EP0037026A1 - Process for the preparation of a storage-stable, easily soluble granulated compound containing a bleach activator - Google Patents
Process for the preparation of a storage-stable, easily soluble granulated compound containing a bleach activator Download PDFInfo
- Publication number
- EP0037026A1 EP0037026A1 EP81102083A EP81102083A EP0037026A1 EP 0037026 A1 EP0037026 A1 EP 0037026A1 EP 81102083 A EP81102083 A EP 81102083A EP 81102083 A EP81102083 A EP 81102083A EP 0037026 A1 EP0037026 A1 EP 0037026A1
- Authority
- EP
- European Patent Office
- Prior art keywords
- weight
- percent
- granulating
- mixing
- water
- 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
- 239000012190 activator Substances 0.000 title claims abstract description 37
- 239000007844 bleaching agent Substances 0.000 title claims abstract description 32
- 238000000034 method Methods 0.000 title claims description 36
- 150000001875 compounds Chemical class 0.000 title claims description 4
- 238000002360 preparation method Methods 0.000 title description 5
- 239000008187 granular material Substances 0.000 claims abstract description 43
- 238000002156 mixing Methods 0.000 claims abstract description 36
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 33
- 239000000203 mixture Substances 0.000 claims abstract description 24
- 239000000243 solution Substances 0.000 claims abstract description 23
- 229920002472 Starch Polymers 0.000 claims abstract description 16
- 235000019698 starch Nutrition 0.000 claims abstract description 16
- 239000008107 starch Substances 0.000 claims abstract description 15
- 239000007864 aqueous solution Substances 0.000 claims abstract description 13
- 239000002245 particle Substances 0.000 claims abstract description 13
- -1 polysiloxane Polymers 0.000 claims abstract description 11
- 229920003086 cellulose ether Polymers 0.000 claims abstract description 8
- 239000000843 powder Substances 0.000 claims abstract description 8
- 238000004519 manufacturing process Methods 0.000 claims abstract description 7
- 229920001296 polysiloxane Polymers 0.000 claims abstract description 6
- 238000005469 granulation Methods 0.000 claims description 38
- 230000003179 granulation Effects 0.000 claims description 38
- 239000001768 carboxy methyl cellulose Substances 0.000 claims description 32
- 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 claims description 12
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 10
- 239000007788 liquid Substances 0.000 claims description 10
- 150000003839 salts Chemical class 0.000 claims description 9
- 239000013530 defoamer Substances 0.000 claims description 5
- 239000000377 silicon dioxide Substances 0.000 claims description 5
- 235000019832 sodium triphosphate Nutrition 0.000 claims description 5
- DPXJVFZANSGRMM-UHFFFAOYSA-N acetic acid;2,3,4,5,6-pentahydroxyhexanal;sodium Chemical compound [Na].CC(O)=O.OCC(O)C(O)C(O)C(O)C=O DPXJVFZANSGRMM-UHFFFAOYSA-N 0.000 claims description 4
- 150000001408 amides Chemical class 0.000 claims description 4
- 150000001412 amines Chemical class 0.000 claims description 4
- 125000001046 glycoluril group Chemical group [H]C12N(*)C(=O)N(*)C1([H])N(*)C(=O)N2* 0.000 claims description 4
- 235000019812 sodium carboxymethyl cellulose Nutrition 0.000 claims description 4
- 229920001027 sodium carboxymethylcellulose Polymers 0.000 claims description 4
- 150000002170 ethers Chemical class 0.000 claims description 3
- 239000000470 constituent Substances 0.000 claims description 2
- 238000007580 dry-mixing Methods 0.000 claims description 2
- 239000000049 pigment Substances 0.000 claims description 2
- 239000013078 crystal Substances 0.000 claims 2
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 abstract description 8
- 238000001035 drying Methods 0.000 abstract description 8
- 239000002671 adjuvant Substances 0.000 abstract 4
- 239000002518 antifoaming agent Substances 0.000 abstract 1
- 229920002134 Carboxymethyl cellulose Polymers 0.000 description 28
- 239000008112 carboxymethyl-cellulose Substances 0.000 description 28
- 235000010948 carboxy methyl cellulose Nutrition 0.000 description 19
- 239000003599 detergent Substances 0.000 description 10
- 239000011734 sodium Substances 0.000 description 9
- 239000011248 coating agent Substances 0.000 description 7
- 239000000463 material Substances 0.000 description 7
- 238000005406 washing Methods 0.000 description 5
- 238000004061 bleaching Methods 0.000 description 4
- 238000000576 coating method Methods 0.000 description 4
- 239000000126 substance Substances 0.000 description 4
- WSFSSNUMVMOOMR-UHFFFAOYSA-N Formaldehyde Chemical compound O=C WSFSSNUMVMOOMR-UHFFFAOYSA-N 0.000 description 3
- 238000002425 crystallisation Methods 0.000 description 3
- 230000008025 crystallization Effects 0.000 description 3
- 239000007884 disintegrant Substances 0.000 description 3
- 239000006260 foam Substances 0.000 description 3
- 238000000227 grinding Methods 0.000 description 3
- 238000001228 spectrum Methods 0.000 description 3
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-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
- 239000013543 active substance Substances 0.000 description 2
- 239000000654 additive Substances 0.000 description 2
- 229920002678 cellulose Polymers 0.000 description 2
- 239000001913 cellulose Substances 0.000 description 2
- 239000003795 chemical substances by application Substances 0.000 description 2
- 150000004985 diamines Chemical class 0.000 description 2
- 235000014113 dietary fatty acids Nutrition 0.000 description 2
- 239000004205 dimethyl polysiloxane Substances 0.000 description 2
- 239000000428 dust Substances 0.000 description 2
- 230000000694 effects Effects 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
- 239000010419 fine particle Substances 0.000 description 2
- 238000005187 foaming Methods 0.000 description 2
- 239000003112 inhibitor Substances 0.000 description 2
- 238000005453 pelletization Methods 0.000 description 2
- 229920000435 poly(dimethylsiloxane) Polymers 0.000 description 2
- LNAZSHAWQACDHT-XIYTZBAFSA-N (2r,3r,4s,5r,6s)-4,5-dimethoxy-2-(methoxymethyl)-3-[(2s,3r,4s,5r,6r)-3,4,5-trimethoxy-6-(methoxymethyl)oxan-2-yl]oxy-6-[(2r,3r,4s,5r,6r)-4,5,6-trimethoxy-2-(methoxymethyl)oxan-3-yl]oxyoxane Chemical compound CO[C@@H]1[C@@H](OC)[C@H](OC)[C@@H](COC)O[C@H]1O[C@H]1[C@H](OC)[C@@H](OC)[C@H](O[C@H]2[C@@H]([C@@H](OC)[C@H](OC)O[C@@H]2COC)OC)O[C@@H]1COC LNAZSHAWQACDHT-XIYTZBAFSA-N 0.000 description 1
- HUPQMDDKEZELTH-UHFFFAOYSA-N 1,3-diacetyl-5,5-dimethylimidazolidine-2,4-dione Chemical compound CC(=O)N1C(=O)N(C(C)=O)C(C)(C)C1=O HUPQMDDKEZELTH-UHFFFAOYSA-N 0.000 description 1
- 206010013786 Dry skin Diseases 0.000 description 1
- 239000001856 Ethyl cellulose Substances 0.000 description 1
- ZZSNKZQZMQGXPY-UHFFFAOYSA-N Ethyl cellulose Chemical compound CCOCC1OC(OC)C(OCC)C(OCC)C1OC1C(O)C(O)C(OC)C(CO)O1 ZZSNKZQZMQGXPY-UHFFFAOYSA-N 0.000 description 1
- 229920000663 Hydroxyethyl cellulose Polymers 0.000 description 1
- 239000004354 Hydroxyethyl cellulose Substances 0.000 description 1
- 229920001479 Hydroxyethyl methyl cellulose Polymers 0.000 description 1
- 229920001612 Hydroxyethyl starch Polymers 0.000 description 1
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 description 1
- 229910000503 Na-aluminosilicate Inorganic materials 0.000 description 1
- 229920000388 Polyphosphate Polymers 0.000 description 1
- 239000004115 Sodium Silicate Substances 0.000 description 1
- PMZURENOXWZQFD-UHFFFAOYSA-L Sodium Sulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=O PMZURENOXWZQFD-UHFFFAOYSA-L 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 239000004480 active ingredient Substances 0.000 description 1
- 230000002411 adverse Effects 0.000 description 1
- 230000001476 alcoholic effect Effects 0.000 description 1
- 229910052783 alkali metal Inorganic materials 0.000 description 1
- 150000001340 alkali metals Chemical class 0.000 description 1
- 229910000323 aluminium silicate Inorganic materials 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 150000004649 carbonic acid derivatives Chemical class 0.000 description 1
- 125000002057 carboxymethyl group Chemical group [H]OC(=O)C([H])([H])[*] 0.000 description 1
- 239000005018 casein Substances 0.000 description 1
- BECPQYXYKAMYBN-UHFFFAOYSA-N casein, tech. Chemical compound NCCCCC(C(O)=O)N=C(O)C(CC(O)=O)N=C(O)C(CCC(O)=N)N=C(O)C(CC(C)C)N=C(O)C(CCC(O)=O)N=C(O)C(CC(O)=O)N=C(O)C(CCC(O)=O)N=C(O)C(C(C)O)N=C(O)C(CCC(O)=N)N=C(O)C(CCC(O)=N)N=C(O)C(CCC(O)=N)N=C(O)C(CCC(O)=O)N=C(O)C(CCC(O)=O)N=C(O)C(COP(O)(O)=O)N=C(O)C(CCC(O)=N)N=C(O)C(N)CC1=CC=CC=C1 BECPQYXYKAMYBN-UHFFFAOYSA-N 0.000 description 1
- 235000021240 caseins Nutrition 0.000 description 1
- 239000011247 coating layer Substances 0.000 description 1
- 238000004040 coloring Methods 0.000 description 1
- 239000000645 desinfectant Substances 0.000 description 1
- 239000001177 diphosphate Substances 0.000 description 1
- XPPKVPWEQAFLFU-UHFFFAOYSA-J diphosphate(4-) Chemical compound [O-]P([O-])(=O)OP([O-])([O-])=O XPPKVPWEQAFLFU-UHFFFAOYSA-J 0.000 description 1
- 235000011180 diphosphates Nutrition 0.000 description 1
- 229920001249 ethyl cellulose Polymers 0.000 description 1
- 235000019325 ethyl cellulose Nutrition 0.000 description 1
- 238000004880 explosion Methods 0.000 description 1
- 239000002360 explosive Substances 0.000 description 1
- 238000000605 extraction Methods 0.000 description 1
- 150000002191 fatty alcohols Chemical class 0.000 description 1
- 230000002349 favourable effect Effects 0.000 description 1
- 239000000945 filler Substances 0.000 description 1
- 239000003205 fragrance Substances 0.000 description 1
- 239000008240 homogeneous mixture Substances 0.000 description 1
- 235000019447 hydroxyethyl cellulose Nutrition 0.000 description 1
- 229940050526 hydroxyethylstarch Drugs 0.000 description 1
- 238000009434 installation Methods 0.000 description 1
- 238000005342 ion exchange Methods 0.000 description 1
- 229910052749 magnesium Inorganic materials 0.000 description 1
- 239000011777 magnesium Substances 0.000 description 1
- HCWCAKKEBCNQJP-UHFFFAOYSA-N magnesium orthosilicate Chemical compound [Mg+2].[Mg+2].[O-][Si]([O-])([O-])[O-] HCWCAKKEBCNQJP-UHFFFAOYSA-N 0.000 description 1
- 239000000395 magnesium oxide Substances 0.000 description 1
- CPLXHLVBOLITMK-UHFFFAOYSA-N magnesium oxide Inorganic materials [Mg]=O CPLXHLVBOLITMK-UHFFFAOYSA-N 0.000 description 1
- 239000000391 magnesium silicate Substances 0.000 description 1
- 235000019792 magnesium silicate Nutrition 0.000 description 1
- 229910052919 magnesium silicate Inorganic materials 0.000 description 1
- AXZKOIWUVFPNLO-UHFFFAOYSA-N magnesium;oxygen(2-) Chemical compound [O-2].[Mg+2] AXZKOIWUVFPNLO-UHFFFAOYSA-N 0.000 description 1
- 238000002844 melting Methods 0.000 description 1
- 230000008018 melting Effects 0.000 description 1
- 229920000609 methyl cellulose Polymers 0.000 description 1
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 1
- 239000001923 methylcellulose Substances 0.000 description 1
- 235000010981 methylcellulose Nutrition 0.000 description 1
- UJPCOKISUIXFFR-UHFFFAOYSA-N n-acetyl-n-(4-methylphenyl)acetamide Chemical compound CC(=O)N(C(C)=O)C1=CC=C(C)C=C1 UJPCOKISUIXFFR-UHFFFAOYSA-N 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- 150000004965 peroxy acids Chemical class 0.000 description 1
- 229920001223 polyethylene glycol Polymers 0.000 description 1
- 239000001205 polyphosphate Substances 0.000 description 1
- 235000011176 polyphosphates Nutrition 0.000 description 1
- 239000001253 polyvinylpolypyrrolidone Substances 0.000 description 1
- 235000013809 polyvinylpolypyrrolidone Nutrition 0.000 description 1
- 229920000523 polyvinylpolypyrrolidone Polymers 0.000 description 1
- 108090000623 proteins and genes Proteins 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 238000011084 recovery Methods 0.000 description 1
- 238000005204 segregation Methods 0.000 description 1
- 238000007873 sieving Methods 0.000 description 1
- 150000004760 silicates Chemical class 0.000 description 1
- 235000012217 sodium aluminium silicate Nutrition 0.000 description 1
- 229910000029 sodium carbonate Inorganic materials 0.000 description 1
- 235000017550 sodium carbonate Nutrition 0.000 description 1
- 159000000000 sodium salts Chemical class 0.000 description 1
- NTHWMYGWWRZVTN-UHFFFAOYSA-N sodium silicate Chemical compound [Na+].[Na+].[O-][Si]([O-])=O NTHWMYGWWRZVTN-UHFFFAOYSA-N 0.000 description 1
- 229910052911 sodium silicate Inorganic materials 0.000 description 1
- 235000019794 sodium silicate Nutrition 0.000 description 1
- 229910052938 sodium sulfate Inorganic materials 0.000 description 1
- 235000011152 sodium sulphate Nutrition 0.000 description 1
- RPACBEVZENYWOL-XFULWGLBSA-M sodium;(2r)-2-[6-(4-chlorophenoxy)hexyl]oxirane-2-carboxylate Chemical compound [Na+].C=1C=C(Cl)C=CC=1OCCCCCC[C@]1(C(=O)[O-])CO1 RPACBEVZENYWOL-XFULWGLBSA-M 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 239000007921 spray Substances 0.000 description 1
- 238000001694 spray drying Methods 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
- UNXRWKVEANCORM-UHFFFAOYSA-I triphosphate(5-) Chemical compound [O-]P([O-])(=O)OP([O-])(=O)OP([O-])([O-])=O UNXRWKVEANCORM-UHFFFAOYSA-I 0.000 description 1
- 229920003169 water-soluble polymer Polymers 0.000 description 1
- 239000012463 white pigment 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
- C11D3/39—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
Definitions
- Bleach activators are taken to mean compounds which react in aqueous solutions containing hydrogen peroxide or perhydrates to form peracids which have a bleaching action.
