EP0710716A2 - Granulated bleach actuators and production thereof - Google Patents
Granulated bleach actuators and production thereof Download PDFInfo
- Publication number
- EP0710716A2 EP0710716A2 EP95116730A EP95116730A EP0710716A2 EP 0710716 A2 EP0710716 A2 EP 0710716A2 EP 95116730 A EP95116730 A EP 95116730A EP 95116730 A EP95116730 A EP 95116730A EP 0710716 A2 EP0710716 A2 EP 0710716A2
- Authority
- EP
- European Patent Office
- Prior art keywords
- granules
- binding material
- inorganic
- bleach activator
- weight
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
- 239000007844 bleaching agent Substances 0.000 title claims abstract description 31
- 238000004519 manufacturing process Methods 0.000 title description 5
- 239000008187 granular material Substances 0.000 claims abstract description 59
- 239000012190 activator Substances 0.000 claims abstract description 42
- 239000011230 binding agent Substances 0.000 claims abstract description 10
- 238000002156 mixing Methods 0.000 claims abstract description 5
- 238000000034 method Methods 0.000 claims description 24
- 239000000463 material Substances 0.000 claims description 21
- 239000000203 mixture Substances 0.000 claims description 17
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 9
- 239000000654 additive Substances 0.000 claims description 8
- 238000004061 bleaching Methods 0.000 claims description 8
- 238000005406 washing Methods 0.000 claims description 7
- 150000004760 silicates Chemical class 0.000 claims description 4
- 235000012216 bentonite Nutrition 0.000 claims description 3
- 229910052751 metal Chemical class 0.000 claims description 3
- 239000002184 metal Chemical class 0.000 claims description 3
- 238000003825 pressing Methods 0.000 claims description 3
- 239000002904 solvent Substances 0.000 claims description 3
- 230000000996 additive effect Effects 0.000 claims description 2
- 239000003513 alkali Substances 0.000 claims description 2
- 150000001408 amides Chemical class 0.000 claims description 2
- 150000001412 amines 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
- 238000004140 cleaning Methods 0.000 claims description 2
- 239000012459 cleaning agent Substances 0.000 claims description 2
- 239000008139 complexing agent Chemical class 0.000 claims description 2
- 239000000645 desinfectant Substances 0.000 claims description 2
- 150000002576 ketones Chemical class 0.000 claims description 2
- 229910052901 montmorillonite Inorganic materials 0.000 claims description 2
- 239000011247 coating layer Substances 0.000 claims 1
- 150000003951 lactams Chemical class 0.000 claims 1
- 150000007522 mineralic acids Chemical class 0.000 claims 1
- 150000007524 organic acids Chemical class 0.000 claims 1
- 235000005985 organic acids Nutrition 0.000 claims 1
- 239000002245 particle Substances 0.000 abstract description 9
- 238000003860 storage Methods 0.000 abstract description 8
- 239000003599 detergent Substances 0.000 description 15
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 description 9
- 239000011248 coating agent Substances 0.000 description 9
- 229910052708 sodium Inorganic materials 0.000 description 9
- 239000011734 sodium Substances 0.000 description 9
- 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 9
- 238000000576 coating method Methods 0.000 description 8
- 239000000126 substance Substances 0.000 description 8
- 239000003945 anionic surfactant Substances 0.000 description 6
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 description 5
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 5
- 150000001875 compounds Chemical class 0.000 description 5
- 238000004851 dishwashing Methods 0.000 description 5
- 238000009472 formulation Methods 0.000 description 5
- 238000000227 grinding Methods 0.000 description 5
- 150000003839 salts Chemical class 0.000 description 5
- -1 calcium aluminum silicates Chemical class 0.000 description 4
- 229920003086 cellulose ether Polymers 0.000 description 4
- 150000002191 fatty alcohols Chemical class 0.000 description 4
- 238000005469 granulation Methods 0.000 description 4
- 230000003179 granulation Effects 0.000 description 4
- 238000002844 melting Methods 0.000 description 4
- 230000008018 melting Effects 0.000 description 4
- 239000002736 nonionic surfactant Substances 0.000 description 4
- MWNQXXOSWHCCOZ-UHFFFAOYSA-L sodium;oxido carbonate Chemical compound [Na+].[O-]OC([O-])=O MWNQXXOSWHCCOZ-UHFFFAOYSA-L 0.000 description 4
- SCKXCAADGDQQCS-UHFFFAOYSA-N Performic acid Chemical compound OOC=O SCKXCAADGDQQCS-UHFFFAOYSA-N 0.000 description 3
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 3
- 230000002378 acidificating effect Effects 0.000 description 3
- 125000000129 anionic group Chemical group 0.000 description 3
- 150000001732 carboxylic acid derivatives Chemical class 0.000 description 3
- 230000000052 comparative effect Effects 0.000 description 3
- 239000004744 fabric Substances 0.000 description 3
- 150000004682 monohydrates Chemical class 0.000 description 3
- 239000000344 soap Substances 0.000 description 3
- 150000003871 sulfonates Chemical class 0.000 description 3
- 239000004215 Carbon black (E152) Substances 0.000 description 2
- 102000004190 Enzymes Human genes 0.000 description 2
- 108090000790 Enzymes Proteins 0.000 description 2
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 2
- AEMRFAOFKBGASW-UHFFFAOYSA-N Glycolic acid Chemical compound OCC(O)=O AEMRFAOFKBGASW-UHFFFAOYSA-N 0.000 description 2
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 2
- KFSLWBXXFJQRDL-UHFFFAOYSA-N Peracetic acid Chemical compound CC(=O)OO KFSLWBXXFJQRDL-UHFFFAOYSA-N 0.000 description 2
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 2
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 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
- 235000013877 carbamide Nutrition 0.000 description 2
- 239000012876 carrier material Substances 0.000 description 2
- 239000003093 cationic surfactant Substances 0.000 description 2
- 238000007906 compression Methods 0.000 description 2
- 230000006835 compression Effects 0.000 description 2
- 235000014113 dietary fatty acids Nutrition 0.000 description 2
- 238000009826 distribution Methods 0.000 description 2
- 239000000194 fatty acid Substances 0.000 description 2
- 229930195729 fatty acid Natural products 0.000 description 2
- 150000004665 fatty acids Chemical class 0.000 description 2
- 229930195733 hydrocarbon Natural products 0.000 description 2
- JVTAAEKCZFNVCJ-UHFFFAOYSA-N lactic acid Chemical compound CC(O)C(O)=O JVTAAEKCZFNVCJ-UHFFFAOYSA-N 0.000 description 2
- 239000003960 organic solvent Substances 0.000 description 2
- 150000004965 peroxy acids Chemical class 0.000 description 2
- 229920000642 polymer Polymers 0.000 description 2
- 239000000843 powder Substances 0.000 description 2
- 230000009257 reactivity Effects 0.000 description 2
- 229910021647 smectite Inorganic materials 0.000 description 2
- 239000007787 solid Substances 0.000 description 2
- 239000001993 wax Substances 0.000 description 2
- KYVZSRPVPDAAKQ-UHFFFAOYSA-N 2-benzoyloxybenzenesulfonic acid Chemical compound OS(=O)(=O)C1=CC=CC=C1OC(=O)C1=CC=CC=C1 KYVZSRPVPDAAKQ-UHFFFAOYSA-N 0.000 description 1
- BVKZGUZCCUSVTD-UHFFFAOYSA-M Bicarbonate Chemical compound OC([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-M 0.000 description 1
- 244000025254 Cannabis sativa Species 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- IAYPIBMASNFSPL-UHFFFAOYSA-N Ethylene oxide Chemical compound C1CO1 IAYPIBMASNFSPL-UHFFFAOYSA-N 0.000 description 1
- 239000005909 Kieselgur Substances 0.000 description 1
- QISSLHPKTCLLDL-UHFFFAOYSA-N N-Acetylcaprolactam Chemical compound CC(=O)N1CCCCCC1=O QISSLHPKTCLLDL-UHFFFAOYSA-N 0.000 description 1
- YIKSCQDJHCMVMK-UHFFFAOYSA-N Oxamide Chemical class NC(=O)C(N)=O YIKSCQDJHCMVMK-UHFFFAOYSA-N 0.000 description 1
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 description 1
- OFOBLEOULBTSOW-UHFFFAOYSA-N Propanedioic acid Natural products OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 0.000 description 1
- GOOHAUXETOMSMM-UHFFFAOYSA-N Propylene oxide Chemical group CC1CO1 GOOHAUXETOMSMM-UHFFFAOYSA-N 0.000 description 1
- 239000004115 Sodium Silicate Substances 0.000 description 1
- 229920002125 Sokalan® Polymers 0.000 description 1
- 229920002472 Starch Polymers 0.000 description 1
- KDYFGRWQOYBRFD-UHFFFAOYSA-N Succinic acid Natural products OC(=O)CCC(O)=O KDYFGRWQOYBRFD-UHFFFAOYSA-N 0.000 description 1
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 description 1
- 244000269722 Thea sinensis Species 0.000 description 1
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Chemical compound NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 description 1
- 150000008063 acylals Chemical class 0.000 description 1
- 239000003463 adsorbent Substances 0.000 description 1
- 150000001447 alkali salts Chemical class 0.000 description 1
- 125000000217 alkyl group Chemical group 0.000 description 1
- 229910052782 aluminium Inorganic materials 0.000 description 1
- SNAAJJQQZSMGQD-UHFFFAOYSA-N aluminum magnesium Chemical compound [Mg].[Al] SNAAJJQQZSMGQD-UHFFFAOYSA-N 0.000 description 1
- 229920006318 anionic polymer Polymers 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- KDYFGRWQOYBRFD-NUQCWPJISA-N butanedioic acid Chemical compound O[14C](=O)CC[14C](O)=O KDYFGRWQOYBRFD-NUQCWPJISA-N 0.000 description 1
