CA2216193C - Process for producing coated bleach activator granules - Google Patents
Process for producing coated bleach activator granules Download PDFInfo
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- CA2216193C CA2216193C CA002216193A CA2216193A CA2216193C CA 2216193 C CA2216193 C CA 2216193C CA 002216193 A CA002216193 A CA 002216193A CA 2216193 A CA2216193 A CA 2216193A CA 2216193 C CA2216193 C CA 2216193C
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- Prior art keywords
- granules
- coating
- 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.)
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- 239000008187 granular material Substances 0.000 title claims abstract description 78
- 239000012190 activator Substances 0.000 title claims abstract description 53
- 238000000034 method Methods 0.000 title claims abstract description 41
- 230000008569 process Effects 0.000 title claims abstract description 30
- 239000007844 bleaching agent Substances 0.000 title claims abstract description 28
- 238000000576 coating method Methods 0.000 claims abstract description 91
- 239000011248 coating agent Substances 0.000 claims abstract description 87
- 239000000126 substance Substances 0.000 claims abstract description 44
- 230000003750 conditioning effect Effects 0.000 claims description 32
- 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
- 150000002191 fatty alcohols 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
- 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
- 150000004665 fatty acids Chemical class 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
- 235000005985 organic acids Nutrition 0.000 claims description 2
- 229920001515 polyalkylene glycol Polymers 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
- 239000003945 anionic surfactant Substances 0.000 claims 1
- 150000002825 nitriles Chemical class 0.000 claims 1
- 239000002736 nonionic surfactant Substances 0.000 claims 1
- 125000001453 quaternary ammonium group Chemical group 0.000 claims 1
- 230000001143 conditioned effect Effects 0.000 abstract description 17
- KFSLWBXXFJQRDL-UHFFFAOYSA-N Peracetic acid Chemical compound CC(=O)OO KFSLWBXXFJQRDL-UHFFFAOYSA-N 0.000 description 53
- 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 26
- 230000015572 biosynthetic process Effects 0.000 description 22
- 239000000203 mixture Substances 0.000 description 15
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 description 12
- 239000002253 acid Substances 0.000 description 12
- 239000002585 base Substances 0.000 description 12
- 239000003599 detergent Substances 0.000 description 12
- 235000021355 Stearic acid Nutrition 0.000 description 11
- QIQXTHQIDYTFRH-UHFFFAOYSA-N octadecanoic acid Chemical compound CCCCCCCCCCCCCCCCCC(O)=O QIQXTHQIDYTFRH-UHFFFAOYSA-N 0.000 description 11
- OQCDKBAXFALNLD-UHFFFAOYSA-N octadecanoic acid Natural products CCCCCCCC(C)CCCCCCCCC(O)=O OQCDKBAXFALNLD-UHFFFAOYSA-N 0.000 description 11
- 239000008117 stearic acid Substances 0.000 description 11
- 238000004061 bleaching Methods 0.000 description 10
- 239000000428 dust Substances 0.000 description 9
- 238000005299 abrasion Methods 0.000 description 8
- 239000000463 material Substances 0.000 description 8
- 102000004190 Enzymes Human genes 0.000 description 6
- 108090000790 Enzymes Proteins 0.000 description 6
- 229920002472 Starch Polymers 0.000 description 6
- -1 ether carboxylic acid Chemical class 0.000 description 6
- 238000002156 mixing Methods 0.000 description 6
- 150000003839 salts Chemical class 0.000 description 6
- 238000000926 separation method Methods 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
- 150000004965 peroxy acids Chemical class 0.000 description 5
- TWJNQYPJQDRXPH-UHFFFAOYSA-N 2-cyanobenzohydrazide Chemical compound NNC(=O)C1=CC=CC=C1C#N TWJNQYPJQDRXPH-UHFFFAOYSA-N 0.000 description 4
- 235000021360 Myristic acid Nutrition 0.000 description 4
- TUNFSRHWOTWDNC-UHFFFAOYSA-N Myristic acid Natural products CCCCCCCCCCCCCC(O)=O TUNFSRHWOTWDNC-UHFFFAOYSA-N 0.000 description 4
- 239000011230 binding agent Substances 0.000 description 4
- 150000001735 carboxylic acids Chemical class 0.000 description 4
- 238000006243 chemical reaction Methods 0.000 description 4
- 230000000694 effects Effects 0.000 description 4
- 238000009472 formulation Methods 0.000 description 4
- 230000006872 improvement Effects 0.000 description 4
- 238000003860 storage Methods 0.000 description 4
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 3
- 239000013543 active substance Substances 0.000 description 3
- 229920003086 cellulose ether Polymers 0.000 description 3
- 239000003795 chemical substances by application Substances 0.000 description 3
- 239000011538 cleaning material Substances 0.000 description 3
- 239000007931 coated granule Substances 0.000 description 3
- RTZKZFJDLAIYFH-UHFFFAOYSA-N ether Substances CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 3
- 150000002170 ethers Chemical class 0.000 description 3
- 238000010438 heat treatment Methods 0.000 description 3
- 239000004615 ingredient Substances 0.000 description 3
- 239000000155 melt Substances 0.000 description 3
- 230000008092 positive effect Effects 0.000 description 3
- NLKNQRATVPKPDG-UHFFFAOYSA-M potassium iodide Chemical compound [K+].[I-] NLKNQRATVPKPDG-UHFFFAOYSA-M 0.000 description 3
- 238000007711 solidification Methods 0.000 description 3
- 230000008023 solidification Effects 0.000 description 3
- TUNFSRHWOTWDNC-HKGQFRNVSA-N tetradecanoic acid Chemical compound CCCCCCCCCCCCC[14C](O)=O TUNFSRHWOTWDNC-HKGQFRNVSA-N 0.000 description 3
- 238000005406 washing Methods 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
- 230000009471 action Effects 0.000 description 2
- 229910052783 alkali metal Inorganic materials 0.000 description 2
- 230000008901 benefit Effects 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
- 229920001577 copolymer Polymers 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
- 150000002148 esters Chemical class 0.000 description 2
- 238000002474 experimental method Methods 0.000 description 2
- 229920000578 graft copolymer Polymers 0.000 description 2
- 229920001519 homopolymer Polymers 0.000 description 2
- 239000010410 layer 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
- 239000000843 powder Substances 0.000 description 2
- 230000009257 reactivity Effects 0.000 description 2
- 238000009991 scouring Methods 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
- 150000003460 sulfonic acids Chemical class 0.000 description 2
- 150000003467 sulfuric acid derivatives Chemical class 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
- 239000004215 Carbon black (E152) Substances 0.000 description 1
- 239000000253 Denture Cleanser 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
- UAOKXEHOENRFMP-ZJIFWQFVSA-N [(2r,3r,4s,5r)-2,3,4,5-tetraacetyloxy-6-oxohexyl] acetate Chemical compound CC(=O)OC[C@@H](OC(C)=O)[C@@H](OC(C)=O)[C@H](OC(C)=O)[C@@H](OC(C)=O)C=O UAOKXEHOENRFMP-ZJIFWQFVSA-N 0.000 description 1
- 230000002378 acidificating effect Effects 0.000 description 1
- 230000004913 activation Effects 0.000 description 1
- 230000000996 additive effect Effects 0.000 description 1
- 239000002390 adhesive tape Substances 0.000 description 1
- 150000001340 alkali metals 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
- 238000004380 ashing 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
- 150000003857 carboxamides Chemical class 0.000 description 1
- 230000015556 catabolic process Effects 0.000 description 1
- 239000003054 catalyst Substances 0.000 description 1
- 229920002678 cellulose Polymers 0.000 description 1
- 239000001913 cellulose Substances 0.000 description 1
- 238000004140 cleaning Methods 0.000 description 1
- 239000003086 colorant Substances 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 230000003111 delayed effect Effects 0.000 description 1
- 230000001419 dependent effect Effects 0.000 description 1
- 235000011180 diphosphates Nutrition 0.000 description 1
- 238000004090 dissolution Methods 0.000 description 1
- 239000004744 fabric Substances 0.000 description 1
- 239000003205 fragrance Substances 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- 239000008240 homogeneous mixture Substances 0.000 description 1
- 239000012943 hotmelt 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
- 238000004519 manufacturing process Methods 0.000 description 1
- 150000004682 monohydrates Chemical class 0.000 description 1
- 239000012170 montan wax Substances 0.000 description 1
- IOVCWXUNBOPUCH-UHFFFAOYSA-M nitrite group Chemical group N(=O)[O-] IOVCWXUNBOPUCH-UHFFFAOYSA-M 0.000 description 1
- 150000002826 nitrites Chemical class 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
- 238000005453 pelletization Methods 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
- 229910052615 phyllosilicate Inorganic materials 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
- 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
- 238000007712 rapid solidification Methods 0.000 description 1
- 230000009467 reduction 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
- 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 ; Methods for using cleaning compositions
- C11D11/0082—Special methods for preparing compositions containing mixtures of detergents ; Methods for using cleaning compositions 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
Landscapes
- 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)
Abstract
A process for producing coated bleach activator granules in which bleach activator base granules are coated with a coating substance and are simultaneously and/or subsequently thermally conditioned.