- the particularly effective bleach activators include N-acylated amines, amides and glycolurils, as are known, for example, from DE-AS 11 62 967, DE-AS 12 91 317, DE-OS 20 38 106 and DE-AS 15 94 865.
- DE-AS 11 62 967 it is proposed to provide these bleach activators with a water-soluble coating agent before further use, in particular before use in detergents and bleaching agents, wherein the coating agent can consist, for example, of carboxymethyl cellulose.
- This coating agent dissolved in water, can be sprayed onto the activator in finely divided form, after which the coated material is dried.
- the recommendation is made to granulate the activator before coating, but there are no indications as to how and with which granulation aids this should be carried out. If one works according to the specifications of DE-AS 11 62 967 and sprays such a bleach activator, for example tetraacetylethylene diamine, with an aqueous carboxymethyl cellulose solution in a granulator, considerable problems arise. This is because aqueous solutions containing more than 5 percent by weight of carboxymethyl cellulose can no longer be handled in industrial granulation processes because of their high viscosity and gel-like nature.
- a process for the production of coated, granulated bleach activators in which the activator is first mixed dry with a suitable coating or granulation agent and sprayed in a second step with water or water-soluble granulation aids or film formers and is granulated.
- a suitable coating or granulation agent for the preparation of the dry premixes, either water-soluble framework salts customary in detergents, such as water of crystallization, are used phates, polyphosphates, carbonates and silicates of alkali metals or water-insoluble fillers such as silica, magnesium silicate or magnesium oxide are proposed.
- the same water-soluble salts which bind water of crystallization can also be used as granulation aids or the dry premixes can be sprayed with an aqueous solution of film-forming substances such as cellulose derivatives or other water-soluble polymers of natural or synthetic origin and granulated at the same time.
- this process is only useful for the production of granules with a comparatively low content of bleach activators, that is to say those with less than 50 percent by weight.
- the granules can therefore only be used in areas where the high proportion of additives does not interfere.
- the invention is based on the object of developing a process for the production of readily pourable, uniformly coated and thus very stable bleach activator granules which have a substantially higher content, for example one of 90 percent by weight and more, of active substance.
- the invention with which this object is achieved is a process for producing a storage-stable, bleach activator-containing granules by dry mixing a powdered bleach activator from the class of N-acylated amines, amides, diketopiperazines and glycolurils with a powdered granulating aid, moistening the dry Premixed with an aqueous solution of the granulating aid and granulating the moist mixture in a niche and granulating device, characterized in that for the preparation of a granulate containing 90 to 98 percent by weight of bleach activator and 10 to 2 percent by weight of granulating aid, based on anhydrous constituents Bleach activator, which is a medium grain Size from 0.01 to 0.8 mm, in a first mixing stage with 50 to 100 percent of the total granulation aid to be used, which consists of a compound from the class of water-soluble cellulose ether, starch and starch ether and as a pourable powder with an average grain
- Average grain size of 0.01 to 0.8 mm is to be understood as meaning that in which more than 50 percent by weight, preferably at least 80 percent by weight of the particles have a grain size of 0.01 to 0.8 mm and not more than 25 percent by weight , preferably not more than 10% by weight have a grain size of 0.8 to at most ii6 mm and not more than 25% by weight, preferably not more than 10% by weight have a grain size of less than 0.01 mm.
- the grain size of the fine particles is not limited at the bottom, but dust-fine particles can also be present. The additional use of such dusty fractions, which are common in technical, unclassified powder products with a broad grain spectrum, represents an additional advantage of the process.
- N-acylated amines, diamines, amides and glycolurils are suitable as bleach activators.
- These are, for example, tetraacetylmethylene diamine, tetraacetylethylene diamine, diacetylaniline, diacetyl-p-toluidine, 1,3-diacetyl-5,5-dimethylhydantoin, tetraacetylglycoluril, tetrapropionylglycoluril, 1,4-diacetyl-2,5-diketo-piperazine -Diacetyl-3,6-dimethyl-2,5-diketopiperazine.
- Tetraacetylethylenediamine is preferably used as the bleach activator.
- the powdery bleach activator is mixed with a part of the granulation aid, which is also in powder form.
- the proportion of the granulation aid used in this stage is 50 to 100, preferably 80 to 95. Weight percent of the total granulation aid used. Accordingly, the total amount or only part of the granulation auxiliary can be added in the 1st mixing stage.
- the second variant, in which only part of the granulation aid is dry-mixed and the rest is introduced as a solution in the second stage, is the preferred method of operation.
- the average grain size of the granulation aid is 0.01 to 0.8 mm according to the above definition.
- the grain size of the powdered granulation aid is expediently as large or smaller than the grain size of the bleach activator.
- the particle size of the granulating aid is advantageously 0.01 to 0.4 mm, the proportion of particles with a particle size of 0.4 to 1.6 mm 25 Weight percent and in particular 10 weight percent does not exceed.
- the granulation aid consists of a water-soluble cellulose ether, water-soluble starch or a water-soluble starch ether.
- cellulose ethers are celluose, methylcellulose, ethylcellulose, hydroxyethyl cellulose, methylhydroxyethylcellulose, methylhydroxypropyl *, carboxymethyl cellulose (as the sodium salt) and methyl carboxymethyl cellulose (Na salt).
- depolymerized starch can be considered as starch.
- the two powdery components can be mixed in conventional batch-wise or continuously operating mixing devices, which are generally equipped with rotating mixing elements. Depending on the effectiveness of the mixing device, the mixing times for a homogeneous mixture are generally between 30 seconds and 5 minutes.
- powdery disintegrants which are common in the tablet industry can also be added, provided that the cellulose and starch ethers used do not automatically develop a certain explosive effect.
- Usable disintegrants are, for example, partially degraded starch, starch ether, polyvinylpolypyrrolidone, formaldehyde casein and swellable magnesium aluminosilicates (Veegum). The proportion of such disintegrants can be 0 to 2 percent by weight of the anhydrous granules.
- the dry powder mixture is then moistened with water or an aqueous solution of the remaining granulating aid and granulated.
- the mixer of the first mixing stage is also suitable for a granulation process, the mix can remain therein during the granulation process.
- a pelletizer for example a pelletizing drum or onto a rotating pelletizer, and to carry out the pelletizing process there or to complete it.
- part of the granulating liquid is expediently introduced into the mixer towards the end of the first mixing stage in order to moisten the material to be mixed and to counteract the formation of dust. For example, 5 to 70 percent of the granulation liquid is added during the post-mixing and 95 to 30 percent of the liquid during the subsequent granulation.
- the granulating aid used in the second mixing and granulation stage is preferably used in a 0.5 to 5 percent by weight solution. Solutions with a higher concentration and containing up to 10 percent by weight of granulation aids are only recommended if they are sufficiently low-viscosity. If sodium carboxymethyl cellulose is used in a provenance as is usually used in detergents, the concentration is advantageously not more than 4 percent by weight.
- the amount of granulation liquid applied is to be measured in such a way that moist granules are formed which are not yet prone to caking. This is achieved when the water content of the moist granules is between 10 and 35, preferably 15 to 25, weight percent. Powder mixtures with a small grain spectrum and a higher proportion of powdered granulating aid can absorb larger amounts of granulating liquid than less fine-grained mixtures with a small proportion of granulating aid.
- a dye or a white pigment can be added to the dry powder mixture or the granulating liquid for coloring or to cover the inherent color of the raw materials.
- a dye or a white pigment can be added to the dry powder mixture or the granulating liquid for coloring or to cover the inherent color of the raw materials.
- generally 0.01 to 0.1 percent by weight, based on the finished product, of dye or pigment is sufficient.
- the water content of the mixture is then reduced to less than 2, preferably less than 1 percent by weight.
- the excess water can be removed by drying with the addition of heat, the temperature of the granules expediently not exceeding 100 ° C. and below the melting temperature of the bleach activator. Dryers that do not adversely change the granular structure of the product are suitable, for example tray, vacuum or fluidized bed dryers.
- the dried granules should contain less than 2, preferably less than 1 percent by weight of water.
- the Extraction of the excess water also by mixing the moist granules with such dehydrating, essentially water-free or low-water salts.
- Such salts are sodium tripolyphosphate, sodium sulfate, sodium carbonate, sodium silicate and low-water sodium aluminosilicates capable of ion exchange and their genes. The amount to be used depends on the water binding capacity of the salts concerned and the water content of the moist granules.
- the mixing ratio of tripolyphosphate to moist granules is, for example, 1: 3 to 1: 1.5, in particular 1: 2 to 1: 1.
- Mixing can be carried out in conventional mixers or granulating devices, with the addition of Production of the moist granules used, equipped with mixing devices mixing device can be used immediately. In this way, simplified, in particular energy-saving, processing is possible since the necessary drying stage can be saved.
- Suitable foam inhibitors are customary known defoamers, preferably polysiloxanes, and mixtures thereof with microfine silica. Examples of these are polydimethylsiloxane with a content of approximately 1 to 10 percent by weight of microfine silica. The proportion of such polysiloxane foaming can be 1 to 5 percent by weight, preferably 2 to 4 percent by weight, based on the finished granulate.
- the defoamer can be added in the first mixing stage; however, the defoamer can also be dispersed in the granulating liquid which, in order to avoid segregation processes, should contain part of the granulating aid in this case.
