EP0835926B1 - Procédé de production d'un activateur de blanchiment sous forme de granules enrobés - Google Patents
Procédé de production d'un activateur de blanchiment sous forme de granules enrobésInfo
- Publication number
- EP0835926B1 EP0835926B1 EP97116693A EP97116693A EP0835926B1 EP 0835926 B1 EP0835926 B1 EP 0835926B1 EP 97116693 A EP97116693 A EP 97116693A EP 97116693 A EP97116693 A EP 97116693A EP 0835926 B1 EP0835926 B1 EP 0835926B1
- Authority
- EP
- European Patent Office
- Prior art keywords
- coating
- granules
- activator
- coated
- coating substance
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Expired - Lifetime
Links
- 239000008187 granular material Substances 0.000 title claims description 67
- 239000012190 activator Substances 0.000 title claims description 44
- 238000000034 method Methods 0.000 title claims description 28
- 239000007844 bleaching agent Substances 0.000 title claims description 25
- 238000004519 manufacturing process Methods 0.000 title description 2
- 238000000576 coating method Methods 0.000 claims description 86
- 239000011248 coating agent Substances 0.000 claims description 83
- 239000000126 substance Substances 0.000 claims description 43
- 230000008569 process Effects 0.000 claims description 18
- 238000002844 melting Methods 0.000 claims description 15
- 230000008018 melting Effects 0.000 claims description 14
- 229920000642 polymer Polymers 0.000 claims description 9
- 239000000654 additive Substances 0.000 claims description 7
- 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
- 229910052751 metal Inorganic materials 0.000 claims description 3
- 239000002184 metal 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
- 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
- 150000008163 sugars Chemical class 0.000 claims description 2
- 150000008063 acylals Chemical class 0.000 claims 1
- 239000003945 anionic surfactant Substances 0.000 claims 1
- 230000003750 conditioning effect Effects 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
- 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
- 238000010438 heat treatment Methods 0.000 description 15
- 239000003599 detergent Substances 0.000 description 13
- 239000000203 mixture Substances 0.000 description 13
- 238000003860 storage Methods 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 9
- 238000005496 tempering Methods 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
- 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
- 239000002585 base Substances 0.000 description 7
- 238000005469 granulation Methods 0.000 description 7
- 230000003179 granulation Effects 0.000 description 7
- 238000002156 mixing Methods 0.000 description 7
- 102000004190 Enzymes Human genes 0.000 description 6
- 108090000790 Enzymes Proteins 0.000 description 6
- 229920002472 Starch Polymers 0.000 description 6
- 150000003839 salts Chemical class 0.000 description 6
- 235000019698 starch Nutrition 0.000 description 6
- 239000008107 starch Substances 0.000 description 6
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 6
- 238000000137 annealing Methods 0.000 description 5
- 230000000694 effects Effects 0.000 description 5
- 238000009472 formulation Methods 0.000 description 5
- 150000004965 peroxy acids Chemical class 0.000 description 5
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 4
- -1 acyl lactams Chemical class 0.000 description 4
- 150000001735 carboxylic acids Chemical class 0.000 description 4
- 238000006243 chemical reaction Methods 0.000 description 4
- 230000000052 comparative effect Effects 0.000 description 4
- 239000000463 material Substances 0.000 description 4
- 239000000155 melt Substances 0.000 description 4
- 230000008092 positive effect Effects 0.000 description 4
- 238000005204 segregation Methods 0.000 description 4
- 238000005406 washing Methods 0.000 description 4
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 3
- 229920003086 cellulose ether Polymers 0.000 description 3
- 239000012943 hotmelt Substances 0.000 description 3
- 230000006872 improvement Effects 0.000 description 3
- 239000004615 ingredient Substances 0.000 description 3
- 239000010410 layer Substances 0.000 description 3
- 239000002245 particle Substances 0.000 description 3
- NLKNQRATVPKPDG-UHFFFAOYSA-M potassium iodide Chemical compound [K+].[I-] NLKNQRATVPKPDG-UHFFFAOYSA-M 0.000 description 3
- 150000004760 silicates Chemical class 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
- 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
- 238000007792 addition Methods 0.000 description 2
- 150000008051 alkyl sulfates Chemical class 0.000 description 2
- 125000000129 anionic group Chemical group 0.000 description 2
- 230000008901 benefit Effects 0.000 description 2
- 239000011230 binding agent Substances 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
- 150000001732 carboxylic acid derivatives Chemical class 0.000 description 2
- 239000003054 catalyst Substances 0.000 description 2
- 239000007795 chemical reaction product Substances 0.000 description 2
- 239000007931 coated granule Substances 0.000 description 2