- 239000004202 carbamide Substances 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 150000001735 carboxylic acids Chemical class 0.000 description 1
- 239000000969 carrier Substances 0.000 description 1
- 239000003054 catalyst Substances 0.000 description 1
- 229920006317 cationic polymer Polymers 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
- 235000021438 curry Nutrition 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 230000003111 delayed effect Effects 0.000 description 1
- 150000004844 dioxiranes Chemical class 0.000 description 1
- 238000004090 dissolution Methods 0.000 description 1
- 238000004821 distillation Methods 0.000 description 1
- 239000012153 distilled water Substances 0.000 description 1
- YRIUSKIDOIARQF-UHFFFAOYSA-N dodecyl benzenesulfonate Chemical compound CCCCCCCCCCCCOS(=O)(=O)C1=CC=CC=C1 YRIUSKIDOIARQF-UHFFFAOYSA-N 0.000 description 1
- 229940071161 dodecylbenzenesulfonate Drugs 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 150000002148 esters Chemical class 0.000 description 1
- RTZKZFJDLAIYFH-UHFFFAOYSA-N ether Substances CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 1
- 150000002170 ethers Chemical class 0.000 description 1
- 238000011156 evaluation Methods 0.000 description 1
- 239000000835 fiber Substances 0.000 description 1
- 239000006260 foam Substances 0.000 description 1
- 238000005187 foaming Methods 0.000 description 1
- 235000021588 free fatty acids Nutrition 0.000 description 1
- 229910052739 hydrogen Chemical group 0.000 description 1
- 239000001257 hydrogen Chemical group 0.000 description 1
- 125000004435 hydrogen atom Chemical group [H]* 0.000 description 1
- 230000007062 hydrolysis Effects 0.000 description 1
- 238000006460 hydrolysis reaction Methods 0.000 description 1
- 229910010272 inorganic material Inorganic materials 0.000 description 1
- 239000011147 inorganic material Substances 0.000 description 1
- 230000003993 interaction Effects 0.000 description 1
- 238000005342 ion exchange Methods 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- 239000004310 lactic acid Substances 0.000 description 1
- 235000014655 lactic acid Nutrition 0.000 description 1
- 150000002596 lactones Chemical class 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- VZCYOOQTPOCHFL-UPHRSURJSA-N maleic acid Chemical compound OC(=O)\C=C/C(O)=O VZCYOOQTPOCHFL-UPHRSURJSA-N 0.000 description 1
- 239000011976 maleic acid Substances 0.000 description 1
- WPBNNNQJVZRUHP-UHFFFAOYSA-L manganese(2+);methyl n-[[2-(methoxycarbonylcarbamothioylamino)phenyl]carbamothioyl]carbamate;n-[2-(sulfidocarbothioylamino)ethyl]carbamodithioate Chemical compound [Mn+2].[S-]C(=S)NCCNC([S-])=S.COC(=O)NC(=S)NC1=CC=CC=C1NC(=S)NC(=O)OC WPBNNNQJVZRUHP-UHFFFAOYSA-L 0.000 description 1
- 229910021527 natrosilite Inorganic materials 0.000 description 1
- 150000002825 nitriles Chemical class 0.000 description 1
- 230000003287 optical effect Effects 0.000 description 1
- 150000002894 organic compounds Chemical class 0.000 description 1
- 239000011368 organic material Substances 0.000 description 1
- 150000004028 organic sulfates Chemical class 0.000 description 1
- 150000004843 oxaziridines Chemical class 0.000 description 1
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 description 1
- 239000012188 paraffin wax Substances 0.000 description 1
- 239000002304 perfume Substances 0.000 description 1
- 229920005646 polycarboxylate Polymers 0.000 description 1
- 229920001296 polysiloxane Polymers 0.000 description 1
- 229910052700 potassium Inorganic materials 0.000 description 1
- 239000011591 potassium Substances 0.000 description 1
- 230000001681 protective effect Effects 0.000 description 1
- 239000012048 reactive intermediate Substances 0.000 description 1
- 235000020095 red wine Nutrition 0.000 description 1
- 239000002002 slurry Substances 0.000 description 1
- UIIMBOGNXHQVGW-UHFFFAOYSA-M sodium bicarbonate Substances [Na+].OC([O-])=O UIIMBOGNXHQVGW-UHFFFAOYSA-M 0.000 description 1
- 229910000030 sodium bicarbonate Inorganic materials 0.000 description 1
- 235000017557 sodium bicarbonate Nutrition 0.000 description 1
- 229910000029 sodium carbonate Inorganic materials 0.000 description 1
- 235000017550 sodium carbonate Nutrition 0.000 description 1
- 235000019351 sodium silicates Nutrition 0.000 description 1
- 229910052938 sodium sulfate Inorganic materials 0.000 description 1
- 235000011152 sodium sulphate Nutrition 0.000 description 1
- 239000002689 soil Substances 0.000 description 1
- 239000000243 solution Substances 0.000 description 1
- 238000001179 sorption measurement Methods 0.000 description 1
- 238000001694 spray drying Methods 0.000 description 1
- 238000005507 spraying Methods 0.000 description 1
- 239000008107 starch Substances 0.000 description 1
- 235000019698 starch Nutrition 0.000 description 1
- 235000000346 sugar Nutrition 0.000 description 1
- 150000008163 sugars Chemical class 0.000 description 1
- 239000004094 surface-active agent Substances 0.000 description 1
- 235000013616 tea Nutrition 0.000 description 1
- 150000004685 tetrahydrates Chemical class 0.000 description 1
- VZCYOOQTPOCHFL-UHFFFAOYSA-N trans-butenedioic acid Natural products OC(=O)C=CC(O)=O VZCYOOQTPOCHFL-UHFFFAOYSA-N 0.000 description 1
- 150000003672 ureas Chemical class 0.000 description 1
- 239000004711 α-olefin 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
- C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
- C11D3/395—Bleaching agents
-
- 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
- C11D11/00—Special methods for preparing compositions containing mixtures of detergents
-
- 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
- C11D3/02—Inorganic compounds ; Elemental compounds
- C11D3/12—Water-insoluble compounds
- C11D3/124—Silicon containing, e.g. silica, silex, quartz or glass beads
- C11D3/1246—Silicates, e.g. diatomaceous earth
- C11D3/1253—Layer silicates, e.g. talcum, kaolin, clay, bentonite, smectite, montmorillonite, hectorite or attapulgite
- C11D3/126—Layer silicates, e.g. talcum, kaolin, clay, bentonite, smectite, montmorillonite, hectorite or attapulgite in solid compositions
Definitions
- Bleach activators are important components in compact detergents, stain removal salts and machine dishwashing detergents. Already at 40-60 ° C they enable a bleaching result comparable to that of boilers by reacting with hydrogen peroxide dispensers (mostly perborates or percarbonates) to release an organic peroxycarboxylic acid.
- the achievable bleaching result is determined by the type and reactivity of the peroxycarboxylic acid formed, the structure of the bond to be hydrolyzed and the water solubility of the bleach activator. Since it is usually a reactive ester or an amide, it is often necessary to use it in granulated or coated form for the intended application in order to prevent hydrolysis in the presence of alkaline detergent components and to ensure adequate storage stability.
- EP-A-0 037 026 describes a process for producing easily soluble activator granules with active contents between 90-98% by weight.
- the pulverulent bleach activator is homogeneously mixed with likewise pulverulent cellulose or starch ethers and then sprayed with water or an aqueous solution of the cellulose ether, granulated at the same time and then dried.
- granules can be produced by spray-drying aqueous slurries containing the activator and the cellulose ether.
- Granules consisting of bleach activator, cellulose ethers and additives of an organic C3-C6 carbon or -Hydroxycarboxylic acid are described in WO 90/01535 and WO 92/13798. While in WO 90/01535 the organic carboxylic acid is incorporated into the granulate core to accelerate its solubility, in WO 92/13798 the carboxylic acid is applied to the finished granulate in an additional coating step.
- the acidic protective coat is intended to prevent spotting of the bleaching agent and to protect the color of the fabric.
- WO 94/03395 claims the use of acidic polymer compounds with a water solubility> 5 g / L (at 20 ° C.) and molecular weights of 1,000 to 250,000.
- An anhydrous manufacturing process is known from EP-A-0 075 818.
- the bleach activator is used together with an organic binder, e.g. a fatty alcohol ethoxylate, compressed by compression under pressure to form particles with a diameter of 0.5-3 mm.
- an organic binder e.g. a fatty alcohol ethoxylate
- the bleach activator to be granulated is a solid and has a high melting point. This is necessary so that it does not react and decompose with the binder or existing water during production.
- such activators are preferred which have a melting point of preferably at least 100 ° C., in particular at least 150 ° C.
- Suitable granules for use in stain salts represent a further problem.
- Modern formulations consist of mixtures of percarbonate and TAED granules.
- inert materials such as sodium carbonate, hydrogen carbonate or sulfate are often added.
- Inert binders or coating agents would be of great interest for this area of application.
- DE-OS-2 733 849 thus proposes the adsorption of liquid activators, such as diacetylmethylamine, diacetylbutylamine or acetylcaprolactam, onto inorganic adsorbents, such as diatomaceous earth, magnesium-aluminum, sodium or calcium aluminum silicates, activated silica or aluminum oxide.
