplexe hingegen in Konzentrationen im ppm Bereich. 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.
Als Coatingsubstanzen kommen alle Verbindungen oder deren Mischungen in Frage, die bei Raumtemperatur fest sind und im Bereich von 30 bis 100°C erweichen oder schmelzen. Beispiele hierfür sind:All compounds or their mixtures come in as coating substances Question that are solid at room temperature and in the range of 30 to 100 ° C soften or melt. Examples for this are:
C8-C31-Fettsäuren (z.B.: Laurin-, Myristin-, Stearinsäure); C8-C31-Fettalkohole; Polyalkenylglykole (z.B. Polyethylenglykole mit einer Molmasse von 1000 bis 50000 g/mol); Nonionics (z.B. C8-C31-Fettalkoholpolyalkoxylate mit 1 bis 100 Molen EO); Anionics (z.B. Alkansulfonate, Alkylbenzolsulfonate, α-Olefinsulfonate, Alkylsulfate, Alkylethersulfate mit C8-C31-Kohlenwasserstoffresten); Polymere (z.B. Polyvinylalkohole); Wachse (z.B.: Montanwachse, Paraffinwachse, Esterwachse, Polyolefinwachse); Silikone.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); Anionics (for example alkanesulfonates, alkylbenzenesulfonates, α-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.
In der im Bereich von 30 bis 100°C erweichenden oder schmelzenden Coatingsubstanz können darüber hinaus weitere in diesem Temperaturbereich nicht erweichende oder schmelzende Substanzen in gelöster oder suspendierter Form vorliegen, z.B.: Polymere (z.B. Homo-, Co- oder Propfencopolymerisate ungesättigter Carbonsäuren und/oder Sulfonsäuren sowie deren Alkalisalze, Celluloseether, Stärke, Stärkeether, Polyvinylpyrrolidon); Organische Substanzen (z.B. ein- oder mehrwertige Carbonsäuren, Hydroxycarbonsäuren oder Ethercarbonsäuren mit 3 bis 8 C-Atomen sowie deren Salze); Farbstoffe; Anorganische Substanzen (z.B.: Silikate, Carbonate, Bicarbonate, Sulfate, Phosphate, Phosphonate).In the range from 30 to 100 ° C softening or melting Furthermore, coating substance cannot do any more in this temperature range 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).
Je nach den gewünschten Eigenschaften des gecoateten Aktivatorgranulates kann der Gehalt an Hüllsubstanz 1 bis 30 Gew.-%, bevorzugt 5 bis 15 Gew.-%, bezogen auf gecoatetes Aktivatorgranulat, betragen.Depending on the desired properties of the coated activator granules the content of the coating substance is 1 to 30% by weight, preferably 5 to 15% by weight on coated activator granules.
Zum Aufbringen der Hüllsubstanzen können Mischer (mechanisch induzierte Wirbelschicht) und Wirbelschichtapparate (pneumatisch induzierte Wirbelschicht) benutzt werden. Als Mischer sind z.B. Pflugscharmischer (kontinuierlich und chargenweise), Ringschichtmischer oder auch Schugi-Mischer möglich. Die Temperung kann bei Verwendung eines Mischers in einem Granulatvorwärmer und/oder im Mischer direkt und/oder in einem dem Mischer nachgeschalteten Fließbett erfolgen. Zur Kühlung des gecoateten Granulates können Granulatkühler oder Fließbettkühler eingesetzt werden. Im Falle von Wirbelschichtapparaturen erfolgt die Temperung über das zur Aufwirbelung verwendete Heißgas. Das nach dem Wirbelschichtverfahren gecoatete Granulat kann ähnlich wie beim Mischerverfahren über einen Granulatkühler oder einen Fließbettkühler abgekühlt werden. Sowohl beim Mischerverfahren als auch beim Wirbelschichtverfahren kann die Coatingsubstanz über eine Einstoff- oder eine Zweistoffdüsvorrichtung aufgesprüht werden.Mixers (mechanically induced Fluidized bed) and fluidized bed apparatus (pneumatically induced fluidized bed) to be used. As 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. In the case of fluidized bed equipment 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.
Die Temperung besteht in einer Wärmebehandlung bei einer Temperatur von 30 bis 100°C, jedoch gleich oder unterhalb der Schmelz- oder Erweichungstemperatur der jeweiligen Hüllsubstanz. Bevorzugt arbeitet man bei einer Temperatur, die knapp unterhalb der Schmelz oder Erweichungstemperatur liegt.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.