- 150000001875 compounds Chemical class 0.000 description 2
- 230000003247 decreasing effect Effects 0.000 description 2
- 238000004851 dishwashing 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
- 239000003814 drug Substances 0.000 description 2
- 229940079593 drug Drugs 0.000 description 2
- 150000002148 esters Chemical class 0.000 description 2
- 150000002170 ethers Chemical class 0.000 description 2
- 238000002474 experimental method Methods 0.000 description 2
- 239000012530 fluid 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
- 239000000843 powder Substances 0.000 description 2
- 238000002360 preparation method Methods 0.000 description 2
- 238000007712 rapid solidification Methods 0.000 description 2
- 230000009257 reactivity Effects 0.000 description 2
- 230000009467 reduction Effects 0.000 description 2
- 238000000926 separation method Methods 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
- 238000012360 testing method Methods 0.000 description 2
- XSVSPKKXQGNHMD-UHFFFAOYSA-N 5-bromo-3-methyl-1,2-thiazole Chemical compound CC=1C=C(Br)SN=1 XSVSPKKXQGNHMD-UHFFFAOYSA-N 0.000 description 1
- LSNNMFCWUKXFEE-UHFFFAOYSA-M Bisulfite Chemical compound OS([O-])=O LSNNMFCWUKXFEE-UHFFFAOYSA-M 0.000 description 1
- 239000004215 Carbon black (E152) Substances 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
- 230000003213 activating effect Effects 0.000 description 1
- 239000004480 active ingredient Substances 0.000 description 1
- 239000013543 active substance Substances 0.000 description 1
- 125000002252 acyl group Chemical class 0.000 description 1
- 230000000996 additive effect Effects 0.000 description 1
- 239000002671 adjuvant Substances 0.000 description 1
- 150000001447 alkali salts Chemical class 0.000 description 1
- QGZKDVFQNNGYKY-UHFFFAOYSA-O ammonium group Chemical group [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 description 1
- 238000013459 approach Methods 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
- 239000004202 carbamide Substances 0.000 description 1
- 125000004432 carbon atom Chemical group C* 0.000 description 1
- 230000015556 catabolic process Effects 0.000 description 1
- 229920002678 cellulose Polymers 0.000 description 1
- 239000001913 cellulose Substances 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 239000012459 cleaning agent Substances 0.000 description 1
- 238000005056 compaction Methods 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 229920001577 copolymer Polymers 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
- 230000001419 dependent effect Effects 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 238000004090 dissolution Methods 0.000 description 1
- 238000007908 dry granulation Methods 0.000 description 1
- 239000000975 dye Substances 0.000 description 1
- 239000004744 fabric Substances 0.000 description 1
- 238000011049 filling Methods 0.000 description 1
- 230000009969 flowable effect Effects 0.000 description 1
- 229920000578 graft copolymer Polymers 0.000 description 1
- 239000008240 homogeneous mixture Substances 0.000 description 1
- 230000036571 hydration Effects 0.000 description 1
- 238000006703 hydration reaction Methods 0.000 description 1
- 229930195733 hydrocarbon Natural products 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
- 230000014759 maintenance of location Effects 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
- 239000008188 pellet Substances 0.000 description 1
- 239000002304 perfume Substances 0.000 description 1
- 235000019271 petrolatum Nutrition 0.000 description 1
- 239000000546 pharmaceutical excipient Substances 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
- QQONPFPTGQHPMA-UHFFFAOYSA-N propylene Natural products CC=C QQONPFPTGQHPMA-UHFFFAOYSA-N 0.000 description 1
- 239000011241 protective layer Substances 0.000 description 1
- 230000000630 rising effect Effects 0.000 description 1
- 238000012216 screening Methods 0.000 description 1
- RMAQACBXLXPBSY-UHFFFAOYSA-N silicic acid Chemical compound O[Si](O)(O)O RMAQACBXLXPBSY-UHFFFAOYSA-N 0.000 description 1
- 235000012239 silicon dioxide Nutrition 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
- 238000001694 spray drying Methods 0.000 description 1
- 238000005507 spraying 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
- 238000004448 titration Methods 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 ingredients in detergents, stain salts and machine dishwashing detergents. They allow a bleaching effect even at relatively low temperatures by reacting with hydrogen peroxide - usually perborates or percarbonates - to release an organic peroxycarboxylic acid.
- the achievable bleaching result is determined by the nature and reactivity of the peroxycarboxylic acid formed, the structure of the bond to be perhydrolized and the water solubility of the bleach activator. Since it is usually a reactive ester or an amide, it is necessary in many cases to use it for the intended application in granulated form to prevent hydrolysis in the presence of alkaline detergent ingredients and to ensure a sufficient shelf life.