- liquid activators such as diacetylmethylamine, diacetylbutylamine or acetylcaprolactam
- inorganic adsorbents such as diatomaceous earth, magnesium-aluminum, sodium or calcium aluminum silicates, activated silica or aluminum oxide.
- inorganic adsorbents such as diatomaceous earth, magnesium-aluminum, sodium or calcium aluminum silicates, activated silica or aluminum oxide.
- particles can also be produced in which a bleach activator which is solid per se is deposited in finely divided form on an inorganic carrier material.
- activator and carrier material are first mixed intimately and an organic solvent (ethanol or toluene) added, with the activator going into solution. Subsequent distillation of the solvent causes the activator to be deposited on the carrier in finely divided form.
- the preferred particle size distribution of the particles according to the invention is between 60 and 250 ⁇ m. This document does not teach how storage-stable granules can be produced from the particles loaded with activator.
- EP-A-0 240 057 discloses bleach activator granules which are prepared by mixing an activator with inorganic or organic salts, film-forming polymers and small amounts of smectite or aluminum silicates and then granulating in the presence of water. After granulation has taken place, an expensive drying stage is necessary in order to obtain storage-stable granules.
- bleach activators with melting points> 60 ° C can be used.
- Examples include tetraacetylethylenediamine (TAED), tetraacetylglucoluril (TAGU), diacetyldioxohexahydrotriazine (DADHT), Acyloxybenzenesulfonates, such as nonanoyloxybenzenesulfonate sodium (NOBS) or benzoyloxybenzenesulfonate (BOBS) and acylated sugars, such as pentaacetylglucose (PAG) or compounds described in EP-A-0 325 100, EP-A-0 492 000 and WO 91/10719.
- TAED tetraacetylethylenediamine
- TAGU tetraacetylglucoluril
- DADHT diacetyldioxohexahydrotriazine
- NABS nonanoyloxybenzenes
- bleach activators are, according to the state of the art, activated carboxylic acid esters, carboxylic acid anhydrides, lactones, acylals, carboxylic acid amides, acyl lactams, acylated ureas and oxamides, but in particular also nitriles. Mixtures of different bleach activators can also be used.
- Natural and / or artificial bentonites preferably smectite clays from the group of alkali or alkaline earth montmorillonites, saponites or hectorites with ion exchange capacities of preferably 50-100 meq / 100 g, in addition illites, attapulgites and kaolinites, are suitable as inorganic binding materials.
- ®Laundrosil DGA and ®Laundrosil EX 0242 from Süd-Chemie, Kunststoff (DE) are particularly preferred.
- Amorphous and / or crystalline layered silicates preferably crystalline, layered sodium silicates of the formula NaMSi x O 2x + 1 .yH 2 O, where M is sodium or hydrogen, x is a number from 1.9 to 4 and y is a number from 0, are also suitable to 20 and preferred values for x are 2, 3 or 4.
- Such crystalline layered silicates are described, for example, in European patent application EP-A-0 164 514.
- Particularly preferred crystalline layered silicates are those in which M is sodium and x is 2 or 3.
- both ⁇ - and ⁇ -sodium disilicate of the formula Na2Si2O5 ⁇ yH2O are preferred, wherein ⁇ -sodium disilicate can be obtained, for example, by the method described in international patent application WO-A-91/08171.
- ⁇ -sodium disilicate is commercially available under the name SKS7
- ⁇ -sodium disilicate is available under the name SKS6 (commercial products from Hoechst AG, DE).
- These powders generally have a bulk density of less than 600 g / l and have high fines content, usually more than 30 wt .-%, with a particle size below 0.1 mm.
- the aforementioned inorganic binding materials can be used as individual substances or as mixtures.
- Suitable additives are substances that influence the pH during storage and applications. These include organic carboxylic acids or their salts, such as citric acid in anhydrous or hydrated form, glycolic acid, succinic acid, maleic acid or lactic acid.
- additives are possible which influence the bleaching capacity, such as complexing agents, polycarboxylates and metal complexes containing iron or manganese, as described in EP-A-0 458 397 and EP-A-0 458 398.
- Suitable additives are anionic and nonionic surfactants, which contribute to a faster dissolution of the granules according to the invention.
- anionic surfactants are water-soluble alkali salts of organic sulfates, sulfonates and ether sulfonates with C8-C31 hydrocarbon radicals, preferably C8-C22 hydrocarbon radicals.
- anionic surfactants are: paraffin sulfonates, alkylbenzenesulfonates, such as sodium and potassium C9-C18-alkylbenzenesulfonates, preferably dodecylbenzenesulfonate, C10-C20-alpha-olefin sulfonates, C8-C18-alkyl sulfates and C8-C18-alkylethers.
- Fatty alcohol polyalkoxylates are preferred as nonionic surfactants, i.e. C8-C31 alcohols, preferably C8-C22 alcohols with 1-15 ethylene oxide and / or propylene oxide units.
- additives are substances which react in the wash liquor with the peroxycarboxylic acid released from the activator to form reactive intermediates, such as dioxiranes or oxaziridines, and can thus increase the reactivity.
- Corresponding compounds are ketones and sulfonimines corresponding to US-A-3 822 114 and EP-A-0 446 982.
- the ratio of bleach activator to inorganic binding material is usually 50:50 to 98: 2, preferably 70:30 to 96: 4% by weight, based on the total weight of the granules.
- the amount of the additive depends in particular on its type. For example, acidifying additives and organic catalysts for increasing the performance of the peracid are used in amounts of 0-20% by weight, in particular in amounts of 1-10% by weight, based on the total weight. added, however, metal complexes in concentrations in the ppm range.
- the mixture of bleach activator and binder is intimately mixed in a mixing unit (e.g. ploughshare mixer) (step a).
- a mixing unit e.g. ploughshare mixer
- the mixture is pressed into larger particles (step b).
- Suitable for this include Roller compactors.
- the compacts are then subjected to comminution (grinding) and comminuted to the desired grain size (step c). Toothed pulley rollers and / or strainers are suitable for this purpose.
- Fine fraction and coarse material are screened off and returned to the process. While the coarse fraction is directly re-shredded, the fine fraction is added to the compacting stage.
- the grain size of the product is generally in the range of 100-2000 microns, preferably 300-1800 microns.
- the bulk density of the granules according to the invention is thus above 500 kg / m3, preferably above 600 kg / m3.
- the granules obtained in this way are directly suitable for use in detergents and cleaning agents. In a special form of use, however, they can be provided with a coating envelope.
- the granulate according to the invention is coated with a film-forming substance in an additional step d), which improves the product properties can be significantly influenced.
- All film-forming substances such as waxes, silicones, fatty acids, soaps, anionic surfactants, nonionic surfactants, cationic surfactants, as well as anionic and cationic polymers, e.g. Polyacrylic acids.
- the aforementioned anionic and nonionic surfactants are preferably used.
- the preferred cationic surfactants include quaternary alkyl and / or hydroxyalkylammonium compounds.
- the dissolving behavior is delayed in order to prevent interactions between the bleach activator and the enzyme system at the beginning of the washing process.
- waxes with melting points of 40 to 50 ° C. are particularly suitable for this.
- Acidic coating materials increase the storage stability of the granules in percarbonate-containing, highly alkaline formulations and suppress color damage caused by spotting. Additions of a dye are also possible.
- the coating materials are generally applied by spraying the melted coating materials or coating materials dissolved in a solvent.
- the coating material can be applied to the granule core according to the invention in amounts of 0-20, preferably 1-10% by weight, based on the total weight.
- the products according to the invention are characterized by good storage stability in powder detergent, cleaning and disinfectant formulations.
- the granules according to the invention are mostly used in combination with a hydrogen peroxide source.
- a hydrogen peroxide source examples include perborate monohydrate, perborate tetrahydrate, percarbonates and hydrogen peroxide adducts with urea or amine oxides.
- the formulation can have further detergent components, such as organic or inorganic builders and co-builders, surfactants, enzymes, optical brighteners and perfume.
- detergent components such as organic or inorganic builders and co-builders, surfactants, enzymes, optical brighteners and perfume.
- TAED tetraacetylethylenediamine
- ®Laundrosil DGA registered trademark of Süd-Chemie
- Example 2 The procedure is analogous to Example 1. 12.5 kg of a mixture of 82% by weight of TAED, 8% by weight of ®Laundrosil DGA and 10% by weight are used Citric acid. After compacting (pressing pressure 50-60 kN, maximum temperature 57 ° C) and grinding, the following are obtained: 6.5 kg of granules with a grain size between 350-1800 ⁇ m, 4 kg of fine fraction and 2 kg of coarse material.
- Granules 1 Granules according to the invention according to Example 1
- Granules 2 Comparative example, according to EP-A-0 062 523.
- Example 6a 194 remission units
- Example 6b 192 remission units
- Example 6c 167 remission units.
- the example shows that significantly better bleaching results are achieved with the granules according to the invention than with the comparison granules.
- TAED granules are stored together with 1.5 g of perborate monohydrate and 8 g of basic detergent (WMP, laundry research in Krefeld) in folding boxes at 38 ° C and 80% humidity in a climatic cabinet (rapid test) .
- WMP laundry research in Krefeld
- the remaining TAED content is determined iodometrically at certain intervals.
- the example shows that the granulate B1 according to the invention has a storage stability comparable to the prior art, and the granulate B2 according to the invention (with the addition of citric acid) shows an even better stability.