Die Korngröße des gecoateten Bleichaktivatorgranulats beträgt von 0.1 bis 2.0 mm, bevorzugt von 0.2 bis 1.0 mm und besonders bevorzugt von 0.3 bis 0.8 mm.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.
Die genaue Temperatur bei der Temperung bzw. die Temperaturdifferenz zum Schmelzpunkt der Coatingsubstanz ist abhängig von der Coatingmenge, der Temperzeit und den für das gecoatete Bleichaktivatorgranulat gewünschten Eigenschaften und muß für das jeweilige System in Vorversuchen ermittelt werden.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.
Die Zeitdauer für die Temperung beträgt ungefähr 1 bis 180, vorzugsweise 3 bis 60, besonders bevorzugt 5 bis 30 Minuten.The time for the annealing is approximately 1 to 180, preferably 3 to 60, particularly preferably 5 to 30 minutes.
Der Vorteil des neuen Verfahrens gegenüber dem Stand der Technik liegt darin, daß das flüssige Coatingmittel nicht zu schnell erstarrt und dadurch die Möglichkeit hat, als dünner Film auf der Granulatoberfläche zu verlaufen. Man erreicht so ein sehr gleichmäßiges Überziehen des Korns in dünner Schicht mit der Coatingsubstanz und einen optimalen Coatingeffekt bei Einsatz einer minimalen Menge Coatingsubstanz. Bei üblichen Verfahren, d.h. ohne Temperungsschritt, tritt ein zu schnelles Erstarren der Einzeltröpfchen auf der kalten Granulatoberfläche ein. Infolgedessen wird die Oberfläche nur mit feinen Einzeltröpfchen belegt und weist noch große Coatingfehlstellen auf. Der gewünschte Coatingeffekt wird dadurch nur unzureichend erzielt bzw. eine deutlich höhere Menge Coatingsubstanz ist zur Erzielung eines gewünschten Coatingeffektes erforderlich. Letzteres reduziert aber den Gehalt an Aktivatorsubstanz, was vielfach unerwünscht ist.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. You reach one very even coating of the grain in a thin layer with the Coating substance and an optimal coating effect when using a minimal Amount of coating substance. In usual processes, i.e. without tempering step the individual droplets solidify too quickly on the cold granulate surface a. As a result, 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.
Durch das erfindungsgemäße Verfahren können die Eigenschaften der
Aktivatorgranulate durch geeignete Wahl der Coatingsubstanz, der Coatingmenge
und der Temperaturführung des Prozesses in weiten Bereichen gezielt auf die
gewünschten Anforderungen hin optimiert werden. Dabei ist vor allem die gezielte
Optimierung folgender Aktivatorgranulateigenschaften möglich.
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.
In order to avoid the interaction between the bleaching system and the enzyme system, a slightly delayed reaction and release of active ingredient in the bleaching system with simultaneous rapid enzyme action is advantageous. In this way, the enzymes can fully develop their washing power in the first minutes of the washing process without being damaged by the bleaching system. Only after the enzymes have done their job is the bleaching process started by reaction of the bleach activator with the hydrogen peroxide source. The reactivity, ie the rate of dissolution or the rate of peracid formation, can be tailored to the enzyme system by suitable coating of the bleach activator. The process allows the peracid formation rate to be set in a targeted manner with a minimum amount of coating substance and therefore a maximum activator content.
By coating a granulate with softening or melting substances, the abrasion resistance of an activator granulate can be increased. The higher the abrasion resistance, the better the granulate surface is coated with the coating substance. By means of the coating method according to the invention, the coating substance can optimally run on the granulate surface with a minimal coating amount and thus an optimal improvement in abrasion resistance.
The coating method according to the invention, in which suitable hardening during and / or after the coating step prevents the softening or melting coating substance from solidifying too quickly, also enables optimal dust removal from the granules with a minimal coating amount, since the coating substance lasts for a longer period of time remains flowable and bindable and is therefore able to bind more dust particles. In the case of the coating according to the prior art, on the other hand, in the worst case, an increase in the dust content due to direct spray drying can be expected.
When a detergent and cleaning agent is stored, a reaction with subsequent loss of active oxygen and thus an uncontrolled degradation of the bleaching system can occur at the boundary between the activator grain and the directly adjacent grain of the hydrogen peroxide source. Through an optimal coating, as is only possible with the coating method according to the invention, a complete protective layer is built up on the grain size, which then prevents a reaction of the activator grain with the grain of the hydrogen peroxide source during storage. When using water-soluble and / or low-melting coating substances, the required bleaching performance can nevertheless be achieved in the washing process.