- EP-A-0 037 026 describes a process for preparing a readily soluble activator granulate from 90 to 98% activator with 10 to 2% cellulose ether, starch or starch ether.
- Granules consisting of bleach activator, film-forming polymers and additions of an organic C 3 -C 6 -carboxylic, hydroxycarboxylic or etheric carboxylic acid are mentioned 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 the preparation of an activator granules by mixing a dry bleach activator with a dry, inorganic binder material containing water of hydration, compressing this mixture into larger agglomerates and comminuting these agglomerates onto the catalyst desired grain size.
- An anhydrous preparation process by compaction of the bleach activator without the use of water with at least one water-swellable excipient is known from EP-A-0 075 818.
- a disadvantage of these Aktivatorgranulaten is that the properties of the granules are essentially determined by the binder and the granulation method used and often in addition to the advantages described in the literature also some disadvantages, e.g. not optimal release of active ingredient, low abrasion resistance, high dust content, insufficient storage stability, segregation in the powder or color damage of the fabric when used in detergents and cleaners.
- a coating step is often carried out subsequently to the granulation step.
- Common methods are coating in mixers (mechanically induced fluidized bed) or enveloping in fluidized bed apparatus (pneumatically induced fluidized bed).
- WO-92/13798 describes a coating for a bleach activator with a water-soluble organic acid melting above 30 ° C. and in WO-94/03305 a coating with a water-soluble acidic polymer for reducing the color damage of the laundry.
- WO-94/26862 discloses the coating of a granulate consisting of bleach activator and water- and / or alkali-soluble polymer with an organic compound which melts between 30.degree. C. and 100.degree. C. to reduce segregation in the powdery end product.
- the activator granules are placed in a Lödige ploughshare mixer, circulated at room temperature at 160 to 180 rpm without using the chopper and then sprayed with the hot melt.
- Disadvantage of this method is a very poor coating quality, which indeed causes a reduction of segregation in the powdery end product, but has no effect on the other granule properties, such as drug release, abrasion resistance, dust content or storage stability.
- the positive effect on the segregation behavior is probably on attributable droplet-shaped solidification of the coating substance on the granule surface, whereby a hooking of the granules in the bulk material is effected.
- Object of the present invention was the development of a coating process for activator granules, which allows a targeted adjustment of the granular properties in a wide range with simultaneous optimal utilization of the coating material.
- the invention thus provides a process for producing a coated bleach activator granules, wherein a bleach activator granules in a mechanically induced fluidized bed coated with a coating substance and simultaneously at 30 to 100 ° C, but equal to or below the melting or softening temperature of the coating substance, during a period from 1 to 180 minutes, tempered.
- activators As base granules all activators can be used which have a melting point of above 100 ° C in granulated form.
- activator substances are tetraacetylethylenediamine (TAED), tetraacetylglucoluril (TAGU), diacetyldioxohexahydrotriazine (DADHT), acyloxybenzenesulphonates (eg nonanyloxybenzenesulphonate [NOBS], benzoyloxibenzenesulphonate [BOBS]), acylated sugars (eg: pentaacetylglucose [PAG]) or compounds as described in EP Pat.
- activators are N-acylated amines, amides, lactams, activated carboxylic acid esters, carboxylic anhydrides, lactones, acyls, carboxylic acid amides, acyl lactams, acylated ureas and oxamides, in addition, however, in particular also nitriles, which may also contain a quaternized ammonium group in addition to the nitrile group. Also, mixtures of different bleach activators may be present in the base granules.
- These base granules may contain the usual granulation aids, which should have a melting point of about 100 ° C.
- these granulation aids can be used as
- the bleach activator base granules may contain other additives that improve properties such as storage stability and bleach activating ability.
- additives include inorganic acids, organic acids such as mono- or polybasic carboxylic acids, hydroxycarboxylic acids and / or ether carboxylic acids and their salts, complexing agents, metal complexes and ketones.
- the abovementioned additives can be used as individual substances or as mixtures.
- These base granules are prepared by mixing the dry bleach activator with the dry granulation aid, compressing this mixture to form larger agglomerates and comminuting these agglomerates to the desired particle size.
- the ratio of bleach activator to granulation aid is usually 50:50 to 98: 2, preferably 70:30 to 96: 4 wt .-%.
- the amount of the additive depends in particular on its nature.
- acidifying additives and organic catalysts to increase the performance of the peracid in amounts of 0 to 20 wt .-%, in particular in amounts of 1 to 10 wt .-%, based on the total weight, added, metal complexes in concentrations in the ppm range.