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Abstract
Description
Bleichaktivatoren sind wichtige Bestandteile in Kompaktwaschmitteln, Fleckensalzen und Maschinengeschirrspülmitteln. Sie ermöglichen bereits bei 40-60°C ein der Kochwäsche vergleichbares Bleichergebnis, indem sie mit Wasserstoffperoxidspendern (meist Perborate oder Percarbonate) unter Freisetzung einer organischen Peroxicarbonsäure reagieren.Bleach activators are important components in compact detergents, stain removal salts and machine dishwashing detergents. Already at 40-60 ° C they enable a bleaching result comparable to that of boilers by reacting with hydrogen peroxide dispensers (mostly perborates or percarbonates) to release an organic peroxycarboxylic acid.
Das erzielbare Bleichergebnis wird bestimmt durch Art und Reaktivität der gebildeten Peroxicarbonsäure, die Struktur der zu perhydrolysierenden Bindung sowie die Wasserlöslichkeit des Bleichaktivators. Da es sich meist um einen reaktiven Ester oder ein Amid handelt, ist es in vielen Fällen notwendig, ihn für das vorgesehene Einsatzgebiet in granulierter oder gecoateter Form einzusetzen, um eine Hydrolyse in Gegenwart alkalischer Waschmittelbestandteile zu verhindern und eine ausreichende Lagerstabilität zu gewährleisten.The achievable bleaching result is determined by the type and reactivity of the peroxycarboxylic acid formed, the structure of the bond to be hydrolyzed and the water solubility of the bleach activator. Since it is usually a reactive ester or an amide, it is often necessary to use it in granulated or coated form for the intended application in order to prevent hydrolysis in the presence of alkaline detergent components and to ensure adequate storage stability.
Zur Granulierung dieser Substanzen sind in der Vergangenheit zahlreiche Hilfsstoffe und Verfahren beschrieben worden. In EP-A-0 037 026 wird ein Verfahren zur Herstellung eines leicht löslichen Aktivatorgranulates mit Aktivgehalten zwischen 90-98 Gew.-% beschrieben. Dazu wird der pulverförmige Bleichaktivator mit ebenfalls pulverförmigen Cellulose- oder Stärkeethern homogen vermischt und anschließend mit Wasser oder einer wäßrigen Lösung des Celluloseethers besprüht, gleichzeitig granuliert und anschließend getrocknet.Numerous auxiliaries and processes have been described in the past for granulating these substances. EP-A-0 037 026 describes a process for producing easily soluble activator granules with active contents between 90-98% by weight. For this purpose, the pulverulent bleach activator is homogeneously mixed with likewise pulverulent cellulose or starch ethers and then sprayed with water or an aqueous solution of the cellulose ether, granulated at the same time and then dried.
Nach EP-A-0 070 474 können ähnliche Granulate hergestellt werden, indem wäßrige Aufschlämmungen, enthaltend den Aktivator und den Celluloseether, sprühgetrocknet werden. Granulate bestehend aus Bleichaktivator, Celluloseethern und Zusätzen einer organischen C₃-C₆-Carbon- oder -Hydroxycarbonsäure werden in WO 90/01535 und WO 92/13798 beschrieben. Während in WO 90/01535 die organische Carbonsäure in den Granulatkern eingearbeitet wird, um seine Löslichkeit zu beschleunigen, wird in WO 92/13798 die Carbonsäure in einer zusätzlichen Coatingstufe auf das fertige Granulat aufgebracht. Der saure Schutzmantel soll ein Spotting des Bleichmittels verhindern und zur Farbschonung des Gewebes beitragen. In WO 94/03395 wird zum gleichen Zweck die Verwendung saurer Polymerverbindungen mit einer Wasserlöslichkeit >5 g/L (bei 20°C) und Molekulargewichten von 1 000 bis 250 000 beansprucht.According to EP-A-0 070 474, similar granules can be produced by spray-drying aqueous slurries containing the activator and the cellulose ether. Granules consisting of bleach activator, cellulose ethers and additives of an organic C₃-C₆ carbon or -Hydroxycarboxylic acid are described in WO 90/01535 and WO 92/13798. While in WO 90/01535 the organic carboxylic acid is incorporated into the granulate core to accelerate its solubility, in WO 92/13798 the carboxylic acid is applied to the finished granulate in an additional coating step. The acidic protective coat is intended to prevent spotting of the bleaching agent and to protect the color of the fabric. For the same purpose, WO 94/03395 claims the use of acidic polymer compounds with a water solubility> 5 g / L (at 20 ° C.) and molecular weights of 1,000 to 250,000.
Ebenfalls Stand der Technik (GB-A 1 507 312) sind Granulate von Bleichaktivatoren, in denen Gemische von Seifen und freien Fettsäuren als Granulierhilfsmittel zum Einsatz kommen.Also state of the art (GB-A 1 507 312) are granules of bleach activators, in which mixtures of soaps and free fatty acids are used as granulation aids.
Ein wasserfreies Herstellverfahren ist aus EP-A-0 075 818 bekannt. Dazu wird der Bleichaktivator zusammen mit einem organischen Bindemittel, z.B. einem Fettalkoholethoxylat, durch Kompaktierung unter Druck zu Teilchen mit Durchmessern von 0.5 - 3 mm verpreßt.An anhydrous manufacturing process is known from EP-A-0 075 818. For this purpose the bleach activator is used together with an organic binder, e.g. a fatty alcohol ethoxylate, compressed by compression under pressure to form particles with a diameter of 0.5-3 mm.
Für die meisten der genannten Granulierverfahren ist Voraussetzung, daß der zu granulierende Bleichaktivator ein Feststoff ist und einen hohen Schmelzpunkt aufweist. Dies ist notwendig, damit er bei der Herstellung nicht mit dem Binder oder vorhandenem Wasser abreagiert und zersetzt wird. So werden z.B. in DE-OS-2 048 331 solche Aktivatoren bevorzugt, die einen Schmelzpunkt von vorzugsweise mindestens 100°C, insbesondere wenigstens 150°C aufweisen.For most of the granulation processes mentioned, it is a prerequisite that the bleach activator to be granulated is a solid and has a high melting point. This is necessary so that it does not react and decompose with the binder or existing water during production. For example, in DE-OS-2 048 331 such activators are preferred which have a melting point of preferably at least 100 ° C., in particular at least 150 ° C.
Als Bindemittel wurden bisher überwiegend organische Verbindungen verwendet. Hieraus können sich jedoch Probleme ergeben, die die Verwendung der Granulate einschränken.So far, mostly organic compounds have been used as binders. However, this can result in problems which restrict the use of the granules.
Werden oberflächenaktive Verbindungen eingesetzt, wie Seifen, Fettsäuren, anionische Tenside oder Fettalkoholethoxylate, so sind die damit hergestellten Granulate zum Einsatz in Maschinengeschirrspülmitteln ungeeignet, da unter Waschbedingungen Schaumprobleme auftreten. Dies ist selbst bei Verwendung normalerweise schwach schäumender hochethoxylierter Fettalkohole der Fall. Zum Einsatz in Maschinengeschirrspülmitteln werden daher überwiegend Aktivatorgranulate verwendet, deren Bindemittel aus Celluloseethern besteht. Die biologische Abbaubarkeit dieser Produktgruppe ist jedoch mäßig.If surface-active compounds are used, such as soaps, fatty acids, anionic surfactants or fatty alcohol ethoxylates, then those produced are Granules are unsuitable for use in machine dishwashing detergents because foam problems occur under washing conditions. This is the case even when using normally low-foaming, highly ethoxylated fatty alcohols. Activator granules whose binders consist of cellulose ethers are therefore predominantly used for use in machine dishwashing detergents. However, the biodegradability of this product group is moderate.
Ein weiteres Problem stellen geeignete Granulate zum Einsatz in Fleckensalzen dar. Moderne Formulierungen bestehen aus Mischungen von Percarbonat und TAED-Granulaten. Um eine exotherme Zersetzung dieser Mischungen (Percarbonat als brandfördernder Stoff in Kombination mit organischem Material) bei Herstellung und Lagerung zu unterbinden, werden häufig Inertmaterialien, wie Natriumcarbonat, -hydrogencarbonat oder -sulfat zugegeben. Für diesen Anwendungsbereich wären inerte Binde- oder Coatingmittel von großem Interesse.Suitable granules for use in stain salts represent a further problem. Modern formulations consist of mixtures of percarbonate and TAED granules. In order to prevent exothermic decomposition of these mixtures (percarbonate as a fire-promoting substance in combination with organic material) during manufacture and storage, inert materials such as sodium carbonate, hydrogen carbonate or sulfate are often added. Inert binders or coating agents would be of great interest for this area of application.
Es besteht daher weiterhin Bedarf an geeigneten Aktivator-Granulaten, die aus ökologischer Sicht unproblematisch, universell einsetzbar und kostengünstig herzustellen sind.There is therefore still a need for suitable activator granules which are unproblematic from an ecological point of view, can be used universally and are inexpensive to produce.
Anorganische Materialien als Träger für Bleichaktivatoren sind an sich bekannt. So wird in DE-OS-2 733 849 die Adsorption flüssiger Aktivatoren, wie Diacetylmethylamin, Diacetylbutylamin oder Acetylcaprolactam, an anorganische Adsorbentien, wie Kieselgur, Magnesium-Aluminium-, Natrium- oder Calciumaluminiumsilikate, aktivierte Kieselsäure oder Aluminiumoxid, vorgeschlagen. Es wird jedoch nicht gelehrt, wie diese Teilchen in geeignete, lagerstabile Granulate überführt werden können.Inorganic materials as carriers for bleach activators are known per se. DE-OS-2 733 849 thus proposes the adsorption of liquid activators, such as diacetylmethylamine, diacetylbutylamine or acetylcaprolactam, onto inorganic adsorbents, such as diatomaceous earth, magnesium-aluminum, sodium or calcium aluminum silicates, activated silica or aluminum oxide. However, it is not taught how these particles can be converted into suitable, storage-stable granules.