Description
Process for prodGCing coated bleach activator granules Bleach activators are important ingredients in detergents, scouring salts and dishwashing agents. They permit a bleaching action even at relatively low temperatures in that they react with hydrogen peroxide - usually perborates or percarbonates - to release an organic peroxycarboxylic acid.
The bleaching result obtainable depends on the nature and reactivity of the peroxycarboxylic acid formed, on the structure of the bond that is to be perhydrolyzed and on the solubility of the bleach activator in water. Since the activator is usually a reactive ester or an amide, it is frequently necessary to use it in granulated form for the,intended application in order to prevent hydrolysis in the presence of alkaline detergent ingredients and to ensure an adequate shelf life.
Numerous auxiliaries and processes have been proposed in the past for granulating these substances. EP-A-0 037 026, published October 7, 1981 describes a process for producing readily soluble activator granules comprising 90 to 98% activator with 10 to 2%
cellulose ethers, starch or starch ethers. Granules consisting of bleach activator, film-forming polymers and added organic C3-Cs-carboxylic, hydroxycarboxylic or ether carboxylic acid are specified in WO 90/01535, published February 22, 1990.
EP-A-0 468 824, published January 29, 1992 discloses granules comprising bleach activator and a film-forming polymer which is more soluble at a pH of 10 than at a pH of 7.
DE-A-44 39 039, published May 9, 1996 describes a process for producing activator granules by mixing a dry bleach activator with a dry, inorganic binder material containing water of hydration, compressing this mixture to form relatively large agglomerates, and comminuting these agglomerates to the desired grain size. A waterless , production process, by compacting the bleach activator with at least one water-swellable auxiliary, without the use of water, is known from EP-A-0 075 818, published April 6, 1983.
The bleaching result obtainable depends on the nature and reactivity of the peroxycarboxylic acid formed, on the structure of the bond that is to be perhydrolyzed and on the solubility of the bleach activator in water. Since the activator is usually a reactive ester or an amide, it is frequently necessary to use it in granulated form for the,intended application in order to prevent hydrolysis in the presence of alkaline detergent ingredients and to ensure an adequate shelf life.
Numerous auxiliaries and processes have been proposed in the past for granulating these substances. EP-A-0 037 026, published October 7, 1981 describes a process for producing readily soluble activator granules comprising 90 to 98% activator with 10 to 2%
cellulose ethers, starch or starch ethers. Granules consisting of bleach activator, film-forming polymers and added organic C3-Cs-carboxylic, hydroxycarboxylic or ether carboxylic acid are specified in WO 90/01535, published February 22, 1990.
EP-A-0 468 824, published January 29, 1992 discloses granules comprising bleach activator and a film-forming polymer which is more soluble at a pH of 10 than at a pH of 7.
DE-A-44 39 039, published May 9, 1996 describes a process for producing activator granules by mixing a dry bleach activator with a dry, inorganic binder material containing water of hydration, compressing this mixture to form relatively large agglomerates, and comminuting these agglomerates to the desired grain size. A waterless , production process, by compacting the bleach activator with at least one water-swellable auxiliary, without the use of water, is known from EP-A-0 075 818, published April 6, 1983.
2 Disadvantages of these activator granules are that~the properties of the granules are fixed essentially by the binder and by the granulating method used and that the resulting granules, besides the advantages described in the literature, often have certain disadvantages as well, for example suboptimal release of active substance, low abrasion resistance, high dust content, inadequate shelf life, separation within the powder or damage to the color of the fabric when used in detergents and cleaning materials.
In order to give granules defined properties a coating step is often carried out subsequent to the granulating step. Common methods are coating in mixers (mechanically induced fluidized bed) or coating in fluidized-bed apparatus (pneumatically induced fluidized bed).
For instance, WO 92/13798, published August 20, 1992 describes, for a bleach activator, coating with a water-soluble organic acid which melts at above 30°C, and WO 94/03305, published February 17, 1994 describes coating with a water-soluble acidic polymer in order to reduce color damage to the laundry.
WO 94/26862, published November 24, 1994 discloses the coating of granules consisting of bleach activator and a water- and/or alkali-soluble polymer with an organic compound melting at between 30 and 100°C for reducing separation in the pulverulent end product.
In this case the activator granules are placed in a L~dige plowshare mixer, circulated at from 160 to 180 rpm at room temperature, without using the pelletizer, and then sprayed with the hot melt. A disadvantage of this process is the very poor coating quality, which, although it brings about a reduction in separation in the pulverulent end product, has no effect on the other granule properties, such as release of active substance, abrasion resistance, dust content or shelf life, for example. The positive effect on the separation behavior can probably be attributed to a droplet-like solidification of the coating substance on the granule surface allowing the individual grains to hook together in the bulk product.
In order to give granules defined properties a coating step is often carried out subsequent to the granulating step. Common methods are coating in mixers (mechanically induced fluidized bed) or coating in fluidized-bed apparatus (pneumatically induced fluidized bed).
For instance, WO 92/13798, published August 20, 1992 describes, for a bleach activator, coating with a water-soluble organic acid which melts at above 30°C, and WO 94/03305, published February 17, 1994 describes coating with a water-soluble acidic polymer in order to reduce color damage to the laundry.
WO 94/26862, published November 24, 1994 discloses the coating of granules consisting of bleach activator and a water- and/or alkali-soluble polymer with an organic compound melting at between 30 and 100°C for reducing separation in the pulverulent end product.
In this case the activator granules are placed in a L~dige plowshare mixer, circulated at from 160 to 180 rpm at room temperature, without using the pelletizer, and then sprayed with the hot melt. A disadvantage of this process is the very poor coating quality, which, although it brings about a reduction in separation in the pulverulent end product, has no effect on the other granule properties, such as release of active substance, abrasion resistance, dust content or shelf life, for example. The positive effect on the separation behavior can probably be attributed to a droplet-like solidification of the coating substance on the granule surface allowing the individual grains to hook together in the bulk product.
3 The present invention provides a coating process for activator granules which makes it possible to tailor the granule properties within a wide range at the same time as making optimum use of the coating material.
This was achieved by a thermal conditioning during and/or after coating.
The invention accordingly provides a process for producing coated bleach activator granules in which bleach activator base granules are coated with a coating sutrstance and are simultaneouslywor-subsequently thermally conditioned.