Die auf diese Weise erhaltenen Granulate sind direkt zum Einsatz in Wasch- und Reinigungsmitteln geeignet. Sie sind ideal zum Einsatz in Vollwaschmitteln, Fleckensalzen, Maschinengeschirrspülmitteln, pulverförmigen Allzweckreinigern und Gebißreinigern. In diesen Formulierungen werden die erfindungsgemäßen Granulate meist in Kombination mit einer Wasserstoffperoxidquelle eingesetzt. Beispiele dafür sind Perborat-Monohydrat, Perborat-Tetrahydrat, Percarbonate sowie Wasserstoffperoxid-Addukte an Harnstoff oder Aminoxiden. Daneben kann die Formulierung dem Stand der Technik entsprechend weitere Waschmittelbestandteile aufweisen, wie organische oder anorganische Builder und Co-Builder, Tenside, Enzyme, Waschadditive, optische Aufheller und Parfüm.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. In these formulations, 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. Besides that, can the wording according to the state of the art further Have detergent ingredients, such as organic or inorganic builders and Co-builders, surfactants, enzymes, washing additives, optical brighteners and perfume.
TAED 4303 (Hoechst AG) wurde kontinuierlich mit einer Durchsatzleistung von 480 kg/h in einen Schugi-Mischer (Flexomix 160, Fa. Hosokawa Schugi) dosiert und mit einer 75°C heißen Schmelze von Myristinsäure besprüht. Das gecoatete Material fiel direkt in ein nachgeschaltetes Fließbett (Hosokawa Schugi) und wurde dort in einer ersten Kammer für 5 bis 10 Minuten bei Wirbelbett-Temperaturen von ca. 54°C getempert und dann in einer zweiten Kammer bei Wirbelbett-Temperaturen von ca. 35°C gekühlt. Zu Vergleichszwecken (Stand der Technik) wurde TAED 4303 kontinuierlich mit einer Durchsatzleistung von 480 kg/h in den Schugi-Mischer dosiert, mit einer 75°C heißen Schmelze von Myristinsäure besprüht und dann direkt im nachgeschalteten Fließbett bei Wirbelbett-Temperaturen von ca. 35°C gekühlt.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.
Die Coatingqualität der Produkte wurde durch Bestimmung der Geschwindigkeit der Peressigsäurebildung bei einer Temperatur von 20°C beurteilt. Je langsamer die Peressigsäurebildung ist, desto besser ist der erzielte Coatinggrad. 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.
Zur Bestimmung der Geschwindigkeit der Peressigsäurebildung wurden in einem
2 l - Becherglas 1 l destilliertes Wasser, 8.0 g Testwaschmittel WMP und 1.5 g
Natriumperborat Monohydrat bei 20°C vorgelegt und mit einem Magnetrührer mit
250 bis 280 U/min gerührt. Nach 1 bis 2 min wurden dann 0.5 g des gecoateten
TAED-Granulates zugegeben. Nach einer Minute wurde ein Aliquot von 50 ml
abpipettiert und in einen Erlenmeyerkolben auf 150 g Eis und 5 ml 20 %ige
Essigsäure gegeben. Nach Zusatz von 2 bis 3 ml 10 %iger Kaliumiodidlösung wurde
zügig mit 0.01 molarer Natriumthiosulfatlösung bis zum potentiometrischen
Äquivalenzpunkt titriert (Titroprozessor 716 DMS, Fa. Metrohm) und aus der
verbrauchten Menge Natriumthiosulfat die Menge Peressigsäure berechnet. In
Abständen von 2 bis 5 min wurden dann weitere Proben entnommen und wie
beschrieben titriert. Der ganze Vorgang wurde so oft wiederholt, bis nach drei
aufeinanderfolgenden Titrationen gleiche oder sogar fallende
Peressigsäuremengen gefunden wurden. Die maximal gefundene
Peressigsäuremenge wurde dann zu
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.
Set 100% and on this basis finally determined the amount of peracetic acid formed after 5, 10 and 20 minutes as a measure of the rate of peracetic acid formation.
Durch die Temperung läßt sich bei gleicher Coatingmenge die Coatingqualität, ausgedrückt durch die Verzögerung der Peressigsäurebildung, deutlich verbessern (Vergleich der Produkte 3 und 4).By tempering, the coating quality can be expressed by the delay in the formation of peracetic acid, improve significantly (Comparison of products 3 and 4).
Zur Erzielung einer optimalen Coatingqualität ist bei geeigneter Temperung eine Menge von 10 % Coatingsubstanz (Produkt 2) ausreichend.To achieve an optimal coating quality with a suitable tempering is a Amount of 10% coating substance (product 2) sufficient.