- the granules produced in the manner indicated have a favorable grain spectrum. Any overlap and fine fractions can be screened off and returned to the process after grinding the coarse fractions.
- the granules are easy to pour, non-sticky and very stable considering the complete coating of the activator particles. Its high proportion of active substance, 90 and more percent by weight, is particularly advantageous. They can be used with advantage in detergents, bleaches, oxidizers and disinfectants and retain their good properties even when mixed with the active ingredients contained in these agents.
- Tetraacetylethylenediamine with an average grain size of 0.01 to 0.8 mm was used as the bleach activator.
- the grain fraction between 0.8 and 1.6 mm was 5 weight percent, the fraction under 0.01 mm 10 weight percent.
- Example 42.0 kg of the powdery tetraacetylethylenediamine used in Example 1 were in a drum mixer equipped with rotating mixing elements (LöDIGE mixer) with 2.24 kg Na carboxymethyl cellulose of the grain size given in Example 1 (88.2 percent of the total amount used) for 2 minutes mixed and then sprayed with continuous mixing with a solution of 170.4 g Na carboxymethyl cellulose in 5.51 kg water (3 percent by weight) for the purpose of binding dust-like components.
- the mix was transferred to a continuously operating mixing granulator (capacity 800 kg / h).
- the outlet of this mixer was connected to the inlet via conveyor belts so that the product could be circulated.
- the majority of the granules were dried in a vacuum dryer at 50 torr over 24 hours to a water content of less than 1 percent by weight. 3 kg of the moist granules were dried in a fluidized bed dryer with air having an inlet temperature of 57 ° C. for 10 minutes to the same degree of drying. In both cases, the proportion of the granules with a grain size of 0.5 to 1.5 mm was 65 percent by weight. The rollover and fine fractions were sieved out and, after grinding the coarse fractions, entered into the subsequent granulation process.
- 91.45 parts by weight of tetraacetylethylenediamine which had the following grain size (in percent by weight), were obtained in accordance with the preparation procedure given in Example 1: mixed with 3.048 parts by weight of a polysiloxane defoamer (consisting of 93 percent by weight of polydimethylsiloxane and 7 percent by weight of silanized microfine silica) and 4.8 parts by weight of Na carboxymethyl cellulose. Then, through the hollow drive shaft of the mixer, 0.629 parts by weight of sodium carboxymethyl cellulose in the form of a 3% strength aqueous solution were fed in over the course of 5 minutes, and the granulation process was then continued for a further 1 minute.
- Example 4 was repeated, but the polysiloxane defoamer had been dispersed in the aqueous granulation liquid containing carboxymethyl cellulose. In terms of its properties, the product corresponded to that of Example 4.
- Example 42.0 kg of the powdery tetraacetylethylenediamine used in Example 1 were in a drum mixer equipped with rotating mixing elements (L ⁇ DIGE mixer) with 2.24 kg Na carboxymethyl cellulose of the grain size given in Example 1 (88.2 percent of the total amount used) for 2 minutes mixed and then sprayed with continuous mixing with a solution of 170.4 g Na carboxymethyl cellulose in 5.51 kg water (3 percent by weight) for the purpose of binding dust-like components.
- the mix was transferred to a continuously operating mixing granulator (capacity 800 kg / h).
- the outlet of this mixer was connected to the inlet via conveyor belts so that the product could be circulated.
- 4.3 kg of a 3% solution of Na-carboxymethyl cellulose (corresponding to 129 g) were fed in through the rotating shaft of the granulation mixer.
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)
- Cosmetics (AREA)
Abstract
Description
Unter Bleichaktivatoren werden Verbindungen verstanden, die in wäßrigen, Wasserstoffperoxid oder Perhydrate enthaltenden Lösungen unter Bildung von bleichend wirkenden Persäuren reagieren. Zu den besonders wirksamen Bleichaktivatoren zählen N-acylierte Amine, Amide und Glykolurile, wie sie beispielsweise aus der DE-AS 11 62 967, DE-AS 12 91 317, DE-OS 20 38 106 und DE-AS 15 94 865 bekannt sind. In der DE-AS 11 62 967 wird vorgeschlagen, diese Bleichaktivatoren vor der Weiterverwendung, insbesondere vor dem Einsatz in Wasch- und Bleichmitteln mit einem wasserlöslichen Überzugsmittel zu versehen, wobei das überzugsmittel beispielsweise aus Carboxymethylcellulose bestehen kann. Dieses Überzugsmittel kann in Wasser gelöst in feinverteilter Form auf den Aktivator aufgesprüht werden, worauf das überzogene Material getrocknet wird. Es wird die Empfehlung ausgesprochen, den Aktivator vor dem Überziehen zu granulieren, jedoch fehlen Hinweise,in welcher Weise und mit welchen Granulationshilfsmitteln dies durchgeführt werden soll. Arbeitet man nach den Angaben der DE-AS 11 62 967 und besprüht einen derartigen Bleichaktivator, beispielsweise das Tetraacetylethylendiamin, mit einer wäßrigen Carboxymethylcellulose-Lösung in einem Granulator, so treten erhebliche Probleme auf. Es lassen sich nämlich wäßrige Lösungen mit einem Gehalt von mehr als 5 Gewichtsprozent an Carboxymethylcellulose wegen ihrer hohen Viskosität und gelartigen Beschaffenheit bei technichen Granulationsprozessen nicht mehr handhaben. Um eine ausreichend starke Hüllschicht auf den Aktivatorpartikeln zu erzeugen, müssen daher sehr große Mengen an den verhältnismäßig stark verdünnten Celluloseetherlösungen verarbeitet werden. Wenn, wie im Beispiel 10 der DE-AS 11 62 967 angegeben, 18 Gewichtsprozent Carboxymethylcellulose auf den Bleichaktivator aufgebracht werden'sollen und unterstellt man, daß eine hinsichtlich ihrer hohen Viskosität gerade noch verarbeitbare 5-prozentige Lösung benutzt wird, so wären hierfür 360 Gewichtsprozent (bezogen auf Aktivatormenge) an 5-prozentiger Celluloseether-Lösung erforderlich. Es läßt sich jedoch zeigen, daß bei Anwendung von mehr als 20 bis 30 Gewichtsprozent einer derartigen Lösung bereits klumpige bis breiartige Massen anstelle brauchbarer Granulate entstehen. Aus diesem Grund wird auch in Spalte 3 der DE-AS 11 62 967 vorgeschlagen, alkoholische Lösungen der Carboxymethylcellulose zu verwenden. Diese erfordern jedoch die Installation aufwendiger Explosionsschutzvorrichtungen und verursachen hohe Kosten für die Rückgewinnung des Lösungsmittels. Für technische Zwecke ist ein solches Verfahren ungeeignet. Die gleichen Probleme treten auf, wenn man anstelle einer Celluloseether-Lösung,die ebenfalls in der DE-AS 11 62 967 vorgeschlagenen, in organischen Lösungsmitteln gelösten Fettsäuren, Fettsäurealkanolamide, Fettalkohole und Carbowaxe als Hüllmaterial einsetzt. Erschwerend kommt hinzu, daß sich derartige Hüllmaterialien in kalten Bleichlösungen nicht oder nur sehr langsam lösen und daher der gewünschte Kaltbleicheffekt unterdrückt wird.Bleach activators are taken to mean compounds which react in aqueous solutions containing hydrogen peroxide or perhydrates to form peracids which have a bleaching action. The particularly effective bleach activators include N-acylated amines, amides and glycolurils, as are known, for example, from DE-AS 11 62 967, DE-AS 12 91 317, DE-OS 20 38 106 and DE-AS 15 94 865. In DE-AS 11 62 967 it is proposed to provide these bleach activators with a water-soluble coating agent before further use, in particular before use in detergents and bleaching agents, wherein the coating agent can consist, for example, of carboxymethyl cellulose. This coating agent, dissolved in water, can be sprayed onto the activator in finely divided form, after which the coated material is dried. The recommendation is made to granulate the activator before coating, but there are no indications as to how and with which granulation aids this should be carried out. If one works according to the specifications of DE-AS 11 62 967 and sprays such a bleach activator, for example tetraacetylethylene diamine, with an aqueous carboxymethyl cellulose solution in a granulator, considerable problems arise. This is because aqueous solutions containing more than 5 percent by weight of carboxymethyl cellulose can no longer be handled in industrial granulation processes because of their high viscosity and gel-like nature. In order to produce a sufficiently strong coating layer on the activator particles, very large amounts of the must therefore be used highly diluted cellulose ether solutions can be processed. If, as stated in Example 10 of DE-AS 11 62 967, 18 percent by weight of carboxymethyl cellulose should be applied to the bleach activator and it is assumed that a 5 percent solution that can still be processed due to its high viscosity would be 360 percent by weight (based on the amount of activator) 5% cellulose ether solution required. However, it can be shown that when more than 20 to 30 percent by weight of such a solution is used, lumpy to mush-like masses are produced instead of usable granules. For this reason it is also proposed in column 3 of DE-AS 11 62 967 to use alcoholic solutions of carboxymethyl cellulose. However, these require the installation of complex explosion protection devices and cause high costs for the recovery of the solvent. Such a method is unsuitable for technical purposes. The same problems occur if, instead of a cellulose ether solution, the fatty acids, fatty acid alkanolamides, fatty alcohols and carbowaxes dissolved in organic solvents, which are also proposed in DE-AS 11 62 967, are used as the covering material. To make matters worse, such coating materials do not dissolve or only dissolve very slowly in cold bleaching solutions, and the desired cold bleaching effect is therefore suppressed.
Aus der DE-OS 20 48 331 ist ein Verfahren zur Herstellung umhüllter, granulierter Bleichaktivatoren bekannt, bei dem der Aktivator zunächst mit einem zur Umhüllung oder Granulierung geeigneten Mittel trocken vermischt und in einem zweiten Schritt mit Wasser beziehungsweise in Wasser gelösten Granulierhilfsmitteln oder Filmbildnern besprüht und granuliert wird. Zur Herstellung der trockenen Vorgemische werden entweder wasserlösliche, in Waschmitteln übliche Gerüstsalze, wie Kristallwasser bindende Phosphate, Polyphosphate, Carbonate und Silikate von Alkalimetallen oder wasserunlösliche Füllstoffe, wie Kieselsäure, Magnesiumsilikat oder Magnesiumoxid vorgeschlagen. Man kann die gleichen wasserlöslichen, Kristallwasser bindenden Salze auch als Granulierhilfsmittel verwenden oder aber die trockenen Vorgemische mit einer wäßrigen Lösung filmbildender Stoffe, wie Cellulosederivate oder andere wasserlösliche Polymere natürlichen oder synthetischen Ursprungs besprühen und gleichzeitig granulieren. Dieses Verfahren ist jedoch nur zur Herstellung von Granulaten mit einem vergleichsweise niedrigen Gehalt an Bleichaktivatoren, das heißt mit einem solchen von weniger als 50 Gewichtsprozent,brauchbar. Die Granulate lassen sich daher nur auf solchen Gebieten einsetzen, bei denen der hohe Anteil an Zuschlagstoffen nicht stört.From DE-OS 20 48 331 a process for the production of coated, granulated bleach activators is known, in which the activator is first mixed dry with a suitable coating or granulation agent and sprayed in a second step with water or water-soluble granulation aids or film formers and is granulated. For the preparation of the dry premixes, either water-soluble framework salts customary in detergents, such as water of crystallization, are used phates, polyphosphates, carbonates and silicates of alkali metals or water-insoluble fillers such as silica, magnesium silicate or magnesium oxide are proposed. The same water-soluble salts which bind water of crystallization can also be used as granulation aids or the dry premixes can be sprayed with an aqueous solution of film-forming substances such as cellulose derivatives or other water-soluble polymers of natural or synthetic origin and granulated at the same time. However, this process is only useful for the production of granules with a comparatively low content of bleach activators, that is to say those with less than 50 percent by weight. The granules can therefore only be used in areas where the high proportion of additives does not interfere.
Der Erfindung liegt die Aufgabe zugrunde, ein Verfahren zur Herstellung gut schüttfähiger, gleichmäßig umhüllter und damit sehr stabiler Bleichaktivator-Granulate zu entwickeln, die einen wesentlich höheren Gehalt, beispielsweise einen von 90 Gewichtsprozent und mehr an aktiver Wirksubstanz aufweisen.The invention is based on the object of developing a process for the production of readily pourable, uniformly coated and thus very stable bleach activator granules which have a substantially higher content, for example one of 90 percent by weight and more, of active substance.