Base granules which can be used ace all activators which in granulated form have a melting point of above 100°C. Examples of activator substances are tetraacetylethylenediamine (TAED), tetraacetylglycoluril (TAGU), diacetyldioxohexahydrotriazine (DADHT), acyloxybenzenesulfonates (e.g.
acylated sugars (e.g. pentaacetylglucose [PAGJ) or compounds as are described in EP-A-0 325 100, published July 26, 1989, EP-A-0 492 000, published July 1, and WO 91!10719, published July 25, 1991. Other suitable activators are N-acylated amines, amides, lactams, activated carboxylic esters, carboxylic anhydrides, lactones, acylals, carboxamides, acyllactams, acylated ureas and oxamides, and, furthermore, especially nitrites, which in addition to the nitrite group may also contain a quaternized ammonium group. Mixtures of different bleach activators can also be present in the base granules.
These base granules can include the customary granulating auxiliaries, which should have a melting point of more than 100°C. Suitable such auxiliaries are film-forming polymers, for example cellulose ethers, starch, starch ethers, homopolymers, copolymers and graft copolymers of unsaturated carboxylic acids and/or sulfonic acids and also the salts thereof; organic substances, for example cellulose, crosslinked polyvinylpyrrolidone, or inorganic substances, for example silicic acid, amorphous silicates, zeolites, bentonites, alkali metal phyllosilicates of the formula MM'SiXO~_~ * y H20 (M, M' = Na, K, H; x = 1.9 - 23; y = 0 - 25), orthophosphates, pyrophosphates and polyphosphates, phosphonic acids and their
This was achieved by a thermal conditioning during and/or after coating.
The invention accordingly provides a process for producing coated bleach activator granules in which bleach activator base granules are coated with a coating sutrstance and are simultaneouslywor-subsequently thermally conditioned.
Base granules which can be used ace all activators which in granulated form have a melting point of above 100°C. Examples of activator substances are tetraacetylethylenediamine (TAED), tetraacetylglycoluril (TAGU), diacetyldioxohexahydrotriazine (DADHT), acyloxybenzenesulfonates (e.g.
acylated sugars (e.g. pentaacetylglucose [PAGJ) or compounds as are described in EP-A-0 325 100, published July 26, 1989, EP-A-0 492 000, published July 1, and WO 91!10719, published July 25, 1991. Other suitable activators are N-acylated amines, amides, lactams, activated carboxylic esters, carboxylic anhydrides, lactones, acylals, carboxamides, acyllactams, acylated ureas and oxamides, and, furthermore, especially nitrites, which in addition to the nitrite group may also contain a quaternized ammonium group. Mixtures of different bleach activators can also be present in the base granules.
These base granules can include the customary granulating auxiliaries, which should have a melting point of more than 100°C. Suitable such auxiliaries are film-forming polymers, for example cellulose ethers, starch, starch ethers, homopolymers, copolymers and graft copolymers of unsaturated carboxylic acids and/or sulfonic acids and also the salts thereof; organic substances, for example cellulose, crosslinked polyvinylpyrrolidone, or inorganic substances, for example silicic acid, amorphous silicates, zeolites, bentonites, alkali metal phyllosilicates of the formula MM'SiXO~_~ * y H20 (M, M' = Na, K, H; x = 1.9 - 23; y = 0 - 25), orthophosphates, pyrophosphates and polyphosphates, phosphonic acids and their
4 salts, sulfates, carbonates and bicarbonates. Depending on what is required these granulating auxiliaries can be employed as individual substances or as mixtures.
In addition to the bleach activator and the granulating auxiliary the bleach activator base granules may also include further additives which enhance properties such as, for example, shelf life and bleach activation. Such additives include inorganic acids, organic acids, for instance mono- or polybasic carboxylic acids, hydroxycarboxylic acids and/or ether carboxylic acids, and also salts thereof, complexing agents, metal complexes and ketones.
Depending on what is required, the abovementioned additives can be employed as individual substances or as mixtures.
The base granules are made by mixing a dry bleaching activator with a dry inorganic binder material, pressing this mixture to give relatively large agglomerates and comminution of these agglomerates to the desired particle size.
The ratio of bleaching activator to inorganic binder material is usually 50:50 to 98:2, preferably 70:30 to 96:4 % by weight. The amount of additive depends in particular on its nature. Thus, acidifying additives and organic catalysts are added to increase the performance of the peracid in amounts of 0-20 % by weight, in particular in amounts of 1-10 % by weight, based on the total weight, while metal complexes are added in concentrations in the ppm range.
Suitable coating substances are all compounds or mixtures thereof which are solid at room temperature and which soften or melt in the range from 30 to 100°C.
Examples of such are:
C8-C3~ fatty acids (e.g. lauric, myristic, stearic acid); C8-C3~ fatty alcohols;
polyalkylene glycols (e.g. polyethylene glycols having a molar mass of from 1000 to 50,000 g/mol); nonionics (e.g. C$-C3~ fatty alcohol polyalkoxylates with from 1 to 100 moles of EO); anionics (e.g. alkanesulfonates, alkylbenzenesulfonates, a-olefinsulfonates, alkyl sulfates, alkyl ether sulfates having C$-C3~
hydrocarbon radicals); polymers (e.g. polyv_inyl alcohols); waxes(e.g. montan waxes, paraffin waxes, ester waxes, polyolefin waxes); silicones.
Within the coating substance which softens or melts in the range from 30 to 100°C
In addition to the bleach activator and the granulating auxiliary the bleach activator base granules may also include further additives which enhance properties such as, for example, shelf life and bleach activation. Such additives include inorganic acids, organic acids, for instance mono- or polybasic carboxylic acids, hydroxycarboxylic acids and/or ether carboxylic acids, and also salts thereof, complexing agents, metal complexes and ketones.
Depending on what is required, the abovementioned additives can be employed as individual substances or as mixtures.
The base granules are made by mixing a dry bleaching activator with a dry inorganic binder material, pressing this mixture to give relatively large agglomerates and comminution of these agglomerates to the desired particle size.
The ratio of bleaching activator to inorganic binder material is usually 50:50 to 98:2, preferably 70:30 to 96:4 % by weight. The amount of additive depends in particular on its nature. Thus, acidifying additives and organic catalysts are added to increase the performance of the peracid in amounts of 0-20 % by weight, in particular in amounts of 1-10 % by weight, based on the total weight, while metal complexes are added in concentrations in the ppm range.
Suitable coating substances are all compounds or mixtures thereof which are solid at room temperature and which soften or melt in the range from 30 to 100°C.
Examples of such are:
C8-C3~ fatty acids (e.g. lauric, myristic, stearic acid); C8-C3~ fatty alcohols;
polyalkylene glycols (e.g. polyethylene glycols having a molar mass of from 1000 to 50,000 g/mol); nonionics (e.g. C$-C3~ fatty alcohol polyalkoxylates with from 1 to 100 moles of EO); anionics (e.g. alkanesulfonates, alkylbenzenesulfonates, a-olefinsulfonates, alkyl sulfates, alkyl ether sulfates having C$-C3~
hydrocarbon radicals); polymers (e.g. polyv_inyl alcohols); waxes(e.g. montan waxes, paraffin waxes, ester waxes, polyolefin waxes); silicones.
Within the coating substance which softens or melts in the range from 30 to 100°C
5 there may additionally be other substances, not softening or melting in this temperature range, in dissolved or suspended form, examples being polymers (e.g.
homopolymers, copolymers or graft copolymers of unsaturated carboxylic acids and/or sulfonic acids and alkali metal salts thereof, cellulose ethers, starch, starch ethers, polyvinylpyrrolidone); organic substances (e.g. mono- or polybasic carboxylic acids, hydroxycarboxylic acids or ether carboxylic acids having 3 to 8 C-atoms, and the salts thereof); colorants; inorganic substances (e.g.
silicates, carbonates, bicarbonates, sulfates, phosphates, phosphonates).
Depending on the desired properties of the coated activator granules, the content of coating substance can be from 1 to 30% by weight, preferably from 5 to 15% by weight, based on coated activator granules.
The coating substances can be applied using mixers (mechanically induced fluidized bed) and fluidized-bed apparatus (pneumatically induced fluidized bed).
