EP1004656B1 - Verdichtetes Granulat, Herstellungsverfahren und Verwendung als Sprengmittel für gepresste Formkörper - Google Patents
Verdichtetes Granulat, Herstellungsverfahren und Verwendung als Sprengmittel für gepresste Formkörper Download PDFInfo
- Publication number
- EP1004656B1 EP1004656B1 EP98121397A EP98121397A EP1004656B1 EP 1004656 B1 EP1004656 B1 EP 1004656B1 EP 98121397 A EP98121397 A EP 98121397A EP 98121397 A EP98121397 A EP 98121397A EP 1004656 B1 EP1004656 B1 EP 1004656B1
- Authority
- EP
- European Patent Office
- Prior art keywords
- cellulose
- granulate
- meth
- acrylic acid
- copolymers
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Expired - Lifetime
Links
- 239000008187 granular material Substances 0.000 title claims abstract description 60
- 238000004519 manufacturing process Methods 0.000 title claims description 5
- 239000007884 disintegrant Substances 0.000 title abstract description 32
- 238000000465 moulding Methods 0.000 title description 8
- 229920002678 cellulose Polymers 0.000 claims abstract description 70
- 239000001913 cellulose Substances 0.000 claims abstract description 68
- CERQOIWHTDAKMF-UHFFFAOYSA-N Methacrylic acid Chemical compound CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 claims abstract description 35
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 35
- 229920001577 copolymer Polymers 0.000 claims abstract description 30
- 239000003599 detergent Substances 0.000 claims abstract description 24
- 229920000642 polymer Polymers 0.000 claims abstract description 24
- 150000003839 salts Chemical class 0.000 claims abstract description 18
- 239000004094 surface-active agent Substances 0.000 claims abstract description 17
- 239000007788 liquid Substances 0.000 claims abstract description 11
- 238000000034 method Methods 0.000 claims abstract description 9
- 238000002156 mixing Methods 0.000 claims abstract description 7
- 230000008569 process Effects 0.000 claims abstract description 7
- 239000000203 mixture Substances 0.000 claims description 39
- -1 fatty alcohol sulfate Chemical class 0.000 claims description 19
- 239000002245 particle Substances 0.000 claims description 14
- 230000008961 swelling Effects 0.000 claims description 13
- OFOBLEOULBTSOW-UHFFFAOYSA-N Propanedioic acid Natural products OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 0.000 claims description 12
- VZCYOOQTPOCHFL-UPHRSURJSA-N maleic acid Chemical compound OC(=O)\C=C/C(O)=O VZCYOOQTPOCHFL-UPHRSURJSA-N 0.000 claims description 12
- 239000011976 maleic acid Substances 0.000 claims description 12
- VZCYOOQTPOCHFL-UHFFFAOYSA-N trans-butenedioic acid Natural products OC(=O)C=CC(O)=O VZCYOOQTPOCHFL-UHFFFAOYSA-N 0.000 claims description 12
- 239000002736 nonionic surfactant Substances 0.000 claims description 11
- IMROMDMJAWUWLK-UHFFFAOYSA-N Ethenol Chemical compound OC=C IMROMDMJAWUWLK-UHFFFAOYSA-N 0.000 claims description 10
- 125000000129 anionic group Chemical group 0.000 claims description 9
- 239000003945 anionic surfactant Substances 0.000 claims description 8
- 238000010521 absorption reaction Methods 0.000 claims description 7
- 239000003795 chemical substances by application Substances 0.000 claims description 7
- 150000002191 fatty alcohols Chemical class 0.000 claims description 7
- 239000002253 acid Substances 0.000 claims description 6
- 239000002280 amphoteric surfactant Substances 0.000 claims description 6
- 229920003086 cellulose ether Polymers 0.000 claims description 5
- 238000004140 cleaning Methods 0.000 claims description 4
- 230000008719 thickening Effects 0.000 claims description 4
- 238000005056 compaction Methods 0.000 claims description 3
- FPYJFEHAWHCUMM-UHFFFAOYSA-N maleic anhydride Chemical compound O=C1OC(=O)C=C1 FPYJFEHAWHCUMM-UHFFFAOYSA-N 0.000 claims description 3
- 239000000178 monomer Substances 0.000 claims description 3
- 125000000542 sulfonic acid group Chemical group 0.000 claims description 3
- IAYPIBMASNFSPL-UHFFFAOYSA-N Ethylene oxide Chemical compound C1CO1 IAYPIBMASNFSPL-UHFFFAOYSA-N 0.000 claims description 2
- 229920006037 cross link polymer Polymers 0.000 claims description 2
- 238000012986 modification Methods 0.000 claims description 2
- 230000004048 modification Effects 0.000 claims description 2
- 150000003460 sulfonic acids Chemical class 0.000 claims description 2
- 230000001747 exhibiting effect Effects 0.000 claims 1
- 238000009991 scouring Methods 0.000 claims 1
- 239000003826 tablet Substances 0.000 abstract 4
- 239000007891 compressed tablet Substances 0.000 abstract 1
- 235000010980 cellulose Nutrition 0.000 description 50
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 description 27
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 12
- 229920002134 Carboxymethyl cellulose Polymers 0.000 description 10
- 235000010948 carboxy methyl cellulose Nutrition 0.000 description 10
- 235000015165 citric acid Nutrition 0.000 description 9
- 150000001875 compounds Chemical class 0.000 description 9
- 239000002360 explosive Substances 0.000 description 9
- 238000009472 formulation Methods 0.000 description 9
- 150000004760 silicates Chemical class 0.000 description 8
- 102000004190 Enzymes Human genes 0.000 description 7
- 108090000790 Enzymes Proteins 0.000 description 7
- 229920000881 Modified starch Polymers 0.000 description 7
- 229920002125 Sokalan® Polymers 0.000 description 7
- BGRWYDHXPHLNKA-UHFFFAOYSA-N Tetraacetylethylenediamine Chemical compound CC(=O)N(C(C)=O)CCN(C(C)=O)C(C)=O BGRWYDHXPHLNKA-UHFFFAOYSA-N 0.000 description 7
- 150000004649 carbonic acid derivatives Chemical class 0.000 description 7
- 235000019426 modified starch Nutrition 0.000 description 7
- 238000002360 preparation method Methods 0.000 description 7
- 239000002994 raw material Substances 0.000 description 7
- 229940032147 starch Drugs 0.000 description 7
- CSNNHWWHGAXBCP-UHFFFAOYSA-L Magnesium sulfate Chemical compound [Mg+2].[O-][S+2]([O-])([O-])[O-] CSNNHWWHGAXBCP