Gegenstand der Erfindung, mit der diese Aufgabe gelöst wird, ist ein Verfahren zur Herstellung eines lagerstabilen,Bleichaktivatoren enthaltenden Granulates durch trockenes Vermischen eines pulverförmigen Bleichaktivators aus der Klasse der N-acylierten Amine, Amide, Diketopiperazine und Glykolurile mit einem pulverförmigen Granulierhilfsmittel, Befeuchten des trockenen Vorgemisches mit einer wäßrigen Lösung des Granulierhilfsmittels und Granulieren des feuchten Gemisches in einer Nisch- und Granuliervorrichtung, dadurch gekennzeichnet, daß man zwecks Herstellung eines (auf wasserfreie Bestandteile bezogen) 90 bis 98 Gewichtsprozent an Bleichaktivator und 10 bis 2 Gewichtsprozent an Granulierhilfsmittel enthaltenden Granulates den pulverförmigen Bleichaktivator, der eine mittlere Korngröße von 0,01 bis 0,8 mm aufweist, in einer ersten Mischstufe mit 50 bis 100 Prozent des insgesamt anzuwendenden Granulierhilfsmittels, das aus einer Verbindung aus der Klasse der wasserlöslichen Celluloseether, Stärke und Stärkeether besteht und als schüttfähiges Pulver mit einer mittleren Korngröße von 0,01 bis 0,8 mm vorliegt, vermischt, worauf man in einer zweiten Mischstufe das Gemisch mit Wasser oder einer wäßrigen Lösung, die den Rest des Granulierhilfsmittels in 0,1 bis 10-gewichtsprozentiger Lösung enthält, befeuchtet und granuliert, worauf man dem feuchten Granulat soviel Wasser entzieht, daß der Wassergehalt weniger als 2 Gewichtsprozent, vorzugsweise weniger als 1 Gewichtsprozent beträgt.The invention with which this object is achieved is a process for producing a storage-stable, bleach activator-containing granules by dry mixing a powdered bleach activator from the class of N-acylated amines, amides, diketopiperazines and glycolurils with a powdered granulating aid, moistening the dry Premixed with an aqueous solution of the granulating aid and granulating the moist mixture in a niche and granulating device, characterized in that for the preparation of a granulate containing 90 to 98 percent by weight of bleach activator and 10 to 2 percent by weight of granulating aid, based on anhydrous constituents Bleach activator, which is a medium grain Size from 0.01 to 0.8 mm, in a first mixing stage with 50 to 100 percent of the total granulation aid to be used, which consists of a compound from the class of water-soluble cellulose ether, starch and starch ether and as a pourable powder with an average grain size of 0.01 to 0.8 mm is present, mixed, whereupon the mixture is moistened and granulated in a second mixing stage with water or an aqueous solution which contains the rest of the granulating aid in 0.1 to 10% by weight solution, whereupon the so much water is removed from moist granules that the water content is less than 2 percent by weight, preferably less than 1 percent by weight.
Unter "mittlerer Korngröße von 0,01 bis 0,8 mm" ist eine solche zu verstehen, bei der mehr als 50 Gewichtsprozent, vorzugsweise mindestens 80 Gewichtsprozent der Partikel eine Korngröße von 0,01 bis 0,8 mm und nicht mehr als 25 Gewichtsprozent, vorzugsweise nicht mehr als 10 Gewichtsprozent eine Korngröße von 0,8 bis höchstens ii6 mm sowie nicht mehr als 25 Gewichtsprozent, vorzugsweise nicht mehr als 10 Gewichtsprozent eine Korngröße von weniger als 0,01 mm aufweisen. Die Korngröße der Feinanteile ist nach unten nicht begrenzt, vielmehr können auch staubfeine Partikel vorliegen. Die Mitverwendbarkeit solcher staubförmiger Anteile, die in technischen, nichtklassierten Pulverprodukten mit breitem Kornspektrum üblich sind, stellt einen zusätzlichen Vorteil des Verfahrens dar.“Average grain size of 0.01 to 0.8 mm” is to be understood as meaning that in which more than 50 percent by weight, preferably at least 80 percent by weight of the particles have a grain size of 0.01 to 0.8 mm and not more than 25 percent by weight , preferably not more than 10% by weight have a grain size of 0.8 to at most ii6 mm and not more than 25% by weight, preferably not more than 10% by weight have a grain size of less than 0.01 mm. The grain size of the fine particles is not limited at the bottom, but dust-fine particles can also be present. The additional use of such dusty fractions, which are common in technical, unclassified powder products with a broad grain spectrum, represents an additional advantage of the process.
Als Bleichaktivatoren eignen sich die bekannten N-acylierten Amine, Diamine, Amide und Glykolurile, wie sie in den eingangs genannten Patentschriften offenbart sind. Es sind dies zum Beispiel Tetraacetylmethylendiamin, Tetraacetylethylendiamin, Diacetylanilin, Diacetyl-p-toluidin, 1,3-Diacetyl-5,5-dimethylhydantoin, Tetraacetylglykoluril, Tetrapropionylglykoluril, 1,4-Diacetyl-2,5-diketo- piperazin und 1,4-Diacetyl-3,6-dimethyl-2,5-diketopipera- zin. Bevorzugt wird Tetraacetylethylendiamin als Bleichaktivator eingesetzt.The known N-acylated amines, diamines, amides and glycolurils, as disclosed in the patents mentioned at the outset, are suitable as bleach activators. These are, for example, tetraacetylmethylene diamine, tetraacetylethylene diamine, diacetylaniline, diacetyl-p-toluidine, 1,3-diacetyl-5,5-dimethylhydantoin, tetraacetylglycoluril, tetrapropionylglycoluril, 1,4-diacetyl-2,5-diketo-piperazine -Diacetyl-3,6-dimethyl-2,5-diketopiperazine. Tetraacetylethylenediamine is preferably used as the bleach activator.
In der ersten Mischstufe wird der pulverförmige Bleichaktivator mit einem Teil des ebenfalls als Pulver vorliegenden Granulierhilfsmittel vermischt. Der Anteil des in dieser Stufe zur Anwendung kommenden Granulierhilfsmittel beträgt 50 bis 100, vorzugsweise 80 bis 95 . Gewichtsprozent des insgesamt verwendeten Granulierhilfsmittels. Es kann demnach in der 1. Mischstufe die Gesamtmenge oder nur ein Teil des Granulationshilfsnittels zugemischt werden. Die 2. Variante, bei der nur ein Teil des Granulationshilfsmittels trocken zugemischt und der Rest als Lösung in der 2. Stufe eingebracht wird, stellt jedoch die bevorzugte Arbeitsweise dar.In the first mixing stage, the powdery bleach activator is mixed with a part of the granulation aid, which is also in powder form. The proportion of the granulation aid used in this stage is 50 to 100, preferably 80 to 95. Weight percent of the total granulation aid used. Accordingly, the total amount or only part of the granulation auxiliary can be added in the 1st mixing stage. The second variant, in which only part of the granulation aid is dry-mixed and the rest is introduced as a solution in the second stage, is the preferred method of operation.
Die mittlere Korngröße des Granulierhilfsmittels beträgt 0,01 bis 0,8 mm entsprechend der vorstehenden Definition. Zweckmäßigerweise ist die Korngröße des pulverförmigen Granulierhilfsmittels ebenso groß oder geringer als die Korngröße des Bleichaktivators. So beträgt beispielsweise bei einer mittleren Korngröße des Bleichaktivators von 0,01 bis 0,8 mm die Korngröße des Granulierhilfsmittels vorteilhaft 0,01 bis 0,4 mm, wobei der Anteil der Partikel mit einer Korngröße von 0,4 bis 1,6 mm 25 Gewichtsprozent und insbesondere 10 Gewichtsprozent nicht übertrifft.The average grain size of the granulation aid is 0.01 to 0.8 mm according to the above definition. The grain size of the powdered granulation aid is expediently as large or smaller than the grain size of the bleach activator. For example, with an average particle size of the bleach activator of 0.01 to 0.8 mm, the particle size of the granulating aid is advantageously 0.01 to 0.4 mm, the proportion of particles with a particle size of 0.4 to 1.6 mm 25 Weight percent and in particular 10 weight percent does not exceed.
Das Granulierhilfsmittel besteht aus einem wasserlöslichen Celluloseether, wasserlöslicher Stärke oder einem wasserlöslichen Stärkeether. Beispiele für Celluloseether sind Methylcellulose, Ethylcellulose, Hydroxyethylcellulose, Methylhydroxyethylcellulose,*Methylhydroxypropyl- celluose, Carboxymethylcellulose (als Natriumsalz) und Methylcarboxymethylcellulose (Na-Salz). Als Stärke kommt beispielsweise depolymerisierte Stärke in Betracht. Geeignete Stärkeether sind beispielsweise Carboxymethylstärke, Hydroxyethylstärke und Methylstärke. Als besonders geeignet hat sich Natriumcarboxymethylcellulose erwiesen. = The granulation aid consists of a water-soluble cellulose ether, water-soluble starch or a water-soluble starch ether. Examples of cellulose ethers are celluose, methylcellulose, ethylcellulose, hydroxyethyl cellulose, methylhydroxyethylcellulose, methylhydroxypropyl *, carboxymethyl cellulose (as the sodium salt) and methyl carboxymethyl cellulose (Na salt). For example, depolymerized starch can be considered as starch. Suitable starch ethers are, for example, carboxymethyl starch, hydroxyethyl starch and methyl starch. Sodium carboxymethyl cellulose has proven to be particularly suitable. =
Das Mischen der beiden pulverförmigen Komponenten kann in üblichen, chargenweise oder kontinuierlich arbeitenden Mischvorrichtungen, die in der Regel mit rotierenden Mischorganen ausgerüstet sind, erfolgen. Je nach Wirksamkeit der Mischvorrichtung liegen die Mischzeiten für ein homogenes Gemisch im allgemeinen zwischen 30 Sekunden und 5 Minuten.The two powdery components can be mixed in conventional batch-wise or continuously operating mixing devices, which are generally equipped with rotating mixing elements. Depending on the effectiveness of the mixing device, the mixing times for a homogeneous mixture are generally between 30 seconds and 5 minutes.
Zur Beschleunigung des Lösungsprozesses bei der späteren Anwendung im Bleichbad können noch geringe Mengen an bekannten, pulverförmigen, in der Tablettenindustrie gebräuchlichen Sprengmitteln zugesetzt werden, sofern die eingesetzten Cellulose- und Stärkeether nicht bereits von sich aus eine gewisse Sprengwirkung entfalten. Brauchbare Sprengmittel sind zum Beispiel teilweise abgebaute Stärke, Stärkeether, Polyvinylpolypyrrolidon, Formaldehydcasein und quellfähige Magnesiumalumosilikate (Veegum). Der Anteil an derartigen Sprengmitteln kann 0 bis 2 Gewichtsprozent des wasserfreien Granulats betragen.In order to accelerate the dissolving process in the later application in the bleaching bath, small amounts of known powdery disintegrants which are common in the tablet industry can also be added, provided that the cellulose and starch ethers used do not automatically develop a certain explosive effect. Usable disintegrants are, for example, partially degraded starch, starch ether, polyvinylpolypyrrolidone, formaldehyde casein and swellable magnesium aluminosilicates (Veegum). The proportion of such disintegrants can be 0 to 2 percent by weight of the anhydrous granules.
Das trockene Pulvergemisch wird anschließend mit Wasser oder einer wäßrigen Lösung des noch verbliebenen Granulierhilfsmittels befeuchtet und granuliert. Sofern der Mischer der 1. Mischstufe sich auch für einen Granulierprozeß eignet, kann das Mischgut während des Granulationsprozesses darin verbleiben. Man kann aber auch mit Vorteil das Mischgut nach Abschluß des Mischprozesses in einen Granulator überführen, beispielsweise eine Granuliertrommel oder auf einen rotierenden Granulierteller und dort den Granulationsprozeß vornehmen, beziehungsweise zu Ende führen. Bei einer solchen Arbeitsweise werden zweckmäßigerweise ein Teil der Granulierflüssigkeit bereits gegen Ende der 1. Mischstufe in den Mischer eingegeben, um das Mischgut zu befeuchten und der Staubbildung entgegenzuwirken. Beispielsweise werden 5 bis 70 Prozent der Granulierflüssigkeit während des Nachmischens und 95 bis 30 Prozent der Flüssigkeit während des nachfolgenden Granulierens zugeführt.The dry powder mixture is then moistened with water or an aqueous solution of the remaining granulating aid and granulated. If the mixer of the first mixing stage is also suitable for a granulation process, the mix can remain therein during the granulation process. However, it is also advantageous to transfer the material to be mixed into a pelletizer, for example a pelletizing drum or onto a rotating pelletizer, and to carry out the pelletizing process there or to complete it. In such a mode of operation, part of the granulating liquid is expediently introduced into the mixer towards the end of the first mixing stage in order to moisten the material to be mixed and to counteract the formation of dust. For example, 5 to 70 percent of the granulation liquid is added during the post-mixing and 95 to 30 percent of the liquid during the subsequent granulation.