500 - 600 g TAED 4303 wurden in der Wirbelschicht (Wirbelschichtapparatur Strea 1, Fa. Aeromatic) vorgelegt und mit einer ca. 80°C heißen Schmelze von Stearinsäure besprüht. Dabei wurde im einen Fall zu Vergleichszwecken das Wirbelbett mit niedrigen Temperaturen betrieben und nach Beendigung des Aufsprühens nochmals für ca. 5 min nachgekühlt (Stand der Technik). Im anderen Fall wurde nach dem erfindungsgemäßen Verfahren das gecoatete Granulat erneut in der Wirbelschicht vorgelegt und getempert. Dazu wurde das Wirbelbett schrittweise auf Temperaturen von etwa 65 bis 70°C erwärmt und diese Produkttemperatur für etwa 5 bis 8 min. konstant gehalten. Anschließend wurde das getemperte Produkt schrittweise wieder abgekühlt.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.
Die Coatingqualität wurde wiederum durch Bestimmung der
Bildungsgeschwindigkeit der Peressigsäure bei einer Temperatur von 20°C geprüft.
Je langsamer die Peressigsäurebildung ist, desto besser ist der erzielte
Coatinggrad.
Durch die Temperung läßt sich bei gleicher Coatingmenge die Coatingqualität, ausgedrückt durch die Verzögerung der Peressigsäurebildung, deutlich verbessern (Vergleich der Produkte 6 und 8 bzw. Produkte 7 und 9).By tempering, 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).
Zur Erzielung einer optimalen Coatingqualität ist bei geeigneter Temperung eine Menge von 10 % Coatingsubstanz ausreichend (Produkt 6).To achieve an optimal coating quality with a suitable tempering is a Amount of 10% coating substance sufficient (product 6).
Der Einfluß der Temperung auf die Coatingqualität zeigt sich auch in der Lagerstabilität von TAED-Granulaten in Waschmittelformulierungen.The influence of tempering on the coating quality is also evident in the Storage stability of TAED granules in detergent formulations.
Die Prüfung der Lagerstabilität erfolgte in vorgefertigten Faltschachteln (Höhe:
6,5 cm; Breite 3,2 cm; Tiefe 2,2 cm) bei 38°C und 80 % relativer Luftfeuchtigkeit (rF)
über einen Zeitraum von 28 Tagen. Jede Faltschachtel wurde mit einem homogenen
Gemisch aus 8,0 g Testwaschmittel WMP, 1,5 g Natriumpercarbonat und 0,5 g des
zu prüfenden TAED-Granulates gefüllt und dann oben mit Tesafilm verschlossen.
Alle Proben wurden am gleichen Tag gemischt und abgefüllt. Die gefüllten und
beschrifteten Faltschachteln wurden dann mit genügend Abstand voneinander in
den Klimaschrank gestellt und bei 38°C/80 % rF gelagert. Nach 0, 3, 6, 9, 15, 23
und 28 Tagen Lagerzeit wurden die Proben aus dem Klimaschrank entnommen, die
gesamte Probe bei 20°C in 1 l destilliertes Wasser unter Rühren mit einem
Magnetrührer (250 bis 280 U/min) eingetragen und 1 g Natriumpercarbonat
zugesetzt. Die weitere Bestimmung der gebildeten Menge an Peressigsäure erfolgte
analog den Angaben in Beispiel 1. Aus dem gefundenen Maximalwert der
Peressigsäure wurde dann der TAED-Gehalt der Probe berechnet. Der TAED-Erhaltungsgrad
stellt den prozentualen TAED-Gehalt der Probe nach Lagerung
bezogen auf den TAED-Gehalt der ungelagerten Probe dar.
Bei geringen Coatingmengen von 5 bis 10 % ist eine Verbesserung vieler Produkteigenschaften, hier beispielsweise die Lagerstabilität in Waschmittelformulierungen, nur durch Temperung d.h. nur durch das erfindungsgemäße Verfahren zu erzielen. With small coating quantities of 5 to 10%, an improvement is many Product properties, here for example the storage stability in Detergent formulations, only by tempering i.e. only through that to achieve the inventive method.