- further substances which do not soften or melt in this temperature range can be present in dissolved or suspended form, for example polymers (for example homo-, co- or propylene copolymers of unsaturated carboxylic acids and / or Sulfonic acids and their alkali salts, cellulose ethers, starch, starch ethers, polyvinylpyrrolidone); Organic substances (for example mono- or polybasic carboxylic acids, hydroxycarboxylic acids or ether carboxylic acids having 3 to 8 carbon atoms and salts thereof); dyes; Inorganic substances (for example: silicates, carbonates, bicarbonates, sulfates, phosphates, phosphonates).
- polymers for example homo-, co- or propylene copolymers of unsaturated carboxylic acids and / or Sulfonic acids and their alkali salts, cellulose ethers, starch, starch ethers, polyvinylpyrrolidone
- Organic substances for example mono- or polybasic
- the content of coating substance may be from 1 to 30% by weight, preferably from 5 to 15% by weight, based on coated activator granules.
- mixers mechanically induced fluidized bed
- mixers for example, plowshare mixers (continuous and batchwise), ring layer mixers or even Schugi mixers are possible.
- the heat treatment takes place directly in the mixer.
- Granulated coolers or fluid bed coolers can be used to cool the coated granules.
- the coating substance can be sprayed on via a single-substance or a two-component nozzle device.
- the heat treatment consists in 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. Preference is given to working at a temperature which is just below the melting or softening temperature.
- the particle 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 the heat treatment or the temperature difference to the melting point of the coating substance is dependent on the coating quantity, the annealing time and the properties desired for the coated bleach activator granules and must be determined for the respective system in preliminary experiments.
- the duration of the heat treatment is 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 the liquid coating agent does not solidify too quickly and thereby has the opportunity to run as a thin film on the granule surface. This achieves a very uniform coating of the grain in a thin layer with the coating substance and an optimum coating effect when using a minimal amount of coating substance.
- conventional methods ie without annealing step, occurs too rapid solidification of the individual droplets on the cold granule surface.
- the surface is occupied only with fine single droplets and still has large coating defects.
- the desired coating effect is thereby achieved only insufficient or a significantly higher amount of coating substance is required to achieve a desired coating effect.
- the latter reduces the content of activator substance, which is often undesirable.
- the properties of the activator granules can be optimized in a targeted manner to the desired requirements by suitably selecting the coating substance, the coating quantity and the temperature control of the process. Above all, the targeted optimization of the following Aktivatorgranulateigenschaften is possible.
- a delayed reaction with a slight delay in time and release of active substance from the bleaching system with simultaneous rapid enzyme action is advantageous.
- the enzymes can fully develop their washing power in the first few minutes of the washing process without being damaged by the bleaching system. Only after the enzymes have done their work is then initiated by reaction of the bleach activator with the hydrogen peroxide source, the bleaching process.
- the reactivity i. the dissolution rate or the rate of peracid formation can be tailored to the enzyme system. In the method, a targeted adjustment of the peracid formation rate with a minimum amount of coating substance and therefore maximum activator content is possible.
- the abrasion resistance of an activator granulate By coating a granulate with softening or melting substances, the abrasion resistance of an activator granulate can be increased become.
- the higher the abrasion resistance the greater the better the granulate surface is coated with the coating substance.
- optimum coating of the coating substance on the granule surface and thus optimum improvement of the abrasion resistance can be effected with a minimum amount of coating.
- the granules obtained in this way are directly suitable for use in detergents and cleaners. They are ideal for use in heavy-duty detergents, stain salts, machine dishwashing detergents, powdered all-purpose cleaners and denture cleaners.
- the granules of the invention are usually used in combination with a source of hydrogen peroxide. Examples include perborate monohydrate, perborate tetrahydrate, percarbonates and hydrogen peroxide adducts of urea or amine oxides.
- the formulation according to the prior art may comprise further detergent ingredients, such as organic or inorganic builders and co-builders, surfactants, enzymes, laundry additives, optical brighteners and perfume.
- TAED 4303 (Hoechst AG) was continuously metered at a throughput of 480 kg / h into a Schugi mixer (Flexomix 160, Hosokawa Schugi) and sprayed with a 75 ° C. hot melt of myristic acid.
- the coated material fell directly into a downstream fluidized bed (Hosokawa Schugi) and was tempered there in a first chamber for 5 to 10 minutes at fluidized bed temperatures of about 54 ° C and then in a second chamber at fluidized bed temperatures of about 35 Cooled ° C.
- TAED 4303 was continuously metered into the Schugi mixer with a throughput of 480 kg / h, sprayed with a 75 ° C hot melt of myristic acid and then directly in the downstream fluidized bed at fluidized bed temperatures of about 35 Cooled ° C.