Weiterhin können nach GB-A-2 249 104 Partikel hergestellt werden, in denen ein an sich fester Bleichaktivator in fein verteilter Form auf anorganischem Trägermaterial abgelagert ist. Hierzu werden Aktivator und Trägermaterial zunächst innig gemischt und ein organisches Lösemittel (Ethanol oder Toluol) hinzugefügt, wobei der Aktivator in Lösung geht. Durch anschließende Abdestillation des Lösemittels wird der Aktivator in feinst verteilter Form auf dem Träger abgelagert. Die bevorzugte Korngrößenverteilung der erfindungsgemäßen Partikel liegt zwischen 60 und 250 µm. Diese Schrift lehrt nicht, wie aus den Aktivator-beladenen Partikeln lagerstabile Granulate hergestellt werden können.According to GB-A-2 249 104 particles can also be produced in which a bleach activator which is solid per se is deposited in finely divided form on an inorganic carrier material. For this purpose, activator and carrier material are first mixed intimately and an organic solvent (ethanol or toluene) added, with the activator going into solution. Subsequent distillation of the solvent causes the activator to be deposited on the carrier in finely divided form. The preferred particle size distribution of the particles according to the invention is between 60 and 250 μm. This document does not teach how storage-stable granules can be produced from the particles loaded with activator.
Daneben sind aus EP-A-0 240 057 Bleichaktivator-Granulate bekannt, die durch Vermischen eines Aktivators mit anorganischen oder organischen Salzen, filmbildenden Polymeren und geringen Mengen Smectite oder Aluminiumsilikate und anschließender Granulierung in Gegenwart von Wasser hergestellt werden. Nach erfolgter Granulierung ist eine kostenintensive Trockenstufe notwendig, um lagerstabile Granulate zu erhalten.In addition, EP-A-0 240 057 discloses bleach activator granules which are prepared by mixing an activator with inorganic or organic salts, film-forming polymers and small amounts of smectite or aluminum silicates and then granulating in the presence of water. After granulation has taken place, an expensive drying stage is necessary in order to obtain storage-stable granules.
Überraschenderweise wurde nun gefunden, daß sich lagerstabile Aktivatorgranulate, die die o.g. Eigenschaften aufweisen, auf einfache Weise herstellen lassen, wenn als Bindemittel Bentonite verwendet werden und der Granulierprozeß wasserfrei und ohne Verwendung organischer Lösemittel oder filmbildender Stoffe durchgeführt wird.Surprisingly, it has now been found that storage-stable activator granules which contain the abovementioned. Have properties that can be produced in a simple manner if bentonites are used as the binder and the granulation process is carried out without water and without the use of organic solvents or film-forming substances.
Gegenstand der vorliegenden Erfindung ist ein Verfahren zur Herstellung eines lagerstabilen Granulates bestehend im wesentlichen aus Bleichaktivator und anorganischem Bindematerial, das durch folgende Verfahrensschritte gekennzeichnet ist:
- Vermischen eines trockenen Bleichaktivators mit einem trockenen anorganischen Bindematerial,
- Verpressung dieser Mischung zu größeren Agglomeraten und
- Zerkleinern dieser Agglomerate auf die gewünschte Korngröße.
- Mixing a dry bleach activator with a dry inorganic binding material,
- Compression of this mixture into larger agglomerates and
- Crush these agglomerates to the desired grain size.
Gemäß der Erfindung können als Bleichaktivatoren solche mit Schmelzpunkten >60°C verwendet werden. Beispiele hierfür sind Tetraacetylethylendiamin (TAED), Tetraacetylglukoluril (TAGU), Diacetyldioxohexahydrotriazin (DADHT), Acyloxibenzolsulfonate, wie Nonanoyloxibenzolsulfonat-Natrium (NOBS) oder Benzoyloxibenzolsulfonat (BOBS) und acylierte Zucker, wie Pentaacetylglucose (PAG) oder Verbindungen beschrieben in EP-A-0 325 100, EP-A-0 492 000 und WO 91/10719.According to the invention, bleach activators with melting points> 60 ° C can be used. Examples include tetraacetylethylenediamine (TAED), tetraacetylglucoluril (TAGU), diacetyldioxohexahydrotriazine (DADHT), Acyloxybenzenesulfonates, such as nonanoyloxybenzenesulfonate sodium (NOBS) or benzoyloxybenzenesulfonate (BOBS) and acylated sugars, such as pentaacetylglucose (PAG) or compounds described in EP-A-0 325 100, EP-A-0 492 000 and WO 91/10719.
Weitere geeignete Bleichmittelaktivatoren sind dem Stand der Technik entsprechend aktivierte Carbonsäureester, Carbonsäureanhydride, Lactone, Acylale, Carbonsäureamide, Acyllactame, acylierte Harnstoffe und Oxamide, daneben insbesondere aber auch Nitrile. Mischungen verschiedener Bleichaktivatoren können ebenfalls zum Einsatz kommen.Further suitable bleach activators are, according to the state of the art, activated carboxylic acid esters, carboxylic acid anhydrides, lactones, acylals, carboxylic acid amides, acyl lactams, acylated ureas and oxamides, but in particular also nitriles. Mixtures of different bleach activators can also be used.
Als anorganisches Bindematerial kommen in Frage natürliche und/oder künstliche Bentonite, bevorzugt smektitische Tone aus der Gruppe der Alkali- oder Erdalkali- Montmorillonite, Saponite oder Hectorite mit Ionenaustauschkapazitäten von bevorzugt 50-100 meq/100 g, daneben Illite, Attapulgite und Kaolinite. Besonders bevorzugt werden ®Laundrosil DGA und ®Laundrosil EX 0242 der Firma Süd-Chemie, München (DE).Natural and / or artificial bentonites, preferably smectite clays from the group of alkali or alkaline earth montmorillonites, saponites or hectorites with ion exchange capacities of preferably 50-100 meq / 100 g, in addition illites, attapulgites and kaolinites, are suitable as inorganic binding materials. ®Laundrosil DGA and ®Laundrosil EX 0242 from Süd-Chemie, Munich (DE) are particularly preferred.
Des weiteren kommen in Frage amorphe und/oder kristalline Schichtsilikate, bevorzugt kristalline, schichtförmige Natriumsilikate der Formel NaMSixO2x+1·yH₂O, wobei M Natrium oder Wasserstoff bedeutet, x eine Zahl von 1,9 bis 4 und y eine Zahl von 0 bis 20 ist und bevorzugte Werte für x 2, 3 oder 4 sind. Derartige kristalline Schichtsilikate werden beispielsweise in der europäischen Patentanmeldung EP-A-0 164 514 beschrieben. Besonders bevorzugte kristalline Schichtsilikate sind solche, in denen M für Natrium steht und x die Werte 2 oder 3 annimmt. Insbesondere sind sowohl β- als auch δ-Natriumdisilikate der Formel Na₂Si₂O₅·yH₂O bevorzugt, wobei β-Natriumdisilikat beispielsweise nach dem Verfahren erhalten werden kann, das in der internationalen Patentanmeldung WO-A-91/08171 beschrieben ist. β-Natriumdisilikat ist unter der Bezeichnung SKS7, δ-Natriumdisilikat ist unter der Bezeichnung SKS6 im Handel erhältlich (Handelsprodukte der Hoechst AG, DE). Diese Pulver weisen im allgemeinen ein Schüttgewicht unter 600 g/l auf und besitzen hohe Feinkornanteile, üblicherweise mehr als 30 Gew.-%, mit einer Teilchengröße unterhalb 0,1 mm.Amorphous and / or crystalline layered silicates, preferably crystalline, layered sodium silicates of the formula NaMSi x O 2x + 1 .yH 2 O, where M is sodium or hydrogen, x is a number from 1.9 to 4 and y is a number from 0, are also suitable to 20 and preferred values for x are 2, 3 or 4. Such crystalline layered silicates are described, for example, in European patent application EP-A-0 164 514. Particularly preferred crystalline layered silicates are those in which M is sodium and x is 2 or 3. In particular, both β- and δ-sodium disilicate of the formula Na₂Si₂O₅ · yH₂O are preferred, wherein β-sodium disilicate can be obtained, for example, by the method described in international patent application WO-A-91/08171. β-sodium disilicate is commercially available under the name SKS7, δ-sodium disilicate is available under the name SKS6 (commercial products from Hoechst AG, DE). These powders generally have a bulk density of less than 600 g / l and have high fines content, usually more than 30 wt .-%, with a particle size below 0.1 mm.
Je nach Bedarf können die vorgenannten anorganischen Bindematerialien als Einzelstoffe oder als Gemische eingesetzt werden.Depending on requirements, the aforementioned inorganic binding materials can be used as individual substances or as mixtures.