Examples of possible mixers are plowshare mixers (continuous and batchwise), annular bed mixers or else Schugi mixers. If a mixer is used, the thermal conditioning can take place in a granule preheater andlor directly in the mixer and/or in a fluidized bed downstream of the mixer. The coated granules can be cooled using granule coolers or fluidized-bed coolers. In the case of fluidized-bed apparatus, the thermal conditioning takes place by way of the hot gas used for fluidizing. Tie granules coated by the fluidized-bed method, as with the mixer method, can be cooled by way of a granule cooler or a fluidized-bed cooler. In both the mixer method and the fluidized-bed method the coating substance can be sprayed on by way of a single-substance or dual-substance nozzle apparatus. , The thermal conditioning comprises a heat treatment at a temperature from 30 to 100°C but no higher than the melting or softening temperature of the respective coating substance. It is preferred to operate at a temperature which lies just below
homopolymers, copolymers or graft copolymers of unsaturated carboxylic acids and/or sulfonic acids and alkali metal salts thereof, cellulose ethers, starch, starch ethers, polyvinylpyrrolidone); organic substances (e.g. mono- or polybasic carboxylic acids, hydroxycarboxylic acids or ether carboxylic acids having 3 to 8 C-atoms, and the salts thereof); colorants; inorganic substances (e.g.
silicates, carbonates, bicarbonates, sulfates, phosphates, phosphonates).
Depending on the desired properties of the coated activator granules, the content of coating substance can be from 1 to 30% by weight, preferably from 5 to 15% by weight, based on coated activator granules.
The coating substances can be applied using mixers (mechanically induced fluidized bed) and fluidized-bed apparatus (pneumatically induced fluidized bed).
Examples of possible mixers are plowshare mixers (continuous and batchwise), annular bed mixers or else Schugi mixers. If a mixer is used, the thermal conditioning can take place in a granule preheater andlor directly in the mixer and/or in a fluidized bed downstream of the mixer. The coated granules can be cooled using granule coolers or fluidized-bed coolers. In the case of fluidized-bed apparatus, the thermal conditioning takes place by way of the hot gas used for fluidizing. Tie granules coated by the fluidized-bed method, as with the mixer method, can be cooled by way of a granule cooler or a fluidized-bed cooler. In both the mixer method and the fluidized-bed method the coating substance can be sprayed on by way of a single-substance or dual-substance nozzle apparatus. , The thermal conditioning comprises a heat treatment at a temperature from 30 to 100°C but no higher than the melting or softening temperature of the respective coating substance. It is preferred to operate at a temperature which lies just below
6 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, with particular preference, from 0.3 to 0.8 mm.
The precise temperature during thermal conditioning or the difference in temperature from the melting point of the coating substance is dependent on the amount of the coating material, on the thermal conditioning time and on the properties desired for the coated bleach activator granules, and must be determined in preliminary experiments for the particular system.
The period for thermal conditioning is from approximately 1 to 180, preferably from 3 to 60 and, with particular preference, from 5 to 30 minutes.
The advantage of the new process over the prior art is that the liquid coating material does not solidify too rapidly and thus has the possibility of running as a thin film over the surface of the granules. This produces a highly uniform coating of the grain in a thin layer with the coating substance, and an optimum coating effect for use of a minimum amount of coating substance. In conventional processes, i.e.
those without a thermal conditioning step, solidification of the individual droplets on the cold granule surface is too rapid. Consequently, the surface is covered only with fine individual droplets and still has large coating voids. As a result, the desired coating effect is not fully obtained or a much higher amount of coating substance is required in order to obtain the desired coating effect. In the latter case, however, the content of activator substance is reduced, which in many cases is undesirable.
By means of the novel process it is possible to tailor the properties of the activator granules within broad ranges to the desired specifications by an appropriate choice of the coating substance, the coating rate and the process temperature regime,. In this context it is possible in particular to optimize in a targeted manner the following activator granule properties.
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, with particular preference, from 0.3 to 0.8 mm.
The precise temperature during thermal conditioning or the difference in temperature from the melting point of the coating substance is dependent on the amount of the coating material, on the thermal conditioning time and on the properties desired for the coated bleach activator granules, and must be determined in preliminary experiments for the particular system.
The period for thermal conditioning is from approximately 1 to 180, preferably from 3 to 60 and, with particular preference, from 5 to 30 minutes.
The advantage of the new process over the prior art is that the liquid coating material does not solidify too rapidly and thus has the possibility of running as a thin film over the surface of the granules. This produces a highly uniform coating of the grain in a thin layer with the coating substance, and an optimum coating effect for use of a minimum amount of coating substance. In conventional processes, i.e.
those without a thermal conditioning step, solidification of the individual droplets on the cold granule surface is too rapid. Consequently, the surface is covered only with fine individual droplets and still has large coating voids. As a result, the desired coating effect is not fully obtained or a much higher amount of coating substance is required in order to obtain the desired coating effect. In the latter case, however, the content of activator substance is reduced, which in many cases is undesirable.
By means of the novel process it is possible to tailor the properties of the activator granules within broad ranges to the desired specifications by an appropriate choice of the coating substance, the coating rate and the process temperature regime,. In this context it is possible in particular to optimize in a targeted manner the following activator granule properties.
7 1. Time-optimized release of active substance In order to avoid interaction between the bleaching system and the enzyme system it is advantageous to couple a slightly delayed reaction~and active-s substance release of the bleaching system with rapid enzyme action. In this way the enzymes can develop their washing power fully within the first few minutes of the washing process without being damaged by the bleaching system. Only after the enzymes have done their job is the bleaching process set in motion by reaction of the bleach activator with the hydrogen peroxide source. Appropriate coating of the bleach activator makes it possible to tailor the reactivity, i.e. the rate of dissolution or the rate of formation of the peracid, specifically to the enzyme system. The process permits controlled adjustment of the rate of formation of the peracid at the same time as having a minimal amount of coating substance and thus the maximum activator content.
2. Increasing the abrasion resistance By coating granules with softening or melting substances it is possible to increase the abrasion resistance of activator granules. The increase in abrasion resistance is greater the better the coating of the granule surface with the coating substance. The novel coating process makes it possible, with a minimum coating rate, to bring about optimum flow of the coating substance over the granule surface and thus an optimum enhancement of the abrasion resistance.
3. Reducing the dust content The novel coating process, in which excessively rapid solidification of the softening or melting coating substance is prevented by means of appropriate thermal conditioning during 'and/or after the coating step also makes it possible for granules to be dedusted in an optimum manner with a minimal coating rate, since the coating substance remains floJirable and bindable over a relatively long period_and is thus able to bind more dust particles. With prior art coating, on the other hand, there may at worst even be an increase in the dust content as a result of in some cases direct spray drying.
4. Extending the shelf life When a detergent and cleaning material is stored there may be a reaction at the boundary between activator grain and a directly adjacent grain of the hydrogen peroxide source, with subsequent loss of active oxygen and thus uncontrolled breakdown of the bleaching system. By means of optimum coating, as is possible only through the novel coating process, a complete protective layer is constructed at the grain boundary, which layer then prevents reaction of the activator grain with the grain of the hydrogen peroxide source in the course of storage. When water-soluble and/or low-melting coating substances are used it is nevertheless possible to obtain the required bleaching performance in the washing process.
The granules obtained in this way are directly suitable for use in detergents and cleaning materials. They are ideal for use in heavy-duty detergents, scouring salts, dishwashing agents, general purpose cleaning powders and denture cleansers. In such formulations the granules of the invention are employed usually in combination with a hydrogen peroxide source. Examples thereof are perborate monohydrate, perborate tetrahydrate, percarbonates, and adducts of hydrogen peroxide with urea or with amine oxides. The formuation may also feature further, prior art detergent ingredients, such as organic or inorganic builders and cobuilders, surfactants, enzymes, v~ashing additives, fluorescent whiteners and fragrance.