Soweit nicht Wasser als Granulierflüssigkeit verwendet wird, kommt das in der 2. Misch- und Granulationsstufe eingesetzte Granulierhilfsmittel vorzugsweise in 0,5- bis 5-gewichtsprozentiger Lösung zur Anwendung. Höherkonzentrierte, bis 10 Gewichtsprozent Granulierhilfsmittel enthaltende Lösungen empfehlen sich nur, wenn sie hinreichend niedrigviskos sind. Verwendet man Natriumcarboxymethylcellulose in einer Provenienz, so wie sie üblicherweise in Waschmitteln eingesetzt wird, beträgt die Konzentration zweckmäßigerweise nicht mehr als 4 Gewichtsprozent.If water is not used as the granulating liquid, the granulating aid used in the second mixing and granulation stage is preferably used in a 0.5 to 5 percent by weight solution. Solutions with a higher concentration and containing up to 10 percent by weight of granulation aids are only recommended if they are sufficiently low-viscosity. If sodium carboxymethyl cellulose is used in a provenance as is usually used in detergents, the concentration is advantageously not more than 4 percent by weight.
Die Menge der aufgebrachten Granulierflüssigkeit ist so zu bemessen, daß ein feuchtes, noch nicht zum Zusammenbacken neigendes Granulat entsteht. Dies wird dann erreicht, wenn der Wassergehalt des feuchten Granulates zwischen 10 und 35, vorzugsweise 15 bis 25 Gewichtsprozent beträgt. Pulvergemische mit kleinem Kornspektrum und höherem Anteil an pulverförmigem Granulierhilfsmittel können dabei größere Mengen an Granulierflüssigkeit aufnehmen als weniger feinkörnige Gemische mit geringem Anteil an Granulierhilfsmittel.The amount of granulation liquid applied is to be measured in such a way that moist granules are formed which are not yet prone to caking. This is achieved when the water content of the moist granules is between 10 and 35, preferably 15 to 25, weight percent. Powder mixtures with a small grain spectrum and a higher proportion of powdered granulating aid can absorb larger amounts of granulating liquid than less fine-grained mixtures with a small proportion of granulating aid.
Dem trockenen Pulvergemisch oder der Granulierflüssigkeit kann, sofern gewünscht, ein Farbstoff oder ein Weißpigment zur Anfärbung oder zur Überdeckung der Eigenfarbe der Rohstoffe zugesetzt werden. Hierfür sind im allgemeinen 0,01 bis 0,1 Gewichtsprozent, bezogen auf das Fertigprodukt, an Farbstoff oder Farbpigment ausreichend.If desired, a dye or a white pigment can be added to the dry powder mixture or the granulating liquid for coloring or to cover the inherent color of the raw materials. For this purpose, generally 0.01 to 0.1 percent by weight, based on the finished product, of dye or pigment is sufficient.
Der Wassergehalt des Gemisches wird anschließend auf weniger als 2, vorzugsweise weniger als 1 Gewichtsprozent erniedrigt. Das Entziehen des'überschüssigen Wassers kann durch Trocknen unter Wärmezufuhr erfolgen, wobei die Temperatur des Granulates zweckmäßigerweise 100 °C nicht übersteigt und unterhalb der Schmelztemperatur des Bleichaktivators liegt. Geeignet sind Trockner, die die granulare Struktur des Produktes nicht nachteilig verändern, beispielsweise Horden-, Vakuum- oder Wirbelschichttrockner. Die getrockneten Granulate sollen weniger als 2, vorzugsweise weniger als 1 Gewichtsprozent Wasser enthalten.The water content of the mixture is then reduced to less than 2, preferably less than 1 percent by weight. The excess water can be removed by drying with the addition of heat, the temperature of the granules expediently not exceeding 100 ° C. and below the melting temperature of the bleach activator. Dryers that do not adversely change the granular structure of the product are suitable, for example tray, vacuum or fluidized bed dryers. The dried granules should contain less than 2, preferably less than 1 percent by weight of water.
Sofern das Granulat zum späteren Einsatz in Waschmitteln bestimmt ist bzw. zu Waschzwecken verwendet werden soll, bei denen ein gewisser Gehalt an solchen Salzen nicht stört, die üblicherweise in Waschmitteln oder bei Waschprozessen eingesetzt werden und die unter Aufnahme von Kristallwasser zu kristallisieren vermögen, kann der Entzug des überschüssigen Wassers auch durch Vermischen der feuchten Granulate mit derartigen wasserentziehenden, im wesentlichen wasserfreien oder wasserarmen Salzen erfolgen. Beispiele für derartige Salze sind Natriuntripolyphosphat, Natriumsulfat, Natriumcarbonat, Natriumsilikat und zum Ionpnaustausch befähigte, wasserarme Natriumalumosilikate sowie deren Genische'. Die anzuwendende Menge richtet sich nach dem Wasserbindevermögen der betreffenden Salze sowie dem Wassergehalt des feuchten Granulates. Im Falle des bevorzugt angewendeten wasserfreien Natriumtripolyphosphats beträgt das Mischungsverhältnis von Tripolyphosphat zu feuchtem Granulat beispielsweise 1 : 3 bis 1 : 1,5, insbesondere 1 : 2 bis 1 : 1. Das Vermischen kann in üblichen Mischern oder Granuliervorrichtungen vorgenommen werden, wobei auch die zur Herstellung der feuchten Granulate verwendeten, mit Mischorganen ausgerüsteten Mischvorrichtung unmittelbar weiterbenutzt werden können. Auf diese Weise ist eine vereinfachte, insbesondere energiesparende Verarbeitung möglich, da die notwendige Trockenstufe eingespart werden kann.If the granulate is intended for later use in detergents or is to be used for washing purposes, in which a certain content of such salts does not interfere, which are usually used in detergents or in washing processes and which can crystallize with the absorption of water of crystallization, the Extraction of the excess water also by mixing the moist granules with such dehydrating, essentially water-free or low-water salts. Examples of such salts are sodium tripolyphosphate, sodium sulfate, sodium carbonate, sodium silicate and low-water sodium aluminosilicates capable of ion exchange and their genes. The amount to be used depends on the water binding capacity of the salts concerned and the water content of the moist granules. In the case of the preferably used anhydrous sodium tripolyphosphate, the mixing ratio of tripolyphosphate to moist granules is, for example, 1: 3 to 1: 1.5, in particular 1: 2 to 1: 1. Mixing can be carried out in conventional mixers or granulating devices, with the addition of Production of the moist granules used, equipped with mixing devices mixing device can be used immediately. In this way, simplified, in particular energy-saving, processing is possible since the necessary drying stage can be saved.
Weiterhin ist es möglich, dem zum Einsatz in Waschmitteln beziehungsweise in Waschproxessen bestimmten Granulaten während des Granulierprozesses auch solche Stoffe zuzusetzen, die üblicherweise in sehr geringer Menge den Waschmitteln in einem besonderen Mischprozeß getrennt zugemischt werden. Es handelt sich bei diesen Zusatzstoffen um solche, die bei der üblichen Waschmittelaufbereitung, insbesondere bei der Heißsprühtrocknung, inaktiviert werden beziehungsweise verloren gehen, wie Schauminhibitoren und Duftstoffe. Als Schauminhibitoren kommen übliche bekannte Entschäumungsmittel, vorzugsweise Polysiloxane sowie deren Gemische mit mikrofeiner Kieselsäure in Frage. Beispiele hierfür sind Polydimethylsiloxan mit einem Gehalt von zirka 1 - 10 Gewichtsprozent an mikrofeiner Kieselsäure. Der Anteil an derartigen Polysiloxanentschäumern kann 1 bis 5 Gewichtsprozent, vorzugsweise 2 bis 4 Gewichtsprozent, bezogen auf das fertige Granulat betragen. Das Zumischen des Entschäumers kann bereits in der 1. Mischstufe erfolgen; man kann den Entschäuner aber auch in der Granulierflüssigkeit dispergieren, die zwecks Vermeidung von Entmischungsvorgängen in diesem Falle jedoch ein Teil des Granulierhilfsmittels enthalten soll.It is also possible to add to the granules intended for use in detergents or in washing processes during the granulation process those substances which are usually mixed separately in very small amounts with the detergents in a special mixing process. These additives are those which are inactivated or lost in the conventional detergent preparation, in particular in hot spray drying, such as foam inhibitors and fragrances. Suitable foam inhibitors are customary known defoamers, preferably polysiloxanes, and mixtures thereof with microfine silica. Examples of these are polydimethylsiloxane with a content of approximately 1 to 10 percent by weight of microfine silica. The proportion of such polysiloxane foaming can be 1 to 5 percent by weight, preferably 2 to 4 percent by weight, based on the finished granulate. The defoamer can be added in the first mixing stage; however, the defoamer can also be dispersed in the granulating liquid which, in order to avoid segregation processes, should contain part of the granulating aid in this case.
Die in der angegebenen Weise hergestellten Granulate weisen ein günstiges Kornspektrum auf. Eventuell vorhandene Überschlag- und Feinanteile können abgesiebt und nach dem Mahlen der Grobanteile wieder in den Prozeß zurückgeführt werden. Die Granulate sind gut schüttfähig, nichtklebend und mit Rücksicht auf die vollständige Umhüllung der Aktivatorpartikel sehr beständig. Von besonderem Vorteil ist ihr hoher, 90 und mehr Gewichtsprozent betragender Anteil an Aktivsubstanz. Sie lassen sich mit Vorteil in Wasch-, Bleich-, Oxidations- und desinfizierend wirkenden Mitteln einsetzen und behalten ihre guten Eigenschaften auch im Gemisch mit den in diesen Mitteln enthaltenen Wirkstoffen.The granules produced in the manner indicated have a favorable grain spectrum. Any overlap and fine fractions can be screened off and returned to the process after grinding the coarse fractions. The granules are easy to pour, non-sticky and very stable considering the complete coating of the activator particles. Its high proportion of active substance, 90 and more percent by weight, is particularly advantageous. They can be used with advantage in detergents, bleaches, oxidizers and disinfectants and retain their good properties even when mixed with the active ingredients contained in these agents.
Als Bleichaktivator wurde Tetraacetylethylendiamin mit einer mittleren Korngröße von 0,01 bis 0,8 mm eingesetzt. Der Kornanteil zwischen 0,8 und 1,6 mm betrug 5 Gewichtsprozent, der Anteil unter 0,01 mm 10 Gewichtsprozent.Tetraacetylethylenediamine with an average grain size of 0.01 to 0.8 mm was used as the bleach activator. The grain fraction between 0.8 and 1.6 mm was 5 weight percent, the fraction under 0.01 mm 10 weight percent.
2,817 kg des pulverförmigen Bleichaktivators wurden in einem horizontal drehbar angeordneten Mischer, der mit an einer schnell rotierenden Welle angebrachten Misch- und Zerhackerwerkzeugen ausgerüstet war, mit 0,15 kg Na-Carboxymethylcellulose im Verlauf von 1 Minute gemischt. 94 Gewichtsprozent der Carboxymethylcellulose wiesen eine Korngröße von 0,01 bis 0,8 mm, 1 Gewichtsprozent eine solche von 0,8 bis 1,6 mm und 5 Gewichtsprozent eine solche von weniger als 0,01 mm auf. Der in die erste Mischstufe eingebrachte Anteil der Carboxymethylcellulose betrug 83,3 Prozent der Gesamtmenge.2.817 kg of the powdery bleach activator were mixed with 0.15 kg of Na-carboxymethyl cellulose in the course of 1 minute in a horizontally rotatable mixer which was equipped with mixing and chopping tools attached to a rapidly rotating shaft. 94 percent by weight of the carboxymethyl cellulose had a particle size of 0.01 to 0.8 mm, 1 percent by weight that 0.8 to 1.6 mm and 5 percent by weight that less than 0.01 mm. The proportion of carboxymethyl cellulose introduced into the first mixing stage was 83.3 percent of the total.