Geeignete Zusätze sind Stoffe, die den pH-Wert während Lagerung und Anwendungen beeinflussen. Dazu zählen organische Carbonsäuren oder deren Salze, wie Zitronensäure in wasserfreier oder hydratisierter Form, Glycolsäure, Bernsteinsäure, Maleinsäure oder Milchsäure. Daneben sind Zusätze möglich, die das Bleichvermögen beeinflussen, wie Komplexbildner, Polycarboxylate und Eisen- bzw. Mangan-haltige Metallkomplexe, wie in EP-A-0 458 397 und EP-A-0 458 398 beschrieben.Suitable additives are substances that influence the pH during storage and applications. These include organic carboxylic acids or their salts, such as citric acid in anhydrous or hydrated form, glycolic acid, succinic acid, maleic acid or lactic acid. In addition, additives are possible which influence the bleaching capacity, such as complexing agents, polycarboxylates and metal complexes containing iron or manganese, as described in EP-A-0 458 397 and EP-A-0 458 398.
Ebenfalls geeignete Zusätze sind anionische und nichtionische Tenside, die zu einer schnelleren Auflösung der erfindungsgemäßen Granulate beitragen.Also suitable additives are anionic and nonionic surfactants, which contribute to a faster dissolution of the granules according to the invention.
Bevorzugt anionische Tenside sind wasserlösliche Alkalisalze von organischen Sulfaten, Sulfonaten und Ethersulfonaten mit C₈-C₃₁-Kohlenwasserstoffresten, bevorzugt C₈-C₂₂-Kohlenwasserstoffresten. Beispielhaft für anionische Tenside seien genannt: Paraffinsulfonate, Alkylbenzolsulfonate, wie Natrium- und Kalium-C₉-C₁₈-Alkylbenzolsulfonate, bevorzugt Dodecylbenzolsulfonat, C₁₀-C₂₀-alpha-Olefinsulfonate, C₈-C₁₈-Alkylsulfate und C₈-C₁₈-Alkylethersulfate.Preferred anionic surfactants are water-soluble alkali salts of organic sulfates, sulfonates and ether sulfonates with C₈-C₃₁ hydrocarbon radicals, preferably C₈-C₂₂ hydrocarbon radicals. Examples of anionic surfactants are: paraffin sulfonates, alkylbenzenesulfonates, such as sodium and potassium C₉-C₁₈-alkylbenzenesulfonates, preferably dodecylbenzenesulfonate, C₁₀-C₂₀-alpha-olefin sulfonates, C₈-C₁₈-alkyl sulfates and C₈-C₁₈-alkylethers.
Als nichtionische Tenside werden Fettalkoholpolyalkoxylate bevorzugt, d.h. C₈-C₃₁-Alkohole, bevorzugt C₈-C₂₂-Alkohole mit 1 - 15 Ethylenoxid- und/oder Propylenoxideinheiten.Fatty alcohol polyalkoxylates are preferred as nonionic surfactants, i.e. C₈-C₃₁ alcohols, preferably C₈-C₂₂ alcohols with 1-15 ethylene oxide and / or propylene oxide units.
Weitere Zusätze sind Stoffe, die in der Waschlauge mit der aus dem Aktivator freigesetzten Peroxicarbonsäure unter Bildung reaktiver Zwischenstufen, wie Dioxiranen oder Oxaziridinen, reagieren und auf diese Weise die Reaktivität erhöhen können. Entsprechende Verbindungen sind Ketone und Sulfonimine entsprechend US-A-3 822 114 und EP-A-0 446 982.Other additives are substances which react in the wash liquor with the peroxycarboxylic acid released from the activator to form reactive intermediates, such as dioxiranes or oxaziridines, and can thus increase the reactivity. Corresponding compounds are ketones and sulfonimines corresponding to US-A-3 822 114 and EP-A-0 446 982.
Das Verhältnis von Bleichaktivator zu anorganischem Bindematerial beträgt üblicherweise 50:50 bis 98:2, vorzugsweise 70:30 bis 96:4 Gew.-%, bezogen auf das Gesamtgewicht des Granulats. Die Menge des Zusatzstoffes richtet sich insbesondere nach seiner Art. So werden acidifizierende Zusätze und organische Katalysatoren zur Leistungssteigerung der Persäure in Mengen von 0-20 Gew.-%, insbesondere in Mengen von 1-10 Gew.-%, bezogen auf das Gesamtgewicht, zugesetzt, Metallkomplexe hingegen in Konzentrationen im ppm Bereich.The ratio of bleach activator to inorganic binding material is usually 50:50 to 98: 2, preferably 70:30 to 96: 4% by weight, based on the total weight of the granules. The amount of the additive depends in particular on its type. For example, acidifying additives and organic catalysts for increasing the performance of the peracid are used in amounts of 0-20% by weight, in particular in amounts of 1-10% by weight, based on the total weight. added, however, metal complexes in concentrations in the ppm range.
Zur Herstellung der Granulate wird zunächst in einem Mischaggregat (z.B. Pflugscharmischer) die Mischung aus Bleichaktivator und Bindemittel innig vermischt (Schritt a). In einem zweiten Schritt wird das Gemisch zu größeren Partikeln verpreßt (Schritt b). Geeignet hierfür sind u.a. Walzenkompaktoren. Die Preßlinge werden anschließend der Zerkleinerung (Mahlung) unterworfen und auf die gewünschte Korngröße zerkleinert (Schritt c). Zu diesem Zweck eignen sich Zahnscheibenwalzen und/oder Passiersiebe.To produce the granules, the mixture of bleach activator and binder is intimately mixed in a mixing unit (e.g. ploughshare mixer) (step a). In a second step, the mixture is pressed into larger particles (step b). Suitable for this include Roller compactors. The compacts are then subjected to comminution (grinding) and comminuted to the desired grain size (step c). Toothed pulley rollers and / or strainers are suitable for this purpose.
Feinanteil und Grobgut werden abgesiebt und in den Prozeß zurückgeführt. Während der Grobanteil direkt einer erneuten Zerkleinerung zugeführt wird, wird der Feinanteil der Kompaktierstufe zugesetzt. Die Korngröße des Produktes liegt im allgemeinen im Bereich von 100-2000 µm, vorzugsweise 300-1800 µm. Das Schüttgewicht der erfindungsgemäßen Granulate liegt damit oberhalb 500 kg/m³, vorzugsweise oberhalb 600 kg/m³.Fine fraction and coarse material are screened off and returned to the process. While the coarse fraction is directly re-shredded, the fine fraction is added to the compacting stage. The grain size of the product is generally in the range of 100-2000 microns, preferably 300-1800 microns. The bulk density of the granules according to the invention is thus above 500 kg / m³, preferably above 600 kg / m³.
Die auf diese Weise erhaltenen Granulate sind direkt zum Einsatz in Wasch- und Reinigungsmitteln geeignet. In einer besonderen Verwendungsform können sie jedoch mit einer Coatinghülle versehen werden.The granules obtained in this way are directly suitable for use in detergents and cleaning agents. In a special form of use, however, they can be provided with a coating envelope.
Hierzu wird das erfindungsgemäße Granulat in einem zusätzlichen Schritt d) mit einer filmbildenden Substanz umhüllt, wodurch die Produkteigenschaften erheblich beeinflußt werden können.For this purpose, the granulate according to the invention is coated with a film-forming substance in an additional step d), which improves the product properties can be significantly influenced.
Als Coatingmaterial geeignet sind alle filmbildenden Substanzen, wie Wachse, Silikone, Fettsäuren, Seifen, anionische Tenside, nichtionische Tenside, kationische Tenside, sowie anionische und kationische Polymere, z.B. Polyacrylsäuren.All film-forming substances, such as waxes, silicones, fatty acids, soaps, anionic surfactants, nonionic surfactants, cationic surfactants, as well as anionic and cationic polymers, e.g. Polyacrylic acids.
Bevorzugt werden die zuvor genannten anionischen und nichtionischen Tenside verwendet. Zu den bevorzugten kationischen Tensiden zählen quaternäre Alkyl- und/oder Hydroxyalkylammoniumverbindungen.The aforementioned anionic and nonionic surfactants are preferably used. The preferred cationic surfactants include quaternary alkyl and / or hydroxyalkylammonium compounds.
Durch Verwendung dieser Coatingmaterialien kann u.a. das Auflöseverhalten verzögert werden, um auf diese Weise Wechselwirkungen zwischen dem Bleichaktivator und dem Enzymsystem zu Beginn des Waschprozesses zu unterbinden.By using these coating materials, i.a. the dissolving behavior is delayed in order to prevent interactions between the bleach activator and the enzyme system at the beginning of the washing process.
Soll das erfindungsgemäße Granulat in Maschinengeschirrspülmitteln Verwendung finden, eignen sich hierzu vor allem Wachse mit Schmelzpunkten von 40 bis 50°C.If the granules according to the invention are to be used in machine dishwashing detergents, waxes with melting points of 40 to 50 ° C. are particularly suitable for this.
Saure Coatingmaterialien erhöhen die Lagerstabilität der Granulate in percarbonathaltigen, hochalkalischen Formulierungen und unterdrücken Farbschäden durch Spotting. Zusätze eines Farbstoffes sind ebenfalls möglich.Acidic coating materials increase the storage stability of the granules in percarbonate-containing, highly alkaline formulations and suppress color damage caused by spotting. Additions of a dye are also possible.
Das Aufbringen der Coatingmaterialien erfolgt in der Regel durch Aufsprühen der geschmolzenen oder in einem Lösemittel gelösten Coatingmaterialien. Gemäß der Erfindung kann das Coatingmaterial in Mengen von 0-20, vorzugsweise von 1-10 Gew.-%, bezogen auf das Gesamtgewicht, auf den erfindungsgemäßen Granulatkern aufgebracht werden.The coating materials are generally applied by spraying the melted coating materials or coating materials dissolved in a solvent. According to the invention, the coating material can be applied to the granule core according to the invention in amounts of 0-20, preferably 1-10% by weight, based on the total weight.