Examples Example 1: Coating in a Schugi mixer with downstream fluidized bed for thermal conditioning and cooling TAED 4303 (Hoechst AG) was metered continuously at a throughput of 480 kg/h into a Schugi mixer (Flexomix 160, from Hosokawa Schugi) and sprayed with a hot (75°C) melt of myristic acid. The coated material fell directly into a downstream fluidized bed (Hosokawa Schugi) where it was thermally conditioned at fluidized-bed temperatures of about 54°C in a first chamber for 5 to 10 minutes and then was cooled at fluidized-bed temperatures of about 35°C in a second chamber.
For comparison purposes (prior art) TAED 4303 was metered continuously at a throughput of 480 kg/h into the Schugi mixer, sprayed with a hot (75°C) melt of myristic acid and then cooled directly in a downstream fluidized bed at fluidized-bed temperatures of about 35°C.
The coating quality of the products was assessed by determining the rate of formation of peracetic acid at a temperature of 20°C. The slower the formation of peracetic acid the better the degree of coating achieved.
In order to determine the rate of formation of peracetic acid, 1 I of distilled water,
2. Increasing the abrasion resistance By coating granules with softening or melting substances it is possible to increase the abrasion resistance of activator granules. The increase in abrasion resistance is greater the better the coating of the granule surface with the coating substance. The novel coating process makes it possible, with a minimum coating rate, to bring about optimum flow of the coating substance over the granule surface and thus an optimum enhancement of the abrasion resistance.
3. Reducing the dust content The novel coating process, in which excessively rapid solidification of the softening or melting coating substance is prevented by means of appropriate thermal conditioning during 'and/or after the coating step also makes it possible for granules to be dedusted in an optimum manner with a minimal coating rate, since the coating substance remains floJirable and bindable over a relatively long period_and is thus able to bind more dust particles. With prior art coating, on the other hand, there may at worst even be an increase in the dust content as a result of in some cases direct spray drying.
4. Extending the shelf life When a detergent and cleaning material is stored there may be a reaction at the boundary between activator grain and a directly adjacent grain of the hydrogen peroxide source, with subsequent loss of active oxygen and thus uncontrolled breakdown of the bleaching system. By means of optimum coating, as is possible only through the novel coating process, a complete protective layer is constructed at the grain boundary, which layer then prevents reaction of the activator grain with the grain of the hydrogen peroxide source in the course of storage. When water-soluble and/or low-melting coating substances are used it is nevertheless possible to obtain the required bleaching performance in the washing process.
The granules obtained in this way are directly suitable for use in detergents and cleaning materials. They are ideal for use in heavy-duty detergents, scouring salts, dishwashing agents, general purpose cleaning powders and denture cleansers. In such formulations the granules of the invention are employed usually in combination with a hydrogen peroxide source. Examples thereof are perborate monohydrate, perborate tetrahydrate, percarbonates, and adducts of hydrogen peroxide with urea or with amine oxides. The formuation may also feature further, prior art detergent ingredients, such as organic or inorganic builders and cobuilders, surfactants, enzymes, v~ashing additives, fluorescent whiteners and fragrance.
Examples Example 1: Coating in a Schugi mixer with downstream fluidized bed for thermal conditioning and cooling TAED 4303 (Hoechst AG) was metered continuously at a throughput of 480 kg/h into a Schugi mixer (Flexomix 160, from Hosokawa Schugi) and sprayed with a hot (75°C) melt of myristic acid. The coated material fell directly into a downstream fluidized bed (Hosokawa Schugi) where it was thermally conditioned at fluidized-bed temperatures of about 54°C in a first chamber for 5 to 10 minutes and then was cooled at fluidized-bed temperatures of about 35°C in a second chamber.
For comparison purposes (prior art) TAED 4303 was metered continuously at a throughput of 480 kg/h into the Schugi mixer, sprayed with a hot (75°C) melt of myristic acid and then cooled directly in a downstream fluidized bed at fluidized-bed temperatures of about 35°C.
The coating quality of the products was assessed by determining the rate of formation of peracetic acid at a temperature of 20°C. The slower the formation of peracetic acid the better the degree of coating achieved.
In order to determine the rate of formation of peracetic acid, 1 I of distilled water,
8.0 g of test detergent WMP and 1.5 g of sodium perborate monohydrate were placed in a 2 I glass beaker and the mixture was stirred at from 250 to 280 rpm using a magnetic stirrer. Then, after 1 to 2 minutes, 0.5 g of the coated TAED
granules was added. After one minute an aliquot of 50 ml was removed by pipette and introduced onto 150 g of ice and 5 ml of 20% strength acetic acid in an Erlenmeyer flask. Immediately following the addition of 2 to 3 ml of 10%
strength potassium iodide solution, the sample was titrated to the potentiometric endpoint with 0.01 molar sodium thiosulfate solution (Titroprocessor 716 DMS from Met~ohm) and the amount of peracetic acid was calculated from the amount of sodium thiosulfate consumed. Then further samples were taken at intervals of 2 to 5 minutes and were titrated as described. The entire procedure was repeated until equal or descending amounts of peracetic acid were found after three successive titrations. The maximum amount of peracetic acid found was then taken as being 100% and on this basis, finally, the amount of peracetic acid formed after 5, 10 and minutes was determined in percent as a measure of the rate of formation of peracetic acid.
Table 1: Rate of formation of peracetic acid by the TAED granules coated in the Schugi mixer with downstream fluidized bed (products 1 and 4:
comparison examples) 10 Product No. TAED granules Peracetic acid formed [%]
5 min 10 min 20 min 1 Base granules (BG, 75 95 100 uncoated) 2 BG+ 10% myristic acid,11 21 55 thermally conditioned 3 BG+ 15% myristic acid,9 18 54 thermally conditioned 15 4 BG+ 15% myristic acid,39 59 83 cooled By means of the thermal conditioning it is possible to bring about a marked improvement in the coating quality, expressed by the delay in the formation of peracetic acid, for the same coating rate (comparison of products 3 and 4).
To achieve an optimum coating quality an amount of 10% coating substance (product 2) is sufficient given appropriate thermal conditioning.
Example 2: Coating by the fluidized-bed method_with downstream thermal conditioning 500 - 600 g of TAED 4303 were placed in a fluidized bed (fluidized-bed apparatus Strea 1 from Aeromatic) and sprayed with a hot (about 80°C) melt of stearic acid.
For comparison purposes, in one case the fluidized bed was operated at low temperatures and after the end of spraying was cooled again for about 5 minutes (prior art). In the other case, in accordance with the novel process, the coated granules were placed back in the fluidized bed and subjected to thermal conditioning. To this end the fluidized bed was heated gradually to temperatures of about 65 to 70°C and this product temperature was held constant for about 5 to 8 minutes. The thermally conditioned product was then cooled down again in stages.
The coating quality was again examined by determining the rate of formation of peracetic acid at a temperature of 20°C. The slower the formation of peracetic acid the better the degree of coating achieved.
Table 2: Rate of formation of peracetic acid of TAED granules coated by the fluidized-bed method with subsequent thermal conditioning (products 5, 8 to 10: comparison examples) Product No. TAED granules Peracetic acid formed [%]
5 min 10 min 20 min 5 ,~f Base granules (BG) 75 95 100 6 BG+ 10% stearic acid, 10 21 50 thermally conditioned 7 BG+ 20% stearic acid, 12 22 52 thermally conditioned ~ CA 02216193 1997-09-22 8 BG+ 10% stearic acid; 70 - 85 98 not thermally conditioned
granules was added. After one minute an aliquot of 50 ml was removed by pipette and introduced onto 150 g of ice and 5 ml of 20% strength acetic acid in an Erlenmeyer flask. Immediately following the addition of 2 to 3 ml of 10%
strength potassium iodide solution, the sample was titrated to the potentiometric endpoint with 0.01 molar sodium thiosulfate solution (Titroprocessor 716 DMS from Met~ohm) and the amount of peracetic acid was calculated from the amount of sodium thiosulfate consumed. Then further samples were taken at intervals of 2 to 5 minutes and were titrated as described. The entire procedure was repeated until equal or descending amounts of peracetic acid were found after three successive titrations. The maximum amount of peracetic acid found was then taken as being 100% and on this basis, finally, the amount of peracetic acid formed after 5, 10 and minutes was determined in percent as a measure of the rate of formation of peracetic acid.