- the coating quality of the products was assessed by determining the rate of peracetic acid formation at a temperature of 20 ° C. The slower the peracetic acid formation, the better the degree of coating achieved.
- the coating quality expressed by the delay in peracetic acid formation, can be markedly improved with the same amount of coating (comparison of products 3 and 4).
- Example 2 Coating after the fluidized-bed process with subsequent tempering (not according to the invention)
- 500-600 g of TAED 4303 were introduced into the fluidized bed (fluidized-bed apparatus Strea 1, from Aeromatic) and sprayed with a melt of stearic acid at a temperature of about 80 ° C.
- the fluidized bed was operated at low temperatures and after completion of spraying again after-cooled for about 5 minutes (prior art).
- the coated granules were again introduced into the fluidized bed and tempered by the novel process.
- the fluidized bed was gradually heated to temperatures of about 65 to 70 ° C and this product temperature for about 5 to 8 min. kept constant. Subsequently, the tempered product was gradually cooled again.
- the coating quality expressed by the delay in peracetic acid formation, can be significantly improved for the same amount of coating (comparison of products 6 and 8 or products 7 and 9).
- tempering The influence of tempering on the coating quality is also reflected in the storage stability of TAED granules in detergent formulations.
- the storage stability was tested in prefabricated cartons (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 carton 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 Tesafilm. All samples were mixed and bottled the same day.
- the filled and labeled cartons were then placed in the climatic cabinet at a sufficient distance from each other and stored at 38 ° C / 80% RH.
- the samples were removed from the climatic chamber, the entire sample at 20 ° C in 1 l of distilled water while stirring with a magnetic stirrer (250 to 280 rev / min) registered and 1 g of sodium percarbonate added.
- the further determination of the amount of peracetic acid formed was carried out analogously to the information in Example 1. From the maximum value of peracetic acid found then the TAED content of the sample was calculated.
- the TAED maintenance level represents the percentage TAED content of the sample after storage based on the TAED content of the un-stored sample. Table 3: Storage stability in detergent formulations of TAED granules coated by fluidized bed with subsequent heat treatment Product no.
- TAED granules TAED retention after storage [%] 0d 3d 6d 9d 15d 23d 28d 5
- Basic granulate (BG) 100 24 14 12 10 9 8th 6 BG + 10% stearic acid, annealed 100 88 61 56 47 45 45 8th BG + 10% stearic acid, unannealed 100 52 24 20 18 16 15
- TAED 4303 was continuously metered via a flexible metering screw at 40 kg / h into the fluidized bed apparatus (technical fluidized bed apparatus) and coated with 20% myristic acid.
- the residence time in the fluidized bed was about 30 minutes.
- the product discharged through a rotary valve was transported by means of a metering screw to a screening machine, on which the coarse fraction of greater than 1.0 mm and the fine fraction of less than 0.2 mm were separated.
- the coarse fraction was then comminuted in a mill and then returned together with the fine fraction via a flexible metering screw in the fluidized bed apparatus.
- the fluidized bed temperature was increased from initially 46 ° C to finally 54 ° C.
- TAED granules T fluid bed [° C] Peracetic acid [%] dust content 5 min 10 min 20 min [%] 11 Basic granulate (BG) - 75 95 100 - 12 BG + 20% myristic acid 46 66 81 94 30 13 BG + 20% myristic acid 49 48 68 87 15 14 BG + 20% myristic acid 52 38 60 86 10 15 BG + 20% myristic acid 54 20 36 62 5
- the coating quality as expressed by the retardation of peracid formation, increases significantly and a better dedusting and higher abrasion resistance, expressed by the decreasing dust content ⁇ 0.2 mm of the coated granulate.
- Example 4 Coating in the ploughshare mixer with simultaneous tempering
- 1.2 kg of TAED granules according to EP-A-0 037 026 were initially charged in a batch ploughshare mixer (M5R, Lödige) and mixed with a mixing speed of about 150 rpm with 210 g of an 80 ° C hot stearic acid melt sprayed.
- the contents of the mixer were heated to a temperature of 50 ° C. during the coating step by means of a heating jacket.
- the coating and annealing time was about 10 minutes.
- 1.2 kg of TAED granules according to EP-A-0 037 026 were initially charged in a batch ploughshare mixer and mixed at room temperature with mixing at a speed of the mixing tools of about 150 rev / min with 210 g an 80 ° C hot stearic acid melt sprayed.
- Example 5 Coating in the ploughshare mixer with simultaneous tempering
- TAED 4303 was continuously metered into the ploughshare mixer (KT-160, Drais company) at throughput rates of 100 to 300 kg / h.
- the mixer contents were heated to a temperature in the range of 44 to 52 ° C via a heating mantle.