Die erfindungsgemäßen Produkte zeichnen sich durch eine gute Lagerstabilität in pulverförmigen Wasch-, Reinigungs- und Desinfektionsmittelformulierungen aus.The products according to the invention are characterized by good storage stability in powder detergent, cleaning and disinfectant formulations.
Sie sind ideal zum Einsatz in Vollwaschmitteln, Fleckensalzen, Maschinengeschirrspülmitteln, pulverförmigen Allzweckreinigern und Gebißreinigern.They are ideal for use in heavy-duty detergents, stain salts, machine dishwashing detergents, powdered all-purpose cleaners and denture cleaners.
In diesen Formulierungen werden die erfindungsgemäßen Granulate meist in Kombination mit einer Wasserstoffperoxidquelle eingesetzt. Beispiele dafür sind Perborat-Monohydrat, Perborat-Tetrahydrat, Percarbonate sowie Wasserstoffperoxid-Addukte an Harnstoff oder Aminoxiden.In these formulations, the granules according to the invention are mostly used in combination with a hydrogen peroxide source. Examples include perborate monohydrate, perborate tetrahydrate, percarbonates and hydrogen peroxide adducts with urea or amine oxides.
Daneben kann die Formulierung dem Stand der Technik entsprechend weitere Waschmittelbestandteile aufweisen, wie organische oder anorganische Builder und Co-Builder, Tenside, Enzyme, optische Aufheller und Parfüm.In addition, according to the prior art, the formulation can have further detergent components, such as organic or inorganic builders and co-builders, surfactants, enzymes, optical brighteners and perfume.
In einem 50-l-Lödige-Mischer werden 12,5 kg einer Mischung aus 92 Gew.-% Tetraacetylethylendiamin (TAED) und 8 Gew.-% ®Laundrosil DGA (eingetragenes Warenzeichen der Süd-Chemie) mit einer Drehzahl von 52/min 20 min vermischt. Diese Mischung wird bei 38°C auf einem Walzenkompaktor mit einer Preßkraft von 40-50 kN zu zigarrenförmigen Kissen verpreßt und anschließend der zweistufigen Mahlung zugeführt. Nach einer Vormahlung mit Zahnscheibenwalzen (Alexanderwerk) wird das Produkt in einem Passiersieb (Frewitt) bei einer Maschenweite von 2000 µm zerkleinert. Man erhält 6,3 kg Granulat mit einer Korngrößenverteilung von 350-1800 µm (Ausbeute 50,2%), sowie 3,6 kg Feinanteil (<350 µm), die der erneuten Kompaktierung zugeführt werden und 2,6 kg Grobanteil (>1800 µm), die der erneuten Mahlung zugeführt werden.In a 50 l Lödige mixer, 12.5 kg of a mixture of 92% by weight tetraacetylethylenediamine (TAED) and 8% by weight ®Laundrosil DGA (registered trademark of Süd-Chemie) are run at a speed of 52 rpm Mixed for 20 min. This mixture is pressed at 38 ° C on a roller compactor with a pressing force of 40-50 kN to cigar-shaped pillows and then fed to the two-stage grinding. After pre-grinding with toothed disc rollers (Alexanderwerk), the product is crushed in a pass sieve (Frewitt) with a mesh size of 2000 µm. This gives 6.3 kg of granules with a grain size distribution of 350-1800 μm (yield 50.2%), as well as 3.6 kg of fine fraction (<350 μm), which are fed to the new compacting and 2.6 kg of coarse fraction (> 1800 µm), which are fed to the new grinding.
Es wird analog Beispiel 1 verfahren. Eingesetzt werden 12,5 kg einer Mischung aus 82 Gew.-% TAED, 8 Gew.-% ®Laundrosil DGA und 10 Gew.-% Zitronensäure. Nach Kompaktierung (Preßdruck 50-60 kN, maximale Temperatur 57°C) und Mahlung werden erhalten:
6,5 kg Granulat mit einer Korngröße zwischen 350-1800 µm, 4 kg Feinanteil und 2 kg Grobgut.The procedure is analogous to Example 1. 12.5 kg of a mixture of 82% by weight of TAED, 8% by weight of ®Laundrosil DGA and 10% by weight are used Citric acid. After compacting (pressing pressure 50-60 kN, maximum temperature 57 ° C) and grinding, the following are obtained:
6.5 kg of granules with a grain size between 350-1800 µm, 4 kg of fine fraction and 2 kg of coarse material.
Es wird analog Beispiel 1 verfahren, jedoch an Stelle des ®Laundrosil DGA wird ®Laundrosil EX 0242 (Süd-Chemie) verwendet.The procedure is analogous to Example 1, but ®Laundrosil EX 0242 (Süd-Chemie) is used instead of the ®Laundrosil DGA.
Ausbeuten: 6.5 kg Granulat, 3,8 kg Feinanteil und 2,2 kg Grobgut.Yields: 6.5 kg of granules, 3.8 kg of fines and 2.2 kg of coarse material.
Es wird analog Beispiel 2 verfahren, jedoch an Stelle des ®Laundrosil DGA wird ®Laundrosil EX 0242 (Süd-Chemie) verwendet. Ausbeuten: 6,4 kg Granulat, 3,8 kg Feinanteil und 2,1 kg Grobanteil.The procedure is analogous to Example 2, but ®Laundrosil EX 0242 (Süd-Chemie) is used instead of the ®Laundrosil DGA. Yields: 6.4 kg granulate, 3.8 kg fine fraction and 2.1 kg coarse fraction.
In einem auf 20°C temperierten Becherglas werden 6,75 g Standardwaschmittel ohne Bleichsystem (WMP-Waschmittel, Wäschereiforschung Krefeld (DE)) und 0,75 g Perborat-Monohydrat in 1 l destilliertem Wasser gelöst und anschließend werden 0,3 g des Aktivators hinzugegeben. Als Aktivatoren werden verwendet: Granulat 1: erfindungsgemäßes Granulat nach Beispiel 1 Granulat 2: Vergleichsbeispiel, gemäß EP-A-0 062 523.6.75 g of standard detergent without bleaching system (WMP detergent, laundry research Krefeld (DE)) and 0.75 g of perborate monohydrate are dissolved in 1 l of distilled water in a beaker at 20 ° C and then 0.3 g of the activator are dissolved added. The following are used as activators: Granules 1: Granules according to the invention according to Example 1 Granules 2: Comparative example, according to EP-A-0 062 523.
In Zeitabständen von einer Minute werden Proben entnommen und der Gehalt an gebildeter Peressigsäure jodometrisch bestimmt.
Das Beispiel macht deutlich, daß sich das erfindungsgemäße Granulat besser löst als das Vergleichsgranulat, hergestellt nach EP-A-0 062 523.The example makes it clear that the granules according to the invention dissolve better than the comparative granules produced according to EP-A-0 062 523.
Die Bleichaktivität der erfindungsgemäßen Granulate wird unter praxisnahen Bedingungen in einer Mehrkomponeneten-Waschmaschine Öko-Lavamat 6753 (AEG, Nürnberg) an Bleichtestgeweben in Gegenwart sauberer Testwäsche geprüft. Entsprechend der Dosiervorschrift für Wasserhärtebereich 3 werden 14 g Enthärter (®Skip, Lever Europe) und 70 g Grundwaschmittel ohne Bleiche (®Skip, Lever Europe) in die dafür vorgesehenen Einspülkammern der Waschmaschine gegeben. Als Bleichkomponente werden in die dafür vorgesehene Einspülkammer gegeben 9,6 g NaHCO₃ und 8,0 g Percarbonat sowie
- a) 2,61 g Bleichaktivatorgranulat (92 %ig) gemäß Beispiel 1
- b) 2,93 g Bleichaktivatorgranulat (92 %ig) gemäß Beispiel 3
- c) 2,65 g Bleichaktivatorgranulat (90.5 %ig) gemäß EP 062 523.
- a) 2.61 g of bleach activator granules (92%) according to Example 1
- b) 2.93 g of bleach activator granules (92%) according to Example 3
- c) 2.65 g bleach activator granules (90.5%) according to EP 062 523.
Als Ballaststoff werden 2 kg Frotteegewebe verwendet, als Testanschmutzungen 10 bleichbare Anschmutzungen (Tee, Rotwein, Curry, Gras usw. der Wäschereiforschung Krefeld). Die Wäsche wird im Hauptwaschgang bei 40°C gewaschen. Die Auswertung erfolgt durch Bestimmung des Weißgrades nach der Wäsche durch Addition der Remissionsdifferenzen.2 kg of terry cloth are used as fiber, 10 bleachable stains (tea, red wine, curry, grass etc. from Krefeld laundry research) are used as test soils. The laundry is washed in the main wash cycle at 40 ° C. The evaluation is carried out by determining the degree of whiteness after washing by adding the remission differences.
Summe Weißgrad nach der Wäsche:
Beispiel 6a: 194 Remissionseinheiten
Beispiel 6b: 192 Remissionseinheiten
Beispiel 6c: 167 Remissionseinheiten.Total whiteness after washing:
Example 6a: 194 remission units
Example 6b: 192 remission units
Example 6c: 167 remission units.
Das Beispiel belegt, daß mit den erfindungsgemäßen Granulaten deutlich bessere Bleichergebnisse erzielt werden als mit dem Vergleichsgranulat.The example shows that significantly better bleaching results are achieved with the granules according to the invention than with the comparison granules.