Table 1: Rate of formation of peracetic acid by the TAED granules coated in the Schugi mixer with downstream fluidized bed (products 1 and 4:
comparison examples) 10 Product No. TAED granules Peracetic acid formed [%]
5 min 10 min 20 min 1 Base granules (BG, 75 95 100 uncoated) 2 BG+ 10% myristic acid,11 21 55 thermally conditioned 3 BG+ 15% myristic acid,9 18 54 thermally conditioned 15 4 BG+ 15% myristic acid,39 59 83 cooled By means of the thermal conditioning it is possible to bring about a marked improvement in the coating quality, expressed by the delay in the formation of peracetic acid, for the same coating rate (comparison of products 3 and 4).
To achieve an optimum coating quality an amount of 10% coating substance (product 2) is sufficient given appropriate thermal conditioning.
Example 2: Coating by the fluidized-bed method_with downstream thermal conditioning 500 - 600 g of TAED 4303 were placed in a fluidized bed (fluidized-bed apparatus Strea 1 from Aeromatic) and sprayed with a hot (about 80°C) melt of stearic acid.
For comparison purposes, in one case the fluidized bed was operated at low temperatures and after the end of spraying was cooled again for about 5 minutes (prior art). In the other case, in accordance with the novel process, the coated granules were placed back in the fluidized bed and subjected to thermal conditioning. To this end the fluidized bed was heated gradually to temperatures of about 65 to 70°C and this product temperature was held constant for about 5 to 8 minutes. The thermally conditioned product was then cooled down again in stages.
The coating quality was again examined by determining the rate of formation of peracetic acid at a temperature of 20°C. The slower the formation of peracetic acid the better the degree of coating achieved.
Table 2: Rate of formation of peracetic acid of TAED granules coated by the fluidized-bed method with subsequent thermal conditioning (products 5, 8 to 10: comparison examples) Product No. TAED granules Peracetic acid formed [%]
5 min 10 min 20 min 5 ,~f Base granules (BG) 75 95 100 6 BG+ 10% stearic acid, 10 21 50 thermally conditioned 7 BG+ 20% stearic acid, 12 22 52 thermally conditioned ~ CA 02216193 1997-09-22 8 BG+ 10% stearic acid; 70 - 85 98 not thermally conditioned
9 BG+ 20% stearic acid, 40 60 84 not thermally conditioned BG+ 30% stearic acid, 20 35 60 not thermally conditioned 5 The thermal conditioning makes it possible to bring about a marked improvement in the coating quality, expressed by the delay in the formation of peracetic acid, for the same coating rate (comparison of products 6 and 8 and products 7 and 9, respectively).
10 To achieve an optimum coating quality an amount of 10% coating substance (product 6) is sufficient given appropriate thermal conditioning.
The influence of thermal conditioning on coating quality is also evident in the shelf life of TAED granules in detergent formulations.
The shelf life was tested in ready made-up folding boxes (height: 6.5 cm;
width 3.2 cm; depth 2.2 cm) at 38°C and 80% relative atmospheric humidity (rH) over a period of 28 days. Each folding box was filled with a homogeneous mixture comprising $.0 g of test detergent WMP, 1.5 g of sodium percarbonate and 0.5 g of the test TAED granules and then was sealed at the top with Tesafilm adhesive tape.
All samples were mixed and dispensed into the boxes on the same day. The filled and labeled folding boxes were then placed at a sufficient distance from one another in the climatically controlled cabinet and stored at 38°C/80% rH. After storage periods of 0, 3, 6, 9, 15, 23 and 28 days the samples were removed from the cabinet, the entire sample was introduced at 20°C into 1 I of distilled water, while stirring with a magnetic stirrer (250 to 280 rpm), and 1 g of sodium percarbonate was added. Subsequent determination of the amo~rnt of peracetic acid formed was as indicated in Example 1. The TAED content of the sample was then calculated from the maximum value of peracetic acid found. The TAED durability represents the percentage TAED content of the sample after storage relative to the TAED
content of the unstored sample.
Table 3: Shelf life in detergent formulations of TAED granules coated by the fluidized-bed method with subsequent thermal conditioning Product No. TAED granules TAED durability after storage [%]
Od 3d 6d 9d 15d 23d 28d 5 Base granules (BG) 100 24 14 12 10 9 8 6 BG+ 10% stearic 100 88 61 56 47 45 45 acid, thermally conditioned 8 BG+ 10% stearic 100 52 24 20 18 16 15 acid, not thermally conditioned With small coating quantities of from 5 to 10% an improvement in numerous product properties, for example the shelf life in detergent formulations, can be achieved only by thermal conditioning, i.e. only by the novel process.
Example 3: Coating by the fluidized-bed method with simultaneous thermal .~ conditioning TAED 4303 was metered continuously at 40 kg/h into the fluidized-bed apparatus (pilot plant fluidized-bed apparatus) by way of a flexible metering screw and was coated with 20% myristic acid. The residence time in the fluidized bed was about minutes. The product, discharged through a star wheel sluice, was transported by means of a metering screw onto a screening machine on which the coarse fraction, larger than 1.0 mm, and the fine fraction, less than 0.2 mm, were separated off. The coarse fraction was subsequently comminuted in a mill and then passed together with the fine fraction via a flexible metering screw into the fluidized-bed apparatus. In the course of the experiment the fluidized-bed temperature was raised from an initial 46°C to an ultimate 54°C.
The coating quality was examined by determining the rate of formation of peracetic acid at a temperature of 20°C and by determining the content of dust smaller 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 better the increase in abrasion resistance.
Table 4: Rate of formation of peracetic acid of TAED granules coated by the fluidized-bed method with simultaneous thermal conditioning (product
The influence of thermal conditioning on coating quality is also evident in the shelf life of TAED granules in detergent formulations.
The shelf life was tested in ready made-up folding boxes (height: 6.5 cm;
width 3.2 cm; depth 2.2 cm) at 38°C and 80% relative atmospheric humidity (rH) over a period of 28 days. Each folding box was filled with a homogeneous mixture comprising $.0 g of test detergent WMP, 1.5 g of sodium percarbonate and 0.5 g of the test TAED granules and then was sealed at the top with Tesafilm adhesive tape.
All samples were mixed and dispensed into the boxes on the same day. The filled and labeled folding boxes were then placed at a sufficient distance from one another in the climatically controlled cabinet and stored at 38°C/80% rH. After storage periods of 0, 3, 6, 9, 15, 23 and 28 days the samples were removed from the cabinet, the entire sample was introduced at 20°C into 1 I of distilled water, while stirring with a magnetic stirrer (250 to 280 rpm), and 1 g of sodium percarbonate was added. Subsequent determination of the amo~rnt of peracetic acid formed was as indicated in Example 1. The TAED content of the sample was then calculated from the maximum value of peracetic acid found. The TAED durability represents the percentage TAED content of the sample after storage relative to the TAED
content of the unstored sample.
Table 3: Shelf life in detergent formulations of TAED granules coated by the fluidized-bed method with subsequent thermal conditioning Product No. TAED granules TAED durability after storage [%]
Od 3d 6d 9d 15d 23d 28d 5 Base granules (BG) 100 24 14 12 10 9 8 6 BG+ 10% stearic 100 88 61 56 47 45 45 acid, thermally conditioned 8 BG+ 10% stearic 100 52 24 20 18 16 15 acid, not thermally conditioned With small coating quantities of from 5 to 10% an improvement in numerous product properties, for example the shelf life in detergent formulations, can be achieved only by thermal conditioning, i.e. only by the novel process.