Anschließend wurde durch die rotierende hohle Antriebswelle des Mischers eine Lösung von 30 g Na-Carboxymethylcellulose (16,7 Prozent der Gesamtmenge) und 2,25 g eines Farbstoffes (Pigmosol blau) in 1,18 kg Wasser im Verlauf von 5 Minuten auf das in Bewegung gehaltene Mischgut aufgebracht und anschließend noch 1 Minute nachgranuliert. Nach dem Trocknen auf einen Wassergehalt von weniger als 1 Gewichtsprozent wurden die Fein- und Grobanteile mit einer Korngröße von unter 0,5 mm und über 1,5 mm ausgesiebt. Der Anteil an Granulat mit einem Kornspektrum zwischen 0,5 und 1,5 mm betrug 75 Gewichtsprozent. Das Granulat war homogen, gut schüttfähig und lagerstabil und wies die folgende Zusammensetzung (als wasserfreie Substanz gerechnet) auf:
- 93,95 Gewichtsprozent Tetraacetylethylendiamin
- 5,98 Gewichtsprozent Na-Carboxymethylcellulose
- 0,07 Gewichtsprozent Farbstoff.
- 93.95 percent by weight tetraacetylethylenediamine
- 5.98% by weight Na carboxymethyl cellulose
- 0.07 weight percent dye.
42,0 kg des in Beispiel 1 eingesetzten pulverförmigen Tetraacetylethylendiamins wurden in einem mit rotierenden Mischorganen ausgerüsteten Trommelmischer (LöDIGE-Mischer) mit 2,24 kg Na-Carboxymethylcellulose der in Beispiel 1 angegebenen Korngröße (88,2 Prozent der insgesamt eingesetzten Menge) 2 Minuten gemischt und anschließend unter ständigem weiteren Mischen mit einer Lösung von 170,4 g Na-Carboxymethylcellulose in 5,51 kg Wasser (3-gewichtsprozentig) besprüht zwecks Bindung staubförmiger Anteile. Das Mischgut wurde in einen kontinuierlich arbeitenden Mischgranulator (Leistung 800 kg/h) überführt. Der Auslauf dieses Mischers war über Transportbänder mit dem Einlauf verbunden, so daß das Produkt im Kreislauf geführt werden konnte. Im Verlauf von 9 Minuten wurden 4,3 kg einer 3-prozentigen Lösung von Na-Carboxymethylcellulose (entsprechend 129 g) durch die rotierende Welle des Granulationsmischers zugeführt. Es wurde noch 1 Minute nachgranuliert und dann das Produkt aus dem Kreislauf herausgeführt.42.0 kg of the powdery tetraacetylethylenediamine used in Example 1 were in a drum mixer equipped with rotating mixing elements (LöDIGE mixer) with 2.24 kg Na carboxymethyl cellulose of the grain size given in Example 1 (88.2 percent of the total amount used) for 2 minutes mixed and then sprayed with continuous mixing with a solution of 170.4 g Na carboxymethyl cellulose in 5.51 kg water (3 percent by weight) for the purpose of binding dust-like components. The mix was transferred to a continuously operating mixing granulator (capacity 800 kg / h). The outlet of this mixer was connected to the inlet via conveyor belts so that the product could be circulated. In the course of 9 minutes, 4.3 kg of a 3% solution of Na-carboxymethyl cellulose (corresponding to 129 g) were fed in through the rotating shaft of the granulation mixer. Granulation was continued for 1 minute and then the product was led out of the circuit.
Die Hauptmenge des Granulates wurde in einer Vakuumtrockenvorrichtung bei 50 Torr im Verlauf von 24 Stunden auf einen Wassergehalt von unter 1 Gewichtsprozent getrocknet. 3 kg des feuchten Granulates wurden in einem Wirbelschichttrockner mit Luft, die eine Eintrittstemperatur von 57 °C aufwies, während 10 Minuten auf den gleichen Trocknungsgrad getrocknet. In beiden Fällen betrug der Anteil des Granulates mit einer Korngröße von 0,5 bis 1,5 mm 65 Gewichtsprozent. Überschlag und Feinanteile wurden ausgesiebt und nach Mahlen der Grobanteile in den nachfolgenden Granulationsprozeß eingegeben.The majority of the granules were dried in a vacuum dryer at 50 torr over 24 hours to a water content of less than 1 percent by weight. 3 kg of the moist granules were dried in a fluidized bed dryer with air having an inlet temperature of 57 ° C. for 10 minutes to the same degree of drying. In both cases, the proportion of the granules with a grain size of 0.5 to 1.5 mm was 65 percent by weight. The rollover and fine fractions were sieved out and, after grinding the coarse fractions, entered into the subsequent granulation process.
Das Granulat besaß die gleichen vorteilhaften Eigenschaften wie in Beispiel 1 und wies die folgende Zusammensetzung (wasserfreie Substanz) auf:
- 94,3 Gewichtsprozent Tetraacetylethylendiamin
- 5,7 Gewichtsprozent Na-Carboxymethylcellulose.
- 94.3 percent by weight tetraacetylethylenediamine
- 5.7% by weight Na carboxymethyl cellulose.
In einen kontinuierlich arbeitenden Mischer wurden 95 Gewichtsteile des in Beispiel 1 verwendeten Tetraacetylethylendiamins mit 5 Gewichtsteilen Na-Carboxymethylcellulose kontinuierlich gemischt. Im letzten Drittel des Mischers wurden mittels Düsen 10 Gewichtsteile einer Lösung von 0,34 Gewichtsteile Na-Carboxymethylcellulose in 11 Gewichtsteilen Wasser (3-prozentige Lösung) zwecks Staubbindung kontinuierlich auf das Mischgut aufgesprüht. Das angefeuchtete Gemisch gelangte in einen kontinuierlich arbeitenden Granulator (vgl. Beispiel 2), wo es mit 10 Gewichtsteilen einer Lösung von 96,33 Gewichtsprozent Wasser, 3 Gewichtsprozent Na-Carboxymethylcellulose und 0,67 Gewichtsprozent Farbstoff (vgl. Beispiel 1) besprüht und granuliert wurde. Aus dem Granulator gelangte das Gut auf ein Transportband, von dem aus ein Teilstrom von 70 Gewichtsprozent ausgeschleust und ein Teilstrom von 30 Gewichtsprozent in den Granulator zurückgeführt wurden. Das fertige Granulat wies nach dem Trocknen die folgende Zusammensetzung auf:
- 94,37 Gewichtsprozent Tetraacetylethylendiamin
- 5,56 Gewichtsprozent Na-Carboxymethylcellulose
- 0,07 Gewichtsprozent Farbstoff.
- 94.37 weight percent tetraacetylethylenediamine
- 5.56% by weight Na carboxymethyl cellulose
- 0.07 weight percent dye.
Entsprechend der in Beispiel 1 angegebenen Herstellungsweise wurden 91,45 Gewichtsteile Tetraacetylethylendiamin, das folgende Korngröße aufwies .(in Gewichtsprozent):
Beispiel 4 wurde wiederholt, wobei jedoch der Polysiloxan-Entschäumer in der wäßrigen, Carboxymethylcellulose enthaltenden Granulierflüssigkeit dispergiert worden war. Hinsichtlich seiner Eigenschaften entsprach das Produkt dem des Beispiels 4.Example 4 was repeated, but the polysiloxane defoamer had been dispersed in the aqueous granulation liquid containing carboxymethyl cellulose. In terms of its properties, the product corresponded to that of Example 4.
42,0 kg des in Beispiel 1 eingesetzten pulverförmigen Tetraacetylethylendiamins wurden in einem mit rotierenden Mischorganen ausgerüsteten Trommelmischer (LÖDIGE-Mischer) mit 2,24 kg Na-Carboxymethylcellulose der in Beispiel 1 angegebenen Korngröße (88,2 Prozent der insgesamt eingesetzten Menge) 2 Minuten gemischt und anschließend unter ständigem weiteren Mischen mit einer Lösung von 170,4 g Na-Carboxymethylcellulose in 5,51 kg Wasser (3-gewichtsprozentig) besprüht zwecks Bindung staubförmiger Anteile. Das Mischgut wurde in einen kontinuierlich arbeitenden Mischgranulator (Leistung 800 kg/h) überführt. Der Auslauf dieses Mischers war über Transportbänder mit dem Einlauf verbunden, so daß das Produkt im Kreislauf geführt werden konnte. Im Verlauf von 9 Minuten wurden 4,3 kg einer 3-prozentigen Lösung von Na-Carboxymethylcellulose (entsprechend 129 g) durch die rotierende Welle des Granulationsmischers zugeführt.42.0 kg of the powdery tetraacetylethylenediamine used in Example 1 were in a drum mixer equipped with rotating mixing elements (LÖDIGE mixer) with 2.24 kg Na carboxymethyl cellulose of the grain size given in Example 1 (88.2 percent of the total amount used) for 2 minutes mixed and then sprayed with continuous mixing with a solution of 170.4 g Na carboxymethyl cellulose in 5.51 kg water (3 percent by weight) for the purpose of binding dust-like components. The mix was transferred to a continuously operating mixing granulator (capacity 800 kg / h). The outlet of this mixer was connected to the inlet via conveyor belts so that the product could be circulated. In the course of 9 minutes, 4.3 kg of a 3% solution of Na-carboxymethyl cellulose (corresponding to 129 g) were fed in through the rotating shaft of the granulation mixer.
Im Anschluß daran wurden 40 kg wasserfreies Natriumtripolyphosphat (Phase-II-Gehalt 92 Gewichtsprozent, Diphosphatgehalt 2 Gewichtsprozent) im Verlauf von 3 Minuten zugemischt und der Granulationsprozeß noch 3 Minuten fortgesetzt. Es wurde ein trockenes, gut rieselfähiges Granulat erhalten mit einem Anteil von 58 Gewichtsprozent der Korngröße 0,5 bis 1,5 mm. Überschlag und Feinanteile wurden ausgesiebt und nach Mahlen der Großanteile in den nachfolgenden Granulationsprozeß eingegeben.Subsequently, 40 kg of anhydrous sodium tripolyphosphate (phase II content 92 percent by weight, diphosphate content 2 percent by weight) were mixed in over the course of 3 minutes and the granulation process continued for a further 3 minutes. A dry, free-flowing granulate was obtained with a proportion of 58 percent by weight of the grain size 0.5 to 1.5 mm. The rollover and fine fractions were sieved out and, after grinding the large fractions, entered into the subsequent granulation process.