TAED 4303 wurde über eine flexible Dosierschnecke kontinuierlich mit 40 kg/h in den Wirbelschichtapparat (Technikumswirbelschichtapparatur) eindosiert und mit 20 % Myristinsäure gecoatet. Die Verweilzeit in der Wirbelschicht betrug ca. 30 Minuten. Das durch eine Zellenradschleuse ausgetragene Produkt wurde mittels einer Dosierschnecke auf eine Siebmaschine transportiert, auf der der Grobanteil von größer als 1.0 mm und der Feinanteil von weniger als 0.2 mm abgetrennt wurden. Der Grobanteil wurde anschließend in einer Mühle zerkleinert und dann gemeinsam mit dem Feinanteil über eine flexible Dosierschnecke in den Wirbelschichtapparat zurückgeführt. Im Verlauf des Versuches wurde die Wirbelbettemperatur von anfänglich 46°C auf schließlich 54°C erhöht.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. In the course of the experiment, the Fluid bed temperature increased from initially 46 ° C to finally 54 ° C.
Die Coatingqualität wurde durch Bestimmung der Bildungsgeschwindigkeit der
Peressigsäure bei einer Temperatur von 20°C sowie des Staubanteils von weniger
als 0.2 mm des gecoateten TAED-Granulates geprüft. Je langsamer die
Peressigsäurebildung ist, desto besser ist der erzielte Coatinggrad. Je geringer der
Staubanteil, desto besser ist die durch das Coating erzielte Entstaubung und
Erhöhung der Abriebfestigkeit.
Mit steigender, sich an den Schmelzpunkt der Myristinsäure (55°C) annähernder Wirbelbettemperatur nimmt die Coatingqualität ausgedrückt durch die Verzögerung der Persäurebildung, deutlich zu und man erzielt eine bessere Entstaubung und höhere Abriebfestigkeit, ausgedrückt durch den abnehmenden Staubanteil < 0.2 mm des gecoateten Granulates.With increasing, approaching the melting point of myristic acid (55 ° C) 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.
1,2 kg TAED-Granulat gemäß EP-A-0 037 026 wurden in einem Batch-Pflugscharmischer (M5R, Fa. Lödige) vorgelegt und unter Durchmischung mit einer Drehzahl der Mischwerkzeuge von ca. 150 U/min mit 210 g einer 80°C heißen Stearinsäureschmelze besprüht. Dabei wurde der Mischerinhalt während des Coatingschrittes über einen Heizmantel auf eine Temperatur von 50°C temperiert. Die Coating- und Temperzeit betrug ca. 10 Minuten. Zu Vergleichszwecken wurden gemäß WO-94/26826 1,2 kg TAED-Granulat gemäß EP-A-0 037 026 in einem Batch-Pflugscharmischer vorgelegt und bei Raumtemperatur unter Durchmischung mit einer Drehzahl der Mischwerkzeuge von ca. 150 U/min mit 210 g einer 80°C heißen Stearinsäureschmelze besprüht.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. For comparison purposes according to 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.
Die Coatingqualität wurde durch Bestimmung der Bildungsgeschwindigkeit der
Peressigsäure bei einer Temperatur von 20°C geprüft.
Ohne Temperung läßt sich zwar ein positiver Effekt durch das Coating auf das Entmischungsverhalten im Pulver erzielen (Produkt 18), aber die Verbesserung vieler anderer Eigenschaften, hier beispielsweise die Verzögerung der Peressigsäurebildung, ist nur durch Temperung, d.h. durch das erfindungsgemäße Verfahren möglich (Produkt 17).Without tempering, 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).
Der positive Effekt auf das Entmischungsverhalten, der durch das Coating ohne Temperung erzielt wird, ist vermutlich auf das tröpfchenförmige Erstarren der Coatingsubstanz auf der Granulatoberfläche zurückzuführen, wodurch ein Verhaken des Granulatkorns im Schüttgut bewirkt wird. Damit ist aber kein positiver Effekt auf viele andere Eigenschaften verbunden.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.
TAED 4303 wurde kontinuierlich mit Durchsatzleistungen von 100 bis 300 kg/h in den Pflugscharmischer (KT-160, Fa. Drais) eindosiert. Dabei wurde der Mischerinhalt über einen Heizmantel auf Temperaturen im Bereich von 44 bis 52°C temperiert. Die Verweilzeit im Mischer betrug 8 bis 12 Minuten. Gleichzeitig wurde eine Schmelze von Stearinsäure mit einer Temperatur von 80°C in den vorderen Teil des Mischers (näher zum Produkteintrag) eingedüst. Die Coatingmenge betrug 7 %. Der Mischer wurde mit einer Drehzahl der Mischwerkzeuge von 90 U/min und ohne Einsatz der Zerhackermesser betrieben. Der Füllgrad im Mischer war so eingestellt, daß das Produkt gerade die Mischwelle überdeckte. Das gecoatete Material wurde kontinuierlich aus dem Mischer abgezogen und direkt über ein Sieb (0.2 bis 1.0 mm) geleitet, um Fein- und Grobanteile abzutrennen.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. At the same time 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.