Zur Bestimmung der Lagerstabilität werden 0,5 g der TAED-Granulate zusammen mit 1,5 g Perborat-Monohydrat und 8 g Basis-Waschmittel (WMP, Wäschereiforschung Krefeld) in Faltschachteln bei 38°C und 80 % Luftfeuchte im Klimaschrank gelagert (Schnelltest). In bestimmten Zeitabständen wird der verbleibende TAED-Gehalt jodometrisch bestimmt.To determine the storage stability, 0.5 g of the TAED granules are stored together with 1.5 g of perborate monohydrate and 8 g of basic detergent (WMP, laundry research in Krefeld) in folding boxes at 38 ° C and 80% humidity in a climatic cabinet (rapid test) . The remaining TAED content is determined iodometrically at certain intervals.
- B1: erfindungsgemaßes Granulat gemäß Beispiel 1B1: Granules according to the invention according to Example 1
- B2: erfindungsgemäßes Granulat gemäß Beispiel 2B2: Granules according to the invention according to Example 2
- B3: Vergleichsbeispiel Granulat gemäß EP-A-0 037 026.B3: Comparative example of granules according to EP-A-0 037 026.
Das Beispiel zeigt, daß das erfindungsgemäße Granulat B1 eine dem Stand der Technik vergleichbare Lagerstabilität aufweist, und das erfindungsgemäße Granulat B2 (mit Zusatz von Zitronensäure) ein noch bessere Stabilität zeigt.The example shows that the granulate B1 according to the invention has a storage stability comparable to the prior art, and the granulate B2 according to the invention (with the addition of citric acid) shows an even better stability.
Claims (11)
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| DE4439039A DE4439039A1 (en) | 1994-11-02 | 1994-11-02 | Granulated bleach activators and their manufacture |
| DE4439039 | 1994-11-02 |
Publications (3)
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| EP0710716A2 true EP0710716A2 (en) | 1996-05-08 |
| EP0710716A3 EP0710716A3 (en) | 1998-07-08 |
| EP0710716B1 EP0710716B1 (en) | 2002-07-24 |
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| EP95116730A Expired - Lifetime EP0710716B1 (en) | 1994-11-02 | 1995-10-24 | Granulated bleach activators and production thereof |
Country Status (10)
| Country | Link |
|---|---|
| US (1) | US5716569A (en) |
| EP (1) | EP0710716B1 (en) |
| JP (1) | JP4249271B2 (en) |
| KR (1) | KR100388367B1 (en) |
| AT (1) | ATE221114T1 (en) |
| BR (1) | BR9505059A (en) |
| CA (1) | CA2161943C (en) |
| DE (2) | DE4439039A1 (en) |
| ES (1) | ES2180602T3 (en) |
| TW (1) | TW353114B (en) |
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| WO1999014306A2 (en) * | 1997-09-16 | 1999-03-25 | Clariant Gmbh | Bleaching activators in the form of storage-stable granules |
| CN1081662C (en) * | 1996-02-06 | 2002-03-27 | 狮子株式会社 | Bleaching activator granulate |
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| DE19641708A1 (en) | 1996-10-10 | 1998-04-16 | Clariant Gmbh | Process for the preparation of a coated bleach activator granulate |
| DE19642491A1 (en) * | 1996-10-15 | 1998-04-16 | Basf Ag | Flame retardant thermoplastic molding compounds based on polyphenylene ethers and vinyl aromatic polymers |
| KR100416934B1 (en) * | 1996-10-31 | 2004-05-20 | 주식회사 엘지생활건강 | Ecapsulated Bleaching Activator |
| DE19740671A1 (en) * | 1997-09-16 | 1999-03-18 | Clariant Gmbh | Bleach activator granulate containing ammonium nitrile and layered silicate |
| KR100497521B1 (en) * | 1998-04-08 | 2005-09-14 | 주식회사 엘지생활건강 | Manufacturing method of capsule laundry detergent |
| DE19908051A1 (en) * | 1999-02-25 | 2000-08-31 | Henkel Kgaa | Process for the preparation of compounded acetonitrile derivatives |
| DE10334046A1 (en) * | 2003-07-25 | 2005-02-10 | Clariant Gmbh | Process for the preparation of granulated acyloxybenzenesulfonates or acyloxybenzenecarboxylic acids and their salts |
| JP4929153B2 (en) | 2004-03-05 | 2012-05-09 | ジェン−プロウブ インコーポレイテッド | Reagents, methods, and kits for use in inactivating nucleic acids |
| DE102004043360A1 (en) * | 2004-09-08 | 2006-03-09 | Clariant Gmbh | Bleach activator mixtures |
| KR101069043B1 (en) * | 2005-07-06 | 2011-09-29 | 주식회사 엘지생활건강 | Manufacturing method of bleach activator granule and bleach activator granule formed therefrom |
| ES2427152T3 (en) * | 2006-04-20 | 2013-10-29 | The Procter & Gamble Company | Procedure to produce bleaching particles |
| US7709437B2 (en) * | 2006-04-27 | 2010-05-04 | Oci Chemical Corp. | Co-granulates of bleach activator-peroxide compounds |
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| DE2048331A1 (en) | 1970-10-01 | 1972-04-06 | Henkel & Cie GmbH, 4000 Dusseldorf | Solid, powdery to granular agents for the production of cold-acting bleaching liquors, in particular cold-acting bleaching liquors, and processes for the manufacture of these agents |
| US3822114A (en) | 1971-08-05 | 1974-07-02 | Procter & Gamble | Bleaching process and compositions therefor |
| GB1507312A (en) | 1974-12-04 | 1978-04-12 | Unilever Ltd | Encapsulation of particles |
| DE2733849A1 (en) | 1977-07-27 | 1979-02-15 | Basf Ag | SOLID COLD BLEACH ACTIVATORS FOR COMPOUNDS RELEASING ACTIVE OXYGEN |
| EP0037026A1 (en) | 1980-03-28 | 1981-10-07 | Henkel Kommanditgesellschaft auf Aktien | Process for the preparation of a storage-stable, easily soluble granulated compound containing a bleach activator |
| EP0062523A2 (en) | 1981-04-08 | 1982-10-13 | THE PROCTER & GAMBLE COMPANY | Detergent additive compositions and preparations and use thereof in detergent compositions |
| EP0070474A1 (en) | 1981-07-17 | 1983-01-26 | Henkel Kommanditgesellschaft auf Aktien | Process for the production of enveloped granular bleaching activators |
| EP0075818A2 (en) | 1981-09-28 | 1983-04-06 | BASF Aktiengesellschaft | Granular bleach activator |
| EP0240057A1 (en) | 1986-03-25 | 1987-10-07 | Unilever N.V. | Granular non-phosphorus-containing bleach activator compositions and use thereof in granular detergent bleach compositions |
| EP0325100A2 (en) | 1988-01-21 | 1989-07-26 | Colgate-Palmolive Company | Acetylated sugar ethers as bleach activators and detergency boosters |
| WO1990001535A1 (en) | 1988-08-01 | 1990-02-22 | Henkel Kommanditgesellschaft Auf Aktien | Granular bleaching aid containing bleach activators |
| WO1991010719A1 (en) | 1990-01-22 | 1991-07-25 | Novo Nordisk A/S | Bleaching detergent composition |
| EP0446982A2 (en) | 1990-03-16 | 1991-09-18 | Unilever N.V. | Low-temperature bleaching compositions |
| EP0458398A2 (en) | 1990-05-21 | 1991-11-27 | Unilever N.V. | Bleach activation |
| EP0458397A2 (en) | 1990-05-21 | 1991-11-27 | Unilever N.V. | Bleach activation |
| GB2249104A (en) | 1990-10-23 | 1992-04-29 | Bp Chem Int Ltd | Bleach activators |
| EP0492000A1 (en) | 1990-12-28 | 1992-07-01 | AUSIMONT S.p.A. | Process for increasing the bleaching efficiency of an inorganic persalt |
| WO1992013798A1 (en) | 1991-02-06 | 1992-08-20 | The Procter & Gamble Company | Peroxyacid bleach precursor compositions |
| WO1994003395A1 (en) | 1992-08-01 | 1994-02-17 | The Procter & Gamble Company | Peroxyacid bleach precursor compositions |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1081662C (en) * | 1996-02-06 | 2002-03-27 | 狮子株式会社 | Bleaching activator granulate |
| WO1999014306A2 (en) * | 1997-09-16 | 1999-03-25 | Clariant Gmbh | Bleaching activators in the form of storage-stable granules |
| WO1999014306A3 (en) * | 1997-09-16 | 1999-05-14 | Clariant Gmbh | Bleaching activators in the form of storage-stable granules |
Also Published As
| Publication number | Publication date |
|---|---|
| ES2180602T3 (en) | 2003-02-16 |
| CA2161943A1 (en) | 1996-05-03 |
| DE59510290D1 (en) | 2002-08-29 |
| CA2161943C (en) | 2007-02-06 |
| EP0710716A3 (en) | 1998-07-08 |
| KR100388367B1 (en) | 2003-09-22 |
| BR9505059A (en) | 1997-10-14 |
| ATE221114T1 (en) | 2002-08-15 |
| US5716569A (en) | 1998-02-10 |
| EP0710716B1 (en) | 2002-07-24 |
| JPH08209192A (en) | 1996-08-13 |
| JP4249271B2 (en) | 2009-04-02 |
| TW353114B (en) | 1999-02-21 |
| KR960017832A (en) | 1996-06-17 |
| DE4439039A1 (en) | 1996-05-09 |
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