Claims (15)
Priority Applications (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
AT81102083T ATE14594T1 (en) | 1980-03-28 | 1981-03-20 | PROCESS FOR MAKING A STORAGE STABLE, HIGHLY DISSOLVABLE GRANULE CONTAINING BLEACH ACTIVATORS. |
Applications Claiming Priority (2)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
DE3011998 | 1980-03-28 | ||
DE3011998A DE3011998C2 (en) | 1980-03-28 | 1980-03-28 | Process for the production of a storage-stable, easily soluble granulate with a content of bleach activators |
Publications (2)
Publication Number | Publication Date |
---|---|
EP0037026A1 true EP0037026A1 (en) | 1981-10-07 |
EP0037026B1 EP0037026B1 (en) | 1985-07-31 |
Family
ID=6098590
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
EP81102083A Expired EP0037026B1 (en) | 1980-03-28 | 1981-03-20 | Process for the preparation of a storage-stable, easily soluble granulated compound containing a bleach activator |
Country Status (5)
Country | Link |
---|---|
US (1) | US4372868A (en) |
EP (1) | EP0037026B1 (en) |
JP (1) | JPS56149500A (en) |
AT (1) | ATE14594T1 (en) |
DE (2) | DE3011998C2 (en) |
Cited By (28)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
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 |
DE3208216A1 (en) * | 1982-03-06 | 1983-09-08 | Basf Ag, 6700 Ludwigshafen | Granular bleach activator |
EP0241962A2 (en) * | 1986-03-25 | 1987-10-21 | Unilever N.V. | Granular non-phosphorus detergent bleach compositions |
EP0374867A1 (en) * | 1988-12-22 | 1990-06-27 | Hoechst Aktiengesellschaft | Process for the production of storage-stable, easily soluble granulated block activators |
EP0468824A2 (en) * | 1990-07-27 | 1992-01-29 | WARWICK INTERNATIONAL GROUP LIMITED (Co. n 2864019) | Granular compositions |
WO1992011349A1 (en) * | 1990-12-19 | 1992-07-09 | Henkel Kommanditgesellschaft Auf Aktien | Granulate with encapsulated bleaching activator |
US5334324A (en) * | 1990-08-03 | 1994-08-02 | Henkel Kommanditgesellschaft Auf Aktien | Bleach activators in granular form |
EP0710716A2 (en) | 1994-11-02 | 1996-05-08 | Hoechst Aktiengesellschaft | Granulated bleach actuators and production thereof |
US5691295A (en) * | 1995-01-17 | 1997-11-25 | Cognis Gesellschaft Fuer Biotechnologie Mbh | Detergent compositions |
EP0835926A2 (en) * | 1996-10-10 | 1998-04-15 | Clariant GmbH | Method of production of a coated bleach activator granule |
US5904736A (en) * | 1995-04-28 | 1999-05-18 | Henkel Kommanditgesellschaft Auf Aktien | Cellulase-containing washing agents |
US5972668A (en) * | 1994-06-28 | 1999-10-26 | Henkel Kommanditgesellschaft Auf Aktien | Production of multi-enzyme granules |
WO2000019006A1 (en) * | 1998-09-30 | 2000-04-06 | Warwick International Group Limited | Oxygen bleaching of pulp using an agglomerated bleach activator |
US6063750A (en) * | 1997-09-16 | 2000-05-16 | Clariant Gmbh | Bleach activator granules |
GB2345701A (en) * | 1999-01-12 | 2000-07-19 | Procter & Gamble | Particulate bleaching components |
US6214785B1 (en) | 1998-09-09 | 2001-04-10 | Clariant Gmbh | Bleach activator granules |
US6254892B1 (en) | 1999-03-05 | 2001-07-03 | Rohm And Haas Company | Pellet formulations |
US6270690B1 (en) | 1997-09-16 | 2001-08-07 | Clariant Gmbh | Storage stable bleach activator granules |
US6313081B1 (en) | 1995-04-28 | 2001-11-06 | Henkel Kommanditgesellschaft Auf Aktien (Kgaa) | Detergents comprising cellulases |
US6340662B1 (en) | 1998-12-11 | 2002-01-22 | Henkel Kommanditgesellschaft Auf Aktien (Kgaa) | Aqueous foam regulator emulsion |
US7098179B2 (en) | 2001-10-22 | 2006-08-29 | Henkel Kommanditgesellschaft Auf Aktien (Henkel Kgaa) | Cotton active, dirt removing urethane-based polymers |
US7431739B2 (en) | 2005-06-08 | 2008-10-07 | Henkel Kommanditgesellschaft Auf Aktien | Boosting the cleaning performance of laundry detergents by polymer of styrene/methyl methacrylate/methyl polyethylene glycol |
WO2008149069A1 (en) * | 2007-06-02 | 2008-12-11 | Reckitt Benckiser N.V. | Composition |
EP2021454A1 (en) * | 2006-04-27 | 2009-02-11 | OCI Chemical Corporation | Co-granulates of bleach activator-peroxide compounds |
US7550156B2 (en) | 2001-11-23 | 2009-06-23 | Rohm And Haas Company | Optimised pellet formulations |
US8034123B2 (en) | 2005-06-08 | 2011-10-11 | Henkel Ag & Co., Kgaa | Boosting cleaning power of detergents by means of a polymer |
WO2019233789A1 (en) * | 2018-06-07 | 2019-12-12 | Henkel Ag & Co. Kgaa | Detergent composition with a yield point |
Families Citing this family (35)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
ATE15771T1 (en) * | 1981-09-08 | 1985-10-15 | Interox Chemicals Ltd | GRANULATION. |
GB8310080D0 (en) * | 1983-04-14 | 1983-05-18 | Interox Chemicals Ltd | Bleach composition |
IT1180458B (en) * | 1984-03-22 | 1987-09-23 | Mira Lanza Spa | GRANULAR WHITENING ACTIVATOR AND ITS MANUFACTURING PROCESS |
US4964870A (en) * | 1984-12-14 | 1990-10-23 | The Clorox Company | Bleaching with phenylene diester peracid precursors |
DE3504628A1 (en) * | 1985-02-11 | 1986-08-14 | Henkel KGaA, 4000 Düsseldorf | METHOD FOR PRODUCING GRANULATE GRANULATE |
DE3522359A1 (en) * | 1985-06-22 | 1987-01-02 | Basf Ag | METHOD FOR MAKING CRYSTALINE ORGANIC MATERIALS |
US5433881A (en) * | 1986-03-19 | 1995-07-18 | Warwick International Group Limited | Granulation process for making granular bleach activator compositions and resulting product |
DE3609735A1 (en) | 1986-03-22 | 1987-09-24 | Henkel Kgaa | METHOD FOR PURIFYING TETRAACETYLETHYLENE DIAMINE |
US5112514A (en) * | 1986-11-06 | 1992-05-12 | The Clorox Company | Oxidant detergent containing stable bleach activator granules |
US5002691A (en) * | 1986-11-06 | 1991-03-26 | The Clorox Company | Oxidant detergent containing stable bleach activator granules |
US5269962A (en) | 1988-10-14 | 1993-12-14 | The Clorox Company | Oxidant composition containing stable bleach activator granules |
EP0367339B1 (en) * | 1988-11-02 | 1996-03-13 | Unilever N.V. | Process for preparing a high bulk density granular detergent composition |
GB8907187D0 (en) * | 1989-03-30 | 1989-05-10 | Unilever Plc | Detergent compositions and process for preparing them |
US4988451A (en) * | 1989-06-14 | 1991-01-29 | Lever Brothers Company, Division Of Conopco, Inc. | Stabilization of particles containing quaternary ammonium bleach precursors |
GB8922018D0 (en) * | 1989-09-29 | 1989-11-15 | Unilever Plc | Detergent compositions and process for preparing them |
US5055217A (en) * | 1990-11-20 | 1991-10-08 | Lever Brothers Company, Division Of Conopco, Inc. | Polymer protected bleach precursors |
USH1604H (en) * | 1993-06-25 | 1996-11-05 | Welch; Robert G. | Process for continuous production of high density detergent agglomerates in a single mixer/densifier |
WO1996011167A1 (en) * | 1994-10-07 | 1996-04-18 | Bio-Lab, Inc. | A process for stabilizing biocides and an apparatus for disinfecting water systems using the stabilized biocides |
GB9519094D0 (en) * | 1995-09-19 | 1995-11-22 | Warwick Int Group | Granulated active with controlled release |
DE19535082A1 (en) * | 1995-09-21 | 1997-03-27 | Henkel Ecolab Gmbh & Co Ohg | Paste-like detergent and cleaning agent |
DE19725508A1 (en) | 1997-06-17 | 1998-12-24 | Clariant Gmbh | Detergents and cleaning agents |
WO2002050231A1 (en) * | 2000-12-19 | 2002-06-27 | Fmc Corporation | Disintegrant composition |
DE10108459A1 (en) * | 2001-02-22 | 2002-09-12 | Henkel Kgaa | Stability of foam-regulator granulates for use in detergents is improved by using a carrier containing alkali carbonate and a Bronsted acid |
US20040147427A1 (en) * | 2002-11-14 | 2004-07-29 | The Procter & Gamble Company | Rinse aid containing encapsulated glasscare active salt |
ES2283831T3 (en) | 2002-12-20 | 2007-11-01 | Henkel Kommanditgesellschaft Auf Aktien | DETERGENTS OR CLEANERS CONTAINING WHITENER. |
DE10351325A1 (en) * | 2003-02-10 | 2004-08-26 | Henkel Kgaa | Detergent or cleaning agent with water-soluble builder system and dirt-releasing cellulose derivative |
EP1592765B1 (en) * | 2003-02-10 | 2007-05-30 | Henkel Kommanditgesellschaft auf Aktien | Intensification of the cleaning power of detergents using a cellulose derivative and a hygroscopic polymer |
ATE342953T1 (en) * | 2003-02-10 | 2006-11-15 | Henkel Kgaa | BLEACH-CONTAINED DETERGENT WITH COTTON-ACTIVE DIRT-REMOVING CELLULOSE DERIVATIVE |
DE502004003835D1 (en) * | 2003-02-10 | 2007-06-28 | Henkel Kgaa | BLEACHING DETERGENT WASHING OR CLEANING AGENT WITH WATER-SOLUBLE BUILDING SYSTEM AND DIRT-RELATED CELLULOSE DERIVATIVE |
ES2279344T3 (en) * | 2003-02-10 | 2007-08-16 | Henkel Kommanditgesellschaft Auf Aktien | INCREASED WATER ABSORPTION CAPACITY OF TEXTILES. |
DE10351321A1 (en) * | 2003-02-10 | 2004-08-26 | Henkel Kgaa | Enhancing the cleaning performance of detergents through a combination of cellulose derivatives |
EP1592768A2 (en) * | 2003-02-10 | 2005-11-09 | Henkel Kommanditgesellschaft auf Aktien | Use of cellulose derivatives as foam regulators |
JP2007538120A (en) * | 2004-05-17 | 2007-12-27 | ヘンケル コマンディットゲゼルシャフト アウフ アクチエン | Detergents containing bleach-enhanced transition metal complexes, optionally generated in situ |
EP2103678A1 (en) * | 2008-03-18 | 2009-09-23 | The Procter and Gamble Company | Detergent composition comprising a co-polyester of dicarboxylic acids and diols |
EP2103675A1 (en) * | 2008-03-18 | 2009-09-23 | The Procter and Gamble Company | Detergent composition comprising cellulosic polymer |
Citations (2)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
DE1162967B (en) * | 1959-06-19 | 1964-02-13 | Konink Ind Mij Voorheen Noury | Detergents and / or bleaches |
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 |
Family Cites Families (2)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US4009113A (en) * | 1971-04-30 | 1977-02-22 | Lever Brothers Company | Protection of materials |
AT326611B (en) * | 1972-07-31 | 1975-12-29 | Henkel & Cie Gmbh | BLEACHING AID SUITABLE AS A COMPONENT OF POWDERED DETERGENTS AND BLEACHING AGENTS |
-
1980
- 1980-03-28 DE DE3011998A patent/DE3011998C2/en not_active Expired
-
1981
- 1981-03-20 AT AT81102083T patent/ATE14594T1/en not_active IP Right Cessation
- 1981-03-20 EP EP81102083A patent/EP0037026B1/en not_active Expired
- 1981-03-20 DE DE8181102083T patent/DE3171538D1/en not_active Expired
- 1981-03-20 US US06/246,097 patent/US4372868A/en not_active Expired - Fee Related
- 1981-03-26 JP JP4326981A patent/JPS56149500A/en active Granted
Patent Citations (2)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
DE1162967B (en) * | 1959-06-19 | 1964-02-13 | Konink Ind Mij Voorheen Noury | Detergents and / or bleaches |
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 |
Cited By (41)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
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 |
EP0075818A3 (en) * | 1981-09-28 | 1984-03-07 | Basf Aktiengesellschaft | Granular bleach activator |
US4695397A (en) * | 1981-09-28 | 1987-09-22 | Basf Aktiengesellschaft | Granular bleaching activator |
DE3208216A1 (en) * | 1982-03-06 | 1983-09-08 | Basf Ag, 6700 Ludwigshafen | Granular bleach activator |
EP0241962A3 (en) * | 1986-03-25 | 1988-06-22 | Unilever Nv | Granular non-phosphorus detergent bleach compositions |
EP0241962A2 (en) * | 1986-03-25 | 1987-10-21 | Unilever N.V. | Granular non-phosphorus detergent bleach compositions |
EP0374867A1 (en) * | 1988-12-22 | 1990-06-27 | Hoechst Aktiengesellschaft | Process for the production of storage-stable, easily soluble granulated block activators |