Example 3: Coating by the fluidized-bed method with simultaneous thermal .~ conditioning TAED 4303 was metered continuously at 40 kg/h into the fluidized-bed apparatus (pilot plant fluidized-bed apparatus) by way of a flexible metering screw and was coated with 20% myristic acid. The residence time in the fluidized bed was about minutes. The product, discharged through a star wheel sluice, was transported by means of a metering screw onto a screening machine on which the coarse fraction, larger than 1.0 mm, and the fine fraction, less than 0.2 mm, were separated off. The coarse fraction was subsequently comminuted in a mill and then passed together with the fine fraction via a flexible metering screw into the fluidized-bed apparatus. In the course of the experiment the fluidized-bed temperature was raised from an initial 46°C to an ultimate 54°C.
The coating quality was examined by determining the rate of formation of peracetic acid at a temperature of 20°C and by determining the content of dust smaller 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 better the increase in abrasion resistance.
Table 4: Rate of formation of peracetic acid of TAED granules coated by the fluidized-bed method with simultaneous thermal conditioning (product
11: comparison example) Product TAED granules Tnuid. Peracetic Dust bed acid [%]
No. content [C] 5 min 10 min 20 [%]
min 11 Base granules - 75 95 100 --(BG)
No. content [C] 5 min 10 min 20 [%]
min 11 Base granules - 75 95 100 --(BG)
12 BG+ 20% myristic46 66 81 94 30 acid
13 BG+ 20% myristic49 48 68 87 15 acid
14 BG+ 20% myristic52 38 60 86 10 ' cid .
15 BG+ 20% myristic54 20 36 62 5 acid As the fluidized-bed temperature increases and comes nearer to the melting point of myristic acid (55°C) there is a marked increase in the coating quality, expressed by the delay in the formation of the peracid, and better dedusting and higher abrasion resistance are obtained, expressed by the falling content of dust < 0.2 mm in the coated granules.
Example 4: Coating in a plowshare mixer with simultaneous thermal conditioning 1.2 kg of TAED granules in accordance with EP-A-0 037 026 were placed in a batch plowshare mixer (M5R from Lodige) and, while being thoroughly mixed with a mixing element rotational speed of around 150 rpm, were sprayed with 210 g of a hot (80°C) melt of stearic acid. During the coating step the contents of the mixture were 10 conditioned at a temperature of 50°C by way of a heating jacket. The coating and thermal conditioning time was about 10 minutes. For comparison purposes, in accordance with WO 94/26826, 1.2 kg of TAED granules according to EP-A-0 037 026 were placed in a batch plowshare mixture and sprayed at room temperature, while being thoroughly mixed at a mixing element rotational speed of about 150 rpm, 15 with 210 g of a hot (80°C) melt of stearic acid.
The coating quality was examined by determining the rate of formation of peracetic acid at a temperature of 20°C.
Table 5: Rate of formation of peracetic acid by TAED granules coated in a plowshare mixer with thermal conditioning during the coating step (products 16 and 18; comparison examples)
Example 4: Coating in a plowshare mixer with simultaneous thermal conditioning 1.2 kg of TAED granules in accordance with EP-A-0 037 026 were placed in a batch plowshare mixer (M5R from Lodige) and, while being thoroughly mixed with a mixing element rotational speed of around 150 rpm, were sprayed with 210 g of a hot (80°C) melt of stearic acid. During the coating step the contents of the mixture were 10 conditioned at a temperature of 50°C by way of a heating jacket. The coating and thermal conditioning time was about 10 minutes. For comparison purposes, in accordance with WO 94/26826, 1.2 kg of TAED granules according to EP-A-0 037 026 were placed in a batch plowshare mixture and sprayed at room temperature, while being thoroughly mixed at a mixing element rotational speed of about 150 rpm, 15 with 210 g of a hot (80°C) melt of stearic acid.
The coating quality was examined by determining the rate of formation of peracetic acid at a temperature of 20°C.
Table 5: Rate of formation of peracetic acid by TAED granules coated in a plowshare mixer with thermal conditioning during the coating step (products 16 and 18; comparison examples)
16 Product No. TAED granules - Peracetic acid [%]
5 min 10 min 20 min 16 Base granules 81 96 100
5 min 10 min 20 min 16 Base granules 81 96 100
17 BG+ 15% stearic 44 61 79 acid, thermally conditioned (50C)
18 BG+ 15% stearic 75 90 98 acid, not thermally conditioned Without thermal conditioning, although it is possible by virtue of the coating to exert a positive influence on the separation behaviour (product 18), the improvement of many other properties, for example the delay in the formation of peracetic acid, is possible only by thermal conditioning, i.e. by the novel process (product 17).
The positive effect on the separation behavior which is obtained by the coating without thermal conditioning can probably be attributed to the droplet-like solidification of the coating substance on the granule surface, allowing the individual granules to hook together in the bulk product. However, this is not associated with any positive effect on many other properties.
Example 5: Coating in a plowshare mixer with simultaneous thermal conditioning TAED 4303~was metered continuously at throughputs of from 100 to 300 kg/h into the plowshare mixer (KT-160 from Drais). At the same time the contents of the mixture were conditioned to temperatures in the range from 44 to 52°C
by way of a heating jacket. The residence time in the mixer was 8 to 12 minutes.
Simultaneously, a melt of stearic acid at a temperature of 80°C was sprayed through a nozzle into the front part of the mixer (nearer to the.point of product entry). The coating rate was 7%. The mixer was operated at a mixing element rotational speed of 90 rpm and without deploying the pelletizing blades. The mixer was filled to a level where the product just covered the mixing shaft. The coated material was taken off continuously from the mixer and passed quickly through a screen (0.2 to 1.0 mm) in order to separate off fine and coarse fractions.
The coating quality was examined by determining the rate of formation of peracetic acid at a temperature of 20°C.
Table 6: Rate of formation of peracetic acid by TAED granules coated in a plowshare mixer with simultaneous thermal conditioning (product 19:
comparison example) Prod. No. TAED granulesTm;,~urePeracetic acid [%]
[C] 5 min 10 min 20 min 1 5 19 Base granules- 75 95 100 BG+ 7% stearic44 72 95 99 acid 21 BG+ 7% stearic48 70 90 98 acid 22 BG+ 7% stearic52 60 80 94 acid 20 As the temperature of the mixture increases and comes nearer to the melting point of stearic acid there is an increase in the coating quality, expressed by the delay in the formation of the peracid.
The positive effect on the separation behavior which is obtained by the coating without thermal conditioning can probably be attributed to the droplet-like solidification of the coating substance on the granule surface, allowing the individual granules to hook together in the bulk product. However, this is not associated with any positive effect on many other properties.
Example 5: Coating in a plowshare mixer with simultaneous thermal conditioning TAED 4303~was metered continuously at throughputs of from 100 to 300 kg/h into the plowshare mixer (KT-160 from Drais). At the same time the contents of the mixture were conditioned to temperatures in the range from 44 to 52°C
by way of a heating jacket. The residence time in the mixer was 8 to 12 minutes.
Simultaneously, a melt of stearic acid at a temperature of 80°C was sprayed through a nozzle into the front part of the mixer (nearer to the.point of product entry). The coating rate was 7%. The mixer was operated at a mixing element rotational speed of 90 rpm and without deploying the pelletizing blades. The mixer was filled to a level where the product just covered the mixing shaft. The coated material was taken off continuously from the mixer and passed quickly through a screen (0.2 to 1.0 mm) in order to separate off fine and coarse fractions.
The coating quality was examined by determining the rate of formation of peracetic acid at a temperature of 20°C.