- 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 was injected (closer to the product entry).
- the coating amount was 7%.
- the mixer was operated at a speed of the mixing tools of 90 rpm and without the use of chopper blades.
- the degree of filling in the mixer was adjusted so that the product just covered the mixing shaft.
- the coated material was continuously withdrawn from the mixer and passed directly through a sieve (0.2 to 1.0 mm) to separate fine and coarse fractions.
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- Chemical & Material Sciences (AREA)
- Life Sciences & Earth Sciences (AREA)
- Engineering & Computer Science (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Oil, Petroleum & Natural Gas (AREA)
- Wood Science & Technology (AREA)
- Organic Chemistry (AREA)
- Inorganic Chemistry (AREA)
- Detergent Compositions (AREA)
Claims (9)
- Procédé de production d'un activateur de blanchiment sous forme de granulés enrobés, caractérisé en ce que l'on enrobe un granulé d'activateur de blanchiment avec une substance de revêtement dans un lit fluidisé mécaniquement induit et en ce qu'on étuve en même temps de 30 à 100 °C, cependant à une température égale ou inférieure à la température de fusion ou de ramollissement de la substance de revêtement, pendant une durée de 1 à 180 minutes.
- Procédé selon la revendication 1, caractérisé en ce que le granulé de base de l'activateur présente un point de fusion de plus de.100 °C.
- Procédé selon la revendication 1 ou 2, caractérisé en ce que la substance de revêtement a un point de ramollissement ou de fusion dans la plage de 30 à 100 °C.
- Procédé selon une ou plusieurs des revendications 1 à 3, caractérisé en ce qu'on utilise comme activateurs de blanchiment des amines N-acylées, des amides, des lactames, des acyloxybenzène-sulfonates, des sucres acylés, des carboxylates activés, des anhydrides d'acide carboxylique, des lactones, des acylals, des oxamides et/ou des nitriles, qui peuvent contenir un groupe ammonium quaternaire.
- Procédé selon une ou plusieurs des revendications 1 à 4, caractérisé en ce qu'on utilise comme substances de revêtement des acides gras, des alcools gras, des polyalkylèneglycols, des agents tensio-actifs non ioniques, des agents tensio-actifs anioniques, des polymères, des cires et/ou des silicones.
- Procédé selon une ou plusieurs des revendications 1 à 5, caractérisé en ce que la substance de revêtement contient des polymères, des substances organiques et/ou des substances inorganiques sous forme dissoute ou en suspension.
- Procédé selon une ou plusieurs des revendications 1 à 6, caractérisé en ce que la teneur en substance de revêtement est de 1 à 30 % en poids, de préférence de 5 à 15 % en poids, par rapport au granulé d'activateur revêtu.
- Procédé selon une ou plusieurs des revendications 1 à 7, caractérisé en ce que la taille de grains du granulé d'activateur de blanchiment revêtu est de 0,1 à 2,0 mm, de préférence de 0,2 à 1,0 mm et de manière particulièrement préférée de 0,3 à 0,8 mm.
- Procédé selon une ou plusieurs des revendications 1 à 8, caractérisé en ce que le granulé d'activateur contient jusqu'à 20 % en poids, par rapport au poids du granulé de base de l'activateur, d'un ou de plusieurs additifs choisis dans le groupe constitué des acides inorganiques, des acides organiques, des agents complexants, des cétones et des complexes des métaux.