US5100576A (en) * | 1988-12-22 | 1992-03-31 | Hoechst Aktiengesellschaft | Process for the preparation of a readily soluble bleach activator granulate with a long shelf life |
EP0468824A2 (en) * | 1990-07-27 | 1992-01-29 | WARWICK INTERNATIONAL GROUP LIMITED (Co. n 2864019) | Granular compositions |
EP0468824A3 (en) * | 1990-07-27 | 1992-07-01 | Warwick International Group Plc | Granular compositions |
US5334324A (en) * | 1990-08-03 | 1994-08-02 | Henkel Kommanditgesellschaft Auf Aktien | Bleach activators in granular form |
WO1992011349A1 (en) * | 1990-12-19 | 1992-07-09 | Henkel Kommanditgesellschaft Auf Aktien | Granulate with encapsulated bleaching activator |
US5972668A (en) * | 1994-06-28 | 1999-10-26 | Henkel Kommanditgesellschaft Auf Aktien | Production of multi-enzyme granules |
EP0710716A2 (en) | 1994-11-02 | 1996-05-08 | Hoechst Aktiengesellschaft | Granulated bleach actuators and production thereof |
US5716569A (en) * | 1994-11-02 | 1998-02-10 | Hoechst Aktiengesellschaft | Granulated bleaching activators and their preparation |
US5855625A (en) * | 1995-01-17 | 1999-01-05 | Henkel Kommanditgesellschaft Auf Aktien | Detergent compositions |
US5691295A (en) * | 1995-01-17 | 1997-11-25 | Cognis Gesellschaft Fuer Biotechnologie Mbh | Detergent compositions |
US5904736A (en) * | 1995-04-28 | 1999-05-18 | Henkel Kommanditgesellschaft Auf Aktien | Cellulase-containing washing agents |
US6313081B1 (en) | 1995-04-28 | 2001-11-06 | Henkel Kommanditgesellschaft Auf Aktien (Kgaa) | Detergents comprising cellulases |
EP0835926A3 (en) * | 1996-10-10 | 1999-01-07 | Clariant GmbH | Method of production of a coated bleach activator granule |
EP0835926A2 (en) * | 1996-10-10 | 1998-04-15 | Clariant GmbH | Method of production of a coated bleach activator granule |
US6645927B1 (en) | 1996-10-10 | 2003-11-11 | Clariant Gmbh | Process for producing coated bleach activator granules |
US6107266A (en) * | 1996-10-10 | 2000-08-22 | Clariant Gmbh | Process for producing coated bleach activator granules |
US6270690B1 (en) | 1997-09-16 | 2001-08-07 | Clariant Gmbh | Storage stable bleach activator granules |
US6063750A (en) * | 1997-09-16 | 2000-05-16 | Clariant Gmbh | Bleach activator granules |
US6133216A (en) * | 1997-09-16 | 2000-10-17 | Clariant Gmbh | Coated ammonium nitrile bleach activator granules |
US6214785B1 (en) | 1998-09-09 | 2001-04-10 | Clariant Gmbh | Bleach activator granules |
WO2000019006A1 (en) * | 1998-09-30 | 2000-04-06 | Warwick International Group Limited | Oxygen bleaching of pulp using an agglomerated bleach activator |
US6340662B1 (en) | 1998-12-11 | 2002-01-22 | Henkel Kommanditgesellschaft Auf Aktien (Kgaa) | Aqueous foam regulator emulsion |
GB2345701A (en) * | 1999-01-12 | 2000-07-19 | Procter & Gamble | Particulate bleaching components |
US6254892B1 (en) | 1999-03-05 | 2001-07-03 | Rohm And Haas Company | Pellet formulations |
US7098179B2 (en) | 2001-10-22 | 2006-08-29 | Henkel Kommanditgesellschaft Auf Aktien (Henkel Kgaa) | Cotton active, dirt removing urethane-based polymers |
US7550156B2 (en) | 2001-11-23 | 2009-06-23 | Rohm And Haas Company | Optimised pellet formulations |
US7431739B2 (en) | 2005-06-08 | 2008-10-07 | Henkel Kommanditgesellschaft Auf Aktien | Boosting the cleaning performance of laundry detergents by polymer of styrene/methyl methacrylate/methyl polyethylene glycol |
US8034123B2 (en) | 2005-06-08 | 2011-10-11 | Henkel Ag & Co., Kgaa | Boosting cleaning power of detergents by means of a polymer |
US7709437B2 (en) | 2006-04-27 | 2010-05-04 | Oci Chemical Corp. | Co-granulates of bleach activator-peroxide compounds |
EP2021454A1 (en) * | 2006-04-27 | 2009-02-11 | OCI Chemical Corporation | Co-granulates of bleach activator-peroxide compounds |
US8431519B2 (en) | 2006-04-27 | 2013-04-30 | Oci Chemical Corp. | Co-granulates of bleach activator-peroxide compounds |
WO2008149069A1 (en) * | 2007-06-02 | 2008-12-11 | Reckitt Benckiser N.V. | Composition |
WO2019233789A1 (en) * | 2018-06-07 | 2019-12-12 | Henkel Ag & Co. Kgaa | Detergent composition with a yield point |
Also Published As
Publication number | Publication date |
---|---|
DE3171538D1 (en) | 1985-09-05 |
ATE14594T1 (en) | 1985-08-15 |
JPH0340080B2 (en) | 1991-06-17 |
DE3011998C2 (en) | 1982-06-16 |
US4372868A (en) | 1983-02-08 |
DE3011998A1 (en) | 1981-10-08 |
JPS56149500A (en) | 1981-11-19 |
EP0037026B1 (en) | 1985-07-31 |
Similar Documents
Publication | Publication Date | Title |
---|---|---|
EP0037026B1 (en) | Process for the preparation of a storage-stable, easily soluble granulated compound containing a bleach activator | |
EP0070474B1 (en) | Process for the production of enveloped granular bleaching activators | |
DE69404543T2 (en) | Stabilized sodium percarbonate particles | |
EP0191396B2 (en) | Process for the production of free-flowing granulates | |
DE68921858T2 (en) | Process for the production of bleach granules. | |
DE4435743C2 (en) | Process for the production of a multi-component granulate | |
DE69425534T2 (en) | Mixing process for the formulation of detergents | |
EP0328768A1 (en) | Continuous process for making granules of sodium perborate | |
EP0374867B1 (en) | Process for the production of storage-stable, easily soluble granulated block activators | |
DE69104124T2 (en) | Process for the production of stabilized sodium percarbonate. | |
DE4040654A1 (en) | GRANULES WITH COVERED BLEACH ACTIVATOR | |
DE3926253A1 (en) | Compressed solid granules prepn. of washing agent - by extruding mixt. of solid components and plasticiser, cutting strand to size, treating with further active materials and drying | |
DE2535183A1 (en) | PROCESS FOR COVERING AND GRANULATING TETRAACETYLGLYCOLURIL AND TETRAACETYLAETHYLENEDIAMINE | |
DE1617246C3 (en) | Process for the production of free-flowing washing powder mixtures | |
DE2024439A1 (en) | Process for the production of agglomerates from condensed alkali phosphates | |
EP1451283A1 (en) | Method for producing bleach activator granules | |
DE1037432B (en) | Process for crumbling perborate | |
EP0687245A1 (en) | Process for producing stabilised sodium percarbonate | |
EP0822974B1 (en) | Long shelf life granulate containing bleach activators and its production | |
EP0061600B1 (en) | Process for the preparation of mixed granules of condensed phosphates and builders | |
DE2925137A1 (en) | Granular detergent compsns. - contg. specified amts. of tri:poly:phosphate, water and other ingredients | |
DE2365270A1 (en) | Adding active ingredients to detergents - with melt-sprayed mixt contg natural or partly decomposed starch or starch ether | |
AT213373B (en) | Process for the production of granules of condensed phosphate perhydrates | |
EP0088267B1 (en) | Cogranulate from alkali silicate and alkali phosphate, and process for the preparation of the granulate | |
DD251044A3 (en) | PROCESS FOR PRODUCING GRANULATED WASHING AND CLEANING AGENTS |
Legal Events
Date | Code | Title | Description |
---|---|---|---|
PUAI | Public reference made under article 153(3) epc to a published international application that has entered the european phase |
Free format text: ORIGINAL CODE: 0009012 |
|
AK | Designated contracting states |
Designated state(s): AT BE CH DE FR GB IT LU NL SE |
|
17P | Request for examination filed |
Effective date: 19811029 |
|
RBV | Designated contracting states (corrected) |
Designated state(s): AT BE CH DE FR GB IT LI NL SE |
|
ITF | It: translation for a ep patent filed | ||
GRAA | (expected) grant |
Free format text: ORIGINAL CODE: 0009210 |
|
AK | Designated contracting states |
Designated state(s): AT BE CH DE FR GB IT LI NL SE |
|
REF | Corresponds to: |
Ref document number: 14594 Country of ref document: AT Date of ref document: 19850815 Kind code of ref document: T |
|
REF | Corresponds to: |
Ref document number: 3171538 Country of ref document: DE Date of ref document: 19850905 |
|
ET | Fr: translation filed | ||
PLBI | Opposition filed |
Free format text: ORIGINAL CODE: 0009260 |
|
26 | Opposition filed |
Opponent name: HOECHST AKTIENGESELLSCHAFT, FRANKFURT Effective date: 19860428 |
|
NLR1 | Nl: opposition has been filed with the epo |
Opponent name: HOECHST AKTIENGESELLSCHAFT |
|
PLBN | Opposition rejected |
Free format text: ORIGINAL CODE: 0009273 |
|
STAA | Information on the status of an ep patent application or granted ep patent |
Free format text: STATUS: OPPOSITION REJECTED |
|
27O | Opposition rejected |
Effective date: 19900828 |
|
NLR2 | Nl: decision of opposition | ||
ITTA | It: last paid annual fee | ||
EAL | Se: european patent in force in sweden |
Ref document number: 81102083.3 |
|
PGFP | Annual fee paid to national office [announced via postgrant information from national office to epo] |
Ref country code: DE Payment date: 19991231 Year of fee payment: 20 |
|
PGFP | Annual fee paid to national office [announced via postgrant information from national office to epo] |
Ref country code: SE Payment date: 20000307 Year of fee payment: 20 |
|
PGFP | Annual fee paid to national office [announced via postgrant information from national office to epo] |
Ref country code: FR Payment date: 20000310 Year of fee payment: 20 |
|
PGFP | Annual fee paid to national office [announced via postgrant information from national office to epo] |
Ref country code: AT Payment date: 20000313 Year of fee payment: 20 |
|
PGFP | Annual fee paid to national office [announced via postgrant information from national office to epo] |
Ref country code: GB Payment date: 20000315 Year of fee payment: 20 |
|
PGFP | Annual fee paid to national office [announced via postgrant information from national office to epo] |
Ref country code: CH Payment date: 20000328 Year of fee payment: 20 |
|
PGFP | Annual fee paid to national office [announced via postgrant information from national office to epo] |
Ref country code: NL Payment date: 20000330 Year of fee payment: 20 |
|
PGFP | Annual fee paid to national office [announced via postgrant information from national office to epo] |
Ref country code: BE Payment date: 20000518 Year of fee payment: 20 |
|
BE20 | Be: patent expired |
Free format text: 20010320 *HENKEL K.G.A.A. |
|
PG25 | Lapsed in a contracting state [announced via postgrant information from national office to epo] |
Ref country code: LI Free format text: LAPSE BECAUSE OF EXPIRATION OF PROTECTION Effective date: 20010319 Ref country code: GB Free format text: LAPSE BECAUSE OF EXPIRATION OF PROTECTION Effective date: 20010319 Ref country code: CH Free format text: LAPSE BECAUSE OF EXPIRATION OF PROTECTION Effective date: 20010319 |
|
PG25 | Lapsed in a contracting state [announced via postgrant information from national office to epo] |
Ref country code: NL Free format text: LAPSE BECAUSE OF EXPIRATION OF PROTECTION Effective date: 20010320 Ref country code: AT Free format text: LAPSE BECAUSE OF EXPIRATION OF PROTECTION Effective date: 20010320 |
|
PG25 | Lapsed in a contracting state [announced via postgrant information from national office to epo] |
Ref country code: SE Free format text: THE PATENT HAS BEEN ANNULLED BY A DECISION OF A NATIONAL AUTHORITY Effective date: 20010330 |
|
REG | Reference to a national code |
Ref country code: GB Ref legal event code: PE20 Effective date: 20010319 |
|
REG | Reference to a national code |
Ref country code: CH Ref legal event code: PL |
|
NLV7 | Nl: ceased due to reaching the maximum lifetime of a patent |
Effective date: 20010320 |
|
EUG | Se: european patent has lapsed |
Ref document number: 81102083.3 |
|
APAH | Appeal reference modified |
Free format text: ORIGINAL CODE: EPIDOSCREFNO |