Die Coatingqualität wurde durch Bestimmung der Bildungsgeschwindigkeit der
Peressigsäure bei einer Temperatur von 20°C geprüft.
Mit steigender, sich an den Schmelzpunkt der Stearinsäure annähernder Temperatur des Mischgutes nimmt die Coatingqualität, ausgedrückt durch die Verzögerung der Persäurebildung, zu.With increasing, approaching the melting point of stearic acid The temperature of the mix takes the coating quality, expressed by the Delay in peracid formation, too.
Claims (13)
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| DE19641708 | 1996-10-10 | ||
| DE19641708A DE19641708A1 (en) | 1996-10-10 | 1996-10-10 | Process for the preparation of a coated bleach activator granulate |
Publications (3)
| Publication Number | Publication Date |
|---|---|
| EP0835926A2 true EP0835926A2 (en) | 1998-04-15 |
| EP0835926A3 EP0835926A3 (en) | 1999-01-07 |
| EP0835926B1 EP0835926B1 (en) | 2007-01-24 |
Family
ID=7808324
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| EP97116693A Expired - Lifetime EP0835926B1 (en) | 1996-10-10 | 1997-09-25 | Method of production of a coated bleach activator granule |
Country Status (13)
| Country | Link |
|---|---|
| US (3) | US6107266A (en) |
| EP (1) | EP0835926B1 (en) |
| JP (1) | JP4897988B2 (en) |
| KR (1) | KR100507515B1 (en) |
| AR (1) | AR008887A1 (en) |
| BR (1) | BR9704995A (en) |
| CA (1) | CA2216193C (en) |
| CZ (1) | CZ294306B6 (en) |
| DE (2) | DE19641708A1 (en) |
| ES (1) | ES2276414T3 (en) |
| HU (1) | HUP9701617A3 (en) |
| PL (1) | PL188368B1 (en) |
| TW (1) | TW418252B (en) |
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 (en) * | 2009-04-11 | 2010-10-14 | Clariant International Ltd | Bleach granules comprising an active coating |
| WO2017102473A1 (en) * | 2015-12-18 | 2017-06-22 | Henkel Ag & Co. Kgaa | Particulate agent for increasing the bleaching effect |
| EP2640819B1 (en) | 2010-11-19 | 2018-07-04 | Reckitt Benckiser Finish B.V. | Dyed coated bleach materials |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE19641708A1 (en) * | 1996-10-10 | 1998-04-16 | Clariant Gmbh | Process for the preparation of a coated bleach activator granulate |
| DE10038832A1 (en) * | 2000-08-04 | 2002-03-28 | Henkel Kgaa | Coated bleach activators |
| DE10161766A1 (en) * | 2001-12-15 | 2003-06-26 | Clariant Gmbh | Bleach co-granules |
| DE10304131A1 (en) | 2003-02-03 | 2004-08-05 | Clariant Gmbh | Transition metal complexes with nitrogen-containing ligands are used as catalysts for peroxy compounds, especially in detergent, bleaching and cleansing agents |
| DE10334046A1 (en) * | 2003-07-25 | 2005-02-10 | Clariant Gmbh | Process for the preparation of granulated acyloxybenzenesulfonates or acyloxybenzenecarboxylic acids and their salts |
| DE102004012568A1 (en) * | 2004-03-12 | 2005-12-08 | Henkel Kgaa | Bleach activators and process for their preparation |
| DE102004012915A1 (en) * | 2004-03-17 | 2005-10-13 | Clariant Gmbh | Solid preparations containing a sensitive active ingredient |
| BRPI0709795A2 (en) * | 2006-04-04 | 2011-07-26 | Basf Se | bleach system, process for preparing bleach system, detergent formulation, and use of a bleach system or detergent formulation |
| GB0710559D0 (en) * | 2007-06-02 | 2007-07-11 | Reckitt Benckiser Nv | Composition |
| US20100075883A1 (en) * | 2008-09-24 | 2010-03-25 | Ecolab Inc. | Granular cleaning and disinfecting composition |
| GB0918914D0 (en) | 2009-10-28 | 2009-12-16 | Revolymer Ltd | Composite |
| DE102009057222A1 (en) * | 2009-12-05 | 2011-06-09 | Clariant International Ltd. | Bleach catalyst compounds, process for their preparation and their use |