Applications Claiming Priority (2)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
DE19641708 | 1996-10-10 | ||
DE19641708A DE19641708A1 (de) | 1996-10-10 | 1996-10-10 | Verfahren zur Herstellung eines gecoateten Bleichaktivatorgranulats |
Publications (3)
Publication Number | Publication Date |
---|---|
EP0835926A2 EP0835926A2 (fr) | 1998-04-15 |
EP0835926A3 EP0835926A3 (fr) | 1999-01-07 |
EP0835926B1 true EP0835926B1 (fr) | 2007-01-24 |
Family
ID=7808324
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
EP97116693A Expired - Lifetime EP0835926B1 (fr) | 1996-10-10 | 1997-09-25 | Procédé de production d'un activateur de blanchiment sous forme de granules enrobés |
Country Status (13)
Country | Link |
---|---|
US (3) | US6107266A (fr) |
EP (1) | EP0835926B1 (fr) |
JP (1) | JP4897988B2 (fr) |
KR (1) | KR100507515B1 (fr) |
AR (1) | AR008887A1 (fr) |
BR (1) | BR9704995A (fr) |
CA (1) | CA2216193C (fr) |
CZ (1) | CZ294306B6 (fr) |
DE (2) | DE19641708A1 (fr) |
ES (1) | ES2276414T3 (fr) |
HU (1) | HUP9701617A3 (fr) |
PL (1) | PL188368B1 (fr) |
TW (1) | TW418252B (fr) |
Families Citing this family (30)
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DE19641708A1 (de) * | 1996-10-10 | 1998-04-16 | Clariant Gmbh | Verfahren zur Herstellung eines gecoateten Bleichaktivatorgranulats |
DE10038832A1 (de) * | 2000-08-04 | 2002-03-28 | Henkel Kgaa | Umhüllte Bleichaktivatoren |
DE10057045A1 (de) | 2000-11-17 | 2002-05-23 | Clariant Gmbh | Teilchenförmige Bleichaktivatoren auf der Basis von Acetonitrilen |
DE10161766A1 (de) * | 2001-12-15 | 2003-06-26 | Clariant Gmbh | Bleichaktivator-Co-Granulate |
DE10304131A1 (de) | 2003-02-03 | 2004-08-05 | Clariant Gmbh | Verwendung von Übergangsmetallkomplexen als Bleichkatalysatoren |
DE10334046A1 (de) * | 2003-07-25 | 2005-02-10 | Clariant Gmbh | Verfahren zur Herstellung von granulierten Acyloxybenzolsulfonaten oder Acyloxybenzolcarbonsäuren und deren Salze |
DE102004012568A1 (de) * | 2004-03-12 | 2005-12-08 | Henkel Kgaa | Bleichaktivatoren und Verfahren zu ihrer Herstellung |
DE102004012915A1 (de) * | 2004-03-17 | 2005-10-13 | Clariant Gmbh | Feste Zubereitungen enthaltend einen sensitiven Wirkstoff |
EP2013325B1 (fr) * | 2006-04-04 | 2012-06-13 | Basf Se | Systeme de blanchiment enrobe d'une couche polymere |
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 |
DE102009017722A1 (de) * | 2009-04-11 | 2010-10-14 | Clariant International Limited | Bleichmittelgranulate mit Aktivcoating |
GB0918914D0 (en) | 2009-10-28 | 2009-12-16 | Revolymer Ltd | Composite |
DE102009057222A1 (de) * | 2009-12-05 | 2011-06-09 | Clariant International Ltd. | Bleichkatalysator-Compounds, Verfahren zu ihrer Herstellung und ihre Verwendung |
DE102010028236A1 (de) * | 2010-04-27 | 2011-10-27 | Evonik Degussa Gmbh | Bleichmittelpartikel umfassend Natriumpercarbonat und einen Bleichaktivator |
GB201019628D0 (en) | 2010-11-19 | 2010-12-29 | Reckitt Benckiser Nv | Dyed coated bleach materials |
GB201106377D0 (en) | 2011-04-15 | 2011-06-01 | Reckitt & Colman Overseas | Novel composite |
GB201106408D0 (en) | 2011-04-15 | 2011-06-01 | Revolymer Ltd | Novel composite |
GB201106391D0 (en) | 2011-04-15 | 2011-06-01 | Reckitt & Colman Overseas | Novel composite |
GB201106409D0 (en) | 2011-04-15 | 2011-06-01 | Revolymer Ltd | Novel composite |
US8728454B1 (en) | 2012-10-30 | 2014-05-20 | The Clorox Company | Cationic micelles with anionic polymeric counterions compositions thereof |
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 |
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 |
TR201807228T4 (tr) * | 2014-05-09 | 2018-06-21 | Basf Se | Çamaşır deterjanlarında kullanım için iki katlı kaplamaya sahip asilhidrazon granülat. |
DE102015225882A1 (de) * | 2015-12-18 | 2017-06-22 | Henkel Ag & Co. Kgaa | Partikuläres Mittel zur Verstärkung der Bleichwirkung |
MX2018012291A (es) * | 2016-04-08 | 2019-08-05 | Battelle Memorial Institute | Composiciones de encapsulacion. |
US10053653B2 (en) | 2016-10-18 | 2018-08-21 | Sterilex, Llc | Ambient moisture-activated hard surface treatment powder |
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US5200236A (en) * | 1989-11-15 | 1993-04-06 | Lever Brothers Company, Division Of Conopco, Inc. | Method for wax encapsulating particles |