Table 6: Rate of formation of peracetic acid by TAED granules coated in a plowshare mixer with simultaneous thermal conditioning (product 19:
comparison example) Prod. No. TAED granulesTm;,~urePeracetic acid [%]
[C] 5 min 10 min 20 min 1 5 19 Base granules- 75 95 100 BG+ 7% stearic44 72 95 99 acid 21 BG+ 7% stearic48 70 90 98 acid 22 BG+ 7% stearic52 60 80 94 acid 20 As the temperature of the mixture increases and comes nearer to the melting point of stearic acid there is an increase in the coating quality, expressed by the delay in the formation of the peracid.
Claims (13)
1. A process for producing coated bleach activator granules, which comprises coating bleach activator base granules with a coating substance in a mechanically induced fluidized bed and simultaneously or subsequently thermally conditioning them.
2. The process as claimed in claim 1, wherein the activator base granules have a melting point of above 100°C.
3. The process as claimed in claim 1 or 2, wherein the coating substance has a softening or melting point in the range from 30 to 100°C.
4. The process as claimed in any one of claims 1 to 3, wherein thermal conditioning takes place during or after the coating step at a temperature about the softening or melting point of the coating substance.
5. The process as claimed in any one of claims 1 to 4, wherein bleach activators used are N-acylated amines, amides, lactams, acyloxybenzenesulfonates, acylated sugars, activated carboxylic esters, carboxylic anhydrides, lactones, acylals, oxamides and/or nitriles which may contain a quaternary ammonium group.
6. The process as claimed in any one of claims 1 to 5, wherein coating subtances used are fatty acids, fatty alcohols, polyalkylene glycols, nonionic surfactants, anionic surfactants, polymers, waxes and/or silicones.
7. The process as claimed in any one of claims 1 to 6, wherein the coating substance comprises polymers, organic substances and/or inorganic substances in dissolved or suspended form.
8. The process as claimed in any one of claims 1 to 7, wherein the content of coating substance is from 1 to 30% by weight based on the coated activator granules.
9. The process as claimed in claim 8, wherein the content of coating substance is from 5 to 15% by weight based on the coated activator granules.
10. The process as claimed in any one of claims 1 to 9, wherein the grain size of the coated bleach activator granules is from 0.1 to 2.0 mm.
11. The process as claimed in claim 10, wherein the grain size of the coated bleach activator granules is from 0.2 to 1.0 mm.
12. The process as claimed in claim 11, wherein the grain size of the coated bleach activator granules is from 0.3 to 0.8 mm
13. The process as claimed in any one of claims 1 to 12, wherein the activator base granules contain a maximum of 20% by weight, based on the weight of the activator base granules, of one or more additives selected from the group consisting of inorganic acids, organic acids, complexing agents, ketones and metal complexes.
Applications Claiming Priority (2)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
DE19641708A DE19641708A1 (en) | 1996-10-10 | 1996-10-10 | Process for the preparation of a coated bleach activator granulate |
DE19641708.2 | 1996-10-10 |
Publications (2)
Publication Number | Publication Date |
---|---|
CA2216193A1 CA2216193A1 (en) | 1998-04-10 |
CA2216193C true CA2216193C (en) | 2006-07-04 |
Family
ID=7808324
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
CA002216193A Expired - Fee Related CA2216193C (en) | 1996-10-10 | 1997-09-22 | Process for producing coated bleach activator granules |
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) |
Families Citing this family (30)
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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 |
DE10057045A1 (en) | 2000-11-17 | 2002-05-23 | Clariant Gmbh | Particulate bleach activators based on acetonitriles |
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 |
EP2013325B1 (en) * | 2006-04-04 | 2012-06-13 | Basf Se | Bleach systems enveloped with polymeric layers |
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 (en) * | 2009-04-11 | 2010-10-14 | Clariant International Limited | Bleach granules with active coating |
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 |
GB201019628D0 (en) | 2010-11-19 | 2010-12-29 | Reckitt Benckiser Nv | Dyed coated bleach materials |
GB201106408D0 (en) | 2011-04-15 | 2011-06-01 | Revolymer Ltd | Novel composite |
GB201106409D0 (en) | 2011-04-15 | 2011-06-01 | Revolymer Ltd | Novel composite |
GB201106391D0 (en) | 2011-04-15 | 2011-06-01 | Reckitt & Colman Overseas | Novel composite |
GB201106377D0 (en) | 2011-04-15 | 2011-06-01 | Reckitt & Colman Overseas | Novel composite |
US8728454B1 (en) | 2012-10-30 | 2014-05-20 | The Clorox Company | Cationic micelles with anionic polymeric counterions compositions thereof |
US8883705B2 (en) | 2012-10-30 | 2014-11-11 | The Clorox Company | Cationic micelles with anionic polymeric counterions systems 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 |
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KR20170003922A (en) * | 2014-05-09 | 2017-01-10 | 바스프 에스이 | Acylhydrazone granulate with two - layer coating for use in laundry detergents |
DE102015225882A1 (en) * | 2015-12-18 | 2017-06-22 | Henkel Ag & Co. Kgaa | Particulate agent for enhancing bleaching action |
US11375714B2 (en) * | 2016-04-08 | 2022-07-05 | Battelle Memorial Institute | Encapsulation compositions |
EP3529343A1 (en) | 2016-10-18 | 2019-08-28 | Sterilex LLC | Ambient moisture-activated surface treatment powder |
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US5298061A (en) * | 1993-05-14 | 1994-03-29 | Olin Corporation | Gel-free paint containing zinc pyrithione, cuprous oxide, and amine treated rosin |
DE4316481A1 (en) * | 1993-05-17 | 1994-11-24 | Henkel Kgaa | Bleach and disinfectant |
US5534196A (en) * | 1993-12-23 | 1996-07-09 | The Procter & Gamble Co. | Process for making lactam bleach activator containing particles |
US5480577A (en) * | 1994-06-07 | 1996-01-02 | Lever Brothers Company, Division Of Conopco, Inc. | Encapsulates containing surfactant for improved release and dissolution rates |
DE4439039A1 (en) * | 1994-11-02 | 1996-05-09 | Hoechst Ag | Granulated bleach activators and their manufacture |
GB2299956A (en) * | 1995-04-13 | 1996-10-23 | Procter & Gamble | Detergent compositions for dishwashers |
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 HU HU9701617A patent/HUP9701617A3/en unknown
- 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 TW TW086114779A patent/TW418252B/en not_active IP Right Cessation
- 1997-10-09 JP JP27750497A patent/JP4897988B2/en not_active Expired - Fee Related
- 1997-10-09 BR BR9704995A patent/BR9704995A/en not_active Application Discontinuation
- 1997-10-09 CZ CZ19973198A patent/CZ294306B6/en not_active IP Right Cessation
- 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
Also Published As
Publication number | Publication date |
---|---|
TW418252B (en) | 2001-01-11 |
JPH10152697A (en) | 1998-06-09 |
AR008887A1 (en) | 2000-02-23 |
DE19641708A1 (en) | 1998-04-16 |
EP0835926A3 (en) | 1999-01-07 |
KR19980032630A (en) | 1998-07-25 |
US20030207784A1 (en) | 2003-11-06 |
US6107266A (en) | 2000-08-22 |
PL322521A1 (en) | 1998-04-14 |
JP4897988B2 (en) | 2012-03-14 |
CA2216193A1 (en) | 1998-04-10 |
ES2276414T3 (en) | 2007-06-16 |
EP0835926B1 (en) | 2007-01-24 |
HUP9701617A2 (en) | 1998-07-28 |
CZ294306B6 (en) | 2004-11-10 |
DE59712800D1 (en) | 2007-03-15 |
US6645927B1 (en) | 2003-11-11 |
HUP9701617A3 (en) | 2000-03-28 |
PL188368B1 (en) | 2005-01-31 |
BR9704995A (en) | 1998-11-03 |
HU9701617D0 (en) | 1997-11-28 |
CZ319897A3 (en) | 1998-04-15 |
KR100507515B1 (en) | 2005-11-14 |
EP0835926A2 (en) | 1998-04-15 |
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