| DE102010028236A1 (en) * | 2010-04-27 | 2011-10-27 | Evonik Degussa Gmbh | Bleaching agent particles comprising sodium percarbonate and a bleach activator |
| GB201106408D0 (en) | 2011-04-15 | 2011-06-01 | Revolymer Ltd | Novel composite |
| GB201106409D0 (en) | 2011-04-15 | 2011-06-01 | Revolymer Ltd | Novel composite |
| GB201106377D0 (en) | 2011-04-15 | 2011-06-01 | Reckitt & Colman Overseas | Novel composite |
| GB201106391D0 (en) | 2011-04-15 | 2011-06-01 | Reckitt & Colman Overseas | Novel composite |
| US8765114B2 (en) | 2012-10-30 | 2014-07-01 | The Clorox Company | Anionic micelles with cationic polymeric counterions methods thereof |
| US8728530B1 (en) | 2012-10-30 | 2014-05-20 | The Clorox Company | Anionic micelles with cationic polymeric counterions compositions thereof |
| US8728454B1 (en) | 2012-10-30 | 2014-05-20 | The Clorox Company | Cationic micelles with anionic polymeric counterions compositions thereof |
| US8883706B2 (en) | 2012-10-30 | 2014-11-11 | The Clorox Company | Anionic micelles with cationic polymeric counterions systems thereof |
| US8883705B2 (en) | 2012-10-30 | 2014-11-11 | The Clorox Company | Cationic micelles with anionic polymeric counterions systems thereof |
| US20140227333A1 (en) * | 2013-02-12 | 2014-08-14 | Ecolab Usa Inc. | Dry active oxygen technology |
| WO2015169851A1 (en) * | 2014-05-09 | 2015-11-12 | Basf Se | Acylhydrazone granulate with two - layer coating for use in laundry detergents |
| WO2017177211A1 (en) * | 2016-04-08 | 2017-10-12 | Battelle Memorial Institute | Encapsulation compositions |
| CN110114450B (en) | 2016-10-18 | 2020-07-03 | 斯特里莱克斯有限责任公司 | Ambient moisture activatable surface treatment powders |
Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP0037026A1 (en) * | 1980-03-28 | 1981-10-07 | Henkel Kommanditgesellschaft auf Aktien | Process for the preparation of a storage-stable, easily soluble granulated compound containing a bleach activator |
| 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 (en) * | 1993-05-17 | 1994-11-24 | Henkel Kommanditgesellschaft Auf Aktien | Bleaching and disinfecting agent |
| 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 (en) * | 1995-04-13 | 1996-10-16 | The Procter & Gamble Company | Process for making a detergent particle |
Family Cites Families (23)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| AT339246B (en) * | 1974-08-14 | 1977-10-10 | Henkel & Cie Gmbh | BLEACHING AID SUITABLE AS A COMPONENT OF POWDERED DETERGENTS AND BLEACHING AGENTS |
| ATE12517T1 (en) * | 1980-12-09 | 1985-04-15 | Unilever Nv | BLEACH ACTIVATOR GRANULATE. |
| DE3128336A1 (en) * | 1981-07-17 | 1983-01-27 | Henkel KGaA, 4000 Düsseldorf | "METHOD FOR PRODUCING COATED NUCLEAR BLEACHING ACTIVATORS" |
| 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 |
| US4853143A (en) * | 1987-03-17 | 1989-08-01 | The Procter & Gamble Company | Bleach activator compositions containing an antioxidant |
| US4889651A (en) * | 1988-01-21 | 1989-12-26 | Colgate-Palmolive Company | Acetylated sugar ethers as bleach activators and detergency boosters |
| DE3826092A1 (en) * | 1988-08-01 | 1990-02-08 | Henkel Kgaa | GRANULAR BLEACH ACTIVATOR CONTAINING BLEACH ACTIVATORS WITH IMPROVED PROPERTIES |
| DE3843195A1 (en) * | 1988-12-22 | 1990-06-28 | Hoechst Ag | METHOD FOR PRODUCING STORAGE-STABLE, EASILY SOLUBLE BLEACHING ACTIVATOR GRANULES |
| GB8925621D0 (en) * | 1989-11-13 | 1990-01-04 | Unilever Plc | Process for preparing particulate detergent additive bodies and use thereof in detergent compositions |
| DK17290D0 (en) * | 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 (en) * | 1990-08-03 | 1992-02-06 | Henkel Kgaa | BLEACH ACTIVATORS IN GRANULATE FORM |