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DE3011998C2 (de) * | 1980-03-28 | 1982-06-16 | Henkel KGaA, 4000 Düsseldorf | Verfahren zur Herstellung eines lagerstabilen, leichtlöslichen Granulates mit einem Gehalt an Bleichaktivatoren |
EP0053859B1 (fr) * | 1980-12-09 | 1985-04-03 | Unilever N.V. | Granules d'activateur de blanchiment |
DE3128336A1 (de) * | 1981-07-17 | 1983-01-27 | Henkel KGaA, 4000 Düsseldorf | "verfahren zur herstellung umhuellter koerniger bleichaktivatoren" |
DE3268039D1 (en) * | 1981-09-28 | 1986-01-30 | Basf Ag | Granular bleach activator |
US4486327A (en) * | 1983-12-22 | 1984-12-04 | The Procter & Gamble Company | Bodies containing stabilized bleach activators |
US4678594A (en) * | 1985-07-19 | 1987-07-07 | Colgate-Palmolive Company | Method of encapsulating a bleach and activator therefor in a binder |
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US4889651A (en) * | 1988-01-21 | 1989-12-26 | Colgate-Palmolive Company | Acetylated sugar ethers as bleach activators and detergency boosters |
DE3826092A1 (de) * | 1988-08-01 | 1990-02-08 | Henkel Kgaa | Granulares, bleichaktivatoren enthaltendes bleichhilfsmittel mit verbesserten eigenschaften |
DE3843195A1 (de) * | 1988-12-22 | 1990-06-28 | Hoechst Ag | Verfahren zur herstellung eines lagerstabilen, leicht loeslichen bleichaktivator-granulats |
GB8925621D0 (en) * | 1989-11-13 | 1990-01-04 | Unilever Plc | Process for preparing particulate detergent additive bodies and use thereof in detergent compositions |
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US5534196A (en) * | 1993-12-23 | 1996-07-09 | The Procter & Gamble Co. | Process for making lactam bleach activator containing particles |
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DE4439039A1 (de) * | 1994-11-02 | 1996-05-09 | Hoechst Ag | Granulierte Bleichaktivatoren und ihre Herstellung |
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-
1996
- 1996-10-10 DE DE19641708A patent/DE19641708A1/de not_active Withdrawn
-
1997
- 1997-09-22 CA CA002216193A patent/CA2216193C/fr not_active Expired - Fee Related
- 1997-09-25 DE DE59712800T patent/DE59712800D1/de not_active Expired - Lifetime
- 1997-09-25 EP EP97116693A patent/EP0835926B1/fr not_active Expired - Lifetime
- 1997-09-25 ES ES97116693T patent/ES2276414T3/es not_active Expired - Lifetime
- 1997-10-07 US US08/939,170 patent/US6107266A/en not_active Expired - Lifetime
- 1997-10-08 KR KR1019970051487A patent/KR100507515B1/ko not_active IP Right Cessation
- 1997-10-08 TW TW086114779A patent/TW418252B/zh not_active IP Right Cessation
- 1997-10-08 HU HU9701617A patent/HUP9701617A3/hu unknown
- 1997-10-08 AR ARP970104657A patent/AR008887A1/es unknown
- 1997-10-09 JP JP27750497A patent/JP4897988B2/ja not_active Expired - Fee Related
- 1997-10-09 BR BR9704995A patent/BR9704995A/pt not_active Application Discontinuation
- 1997-10-09 PL PL97322521A patent/PL188368B1/pl not_active IP Right Cessation
- 1997-10-09 CZ CZ19973198A patent/CZ294306B6/cs 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 (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US5200236A (en) * | 1989-11-15 | 1993-04-06 | Lever Brothers Company, Division Of Conopco, Inc. | Method for wax encapsulating particles |
Also Published As
Publication number | Publication date |
---|---|
PL322521A1 (en) | 1998-04-14 |
US6645927B1 (en) | 2003-11-11 |
TW418252B (en) | 2001-01-11 |
HUP9701617A2 (hu) | 1998-07-28 |
JP4897988B2 (ja) | 2012-03-14 |
CZ319897A3 (cs) | 1998-04-15 |
PL188368B1 (pl) | 2005-01-31 |
DE19641708A1 (de) | 1998-04-16 |
CA2216193A1 (fr) | 1998-04-10 |
BR9704995A (pt) | 1998-11-03 |
US20030207784A1 (en) | 2003-11-06 |
CZ294306B6 (cs) | 2004-11-10 |
US6107266A (en) | 2000-08-22 |
AR008887A1 (es) | 2000-02-23 |
CA2216193C (fr) | 2006-07-04 |
KR19980032630A (ko) | 1998-07-25 |
HU9701617D0 (en) | 1997-11-28 |
EP0835926A2 (fr) | 1998-04-15 |
EP0835926A3 (fr) | 1999-01-07 |
ES2276414T3 (es) | 2007-06-16 |
DE59712800D1 (de) | 2007-03-15 |
HUP9701617A3 (en) | 2000-03-28 |
KR100507515B1 (ko) | 2005-11-14 |
JPH10152697A (ja) | 1998-06-09 |
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