| EP0492000B1 (en) * | 1990-12-28 | 1997-04-09 | AUSIMONT S.p.A. | Process for increasing the bleaching efficiency of an inorganic persalt |
| 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 (en) * | 1994-11-02 | 1996-05-09 | Hoechst Ag | Granulated bleach activators and their manufacture |
| DE19641708A1 (en) * | 1996-10-10 | 1998-04-16 | Clariant Gmbh | Process for the preparation of a coated bleach activator granulate |
| DE19740671A1 (en) * | 1997-09-16 | 1999-03-18 | Clariant Gmbh | Bleach activator granulate containing ammonium nitrile and layered silicate |
-
1996
- 1996-10-10 DE DE19641708A patent/DE19641708A1/en not_active Withdrawn
-
1997
- 1997-09-22 CA CA002216193A patent/CA2216193C/en not_active Expired - Fee Related
- 1997-09-25 EP EP97116693A patent/EP0835926B1/en not_active Expired - Lifetime
- 1997-09-25 ES ES97116693T patent/ES2276414T3/en not_active Expired - Lifetime
- 1997-09-25 DE DE59712800T patent/DE59712800D1/en not_active Expired - Lifetime
- 1997-10-07 US US08/939,170 patent/US6107266A/en not_active Expired - Lifetime
- 1997-10-08 TW TW086114779A patent/TW418252B/en not_active IP Right Cessation
- 1997-10-08 AR ARP970104657A patent/AR008887A1/en unknown
- 1997-10-08 KR KR1019970051487A patent/KR100507515B1/en not_active IP Right Cessation
- 1997-10-08 HU HU9701617A patent/HUP9701617A3/en unknown
- 1997-10-09 JP JP27750497A patent/JP4897988B2/en not_active Expired - Fee Related
- 1997-10-09 CZ CZ19973198A patent/CZ294306B6/en not_active IP Right Cessation
- 1997-10-09 BR BR9704995A patent/BR9704995A/en not_active Application Discontinuation
- 1997-10-09 PL PL97322521A patent/PL188368B1/en not_active IP Right Cessation
-
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 (en) * | 1980-03-28 | 1981-10-07 | Henkel Kommanditgesellschaft auf Aktien | Process for the preparation of a storage-stable, easily soluble granulated compound containing a bleach activator |
| 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 (en) * | 1993-05-17 | 1994-11-24 | Henkel Kommanditgesellschaft Auf Aktien | Bleaching and disinfecting agent |
| DE4316481A1 (en) * | 1993-05-17 | 1994-11-24 | Henkel Kgaa | Bleach and disinfectant |
| 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 (en) * | 1995-04-13 | 1996-10-16 | The Procter & Gamble Company | Process for making a detergent particle |
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 (en) * | 2009-04-11 | 2010-10-14 | Clariant International Ltd | Bleach granules comprising an active coating |
| EP2640819B1 (en) | 2010-11-19 | 2018-07-04 | Reckitt Benckiser Finish B.V. | Dyed coated bleach materials |
| WO2017102473A1 (en) * | 2015-12-18 | 2017-06-22 | Henkel Ag & Co. Kgaa | Particulate agent for increasing the bleaching effect |
Also Published As
| Publication number | Publication date |
|---|---|
| BR9704995A (en) | 1998-11-03 |
| HUP9701617A2 (en) | 1998-07-28 |
| KR19980032630A (en) | 1998-07-25 |
| JPH10152697A (en) | 1998-06-09 |
| EP0835926A3 (en) | 1999-01-07 |
| AR008887A1 (en) | 2000-02-23 |
| PL322521A1 (en) | 1998-04-14 |
| CZ294306B6 (en) | 2004-11-10 |
| CA2216193C (en) | 2006-07-04 |
| PL188368B1 (en) | 2005-01-31 |
| DE19641708A1 (en) | 1998-04-16 |
| HU9701617D0 (en) | 1997-11-28 |
| KR100507515B1 (en) | 2005-11-14 |
| US6645927B1 (en) | 2003-11-11 |
| CZ319897A3 (en) | 1998-04-15 |
| CA2216193A1 (en) | 1998-04-10 |
| JP4897988B2 (en) | 2012-03-14 |
| DE59712800D1 (en) | 2007-03-15 |
| HUP9701617A3 (en) | 2000-03-28 |
| US6107266A (en) | 2000-08-22 |
| EP0835926B1 (en) | 2007-01-24 |
| US20030207784A1 (en) | 2003-11-06 |
| TW418252B (en) | 2001-01-11 |
| ES2276414T3 (en) | 2007-06-16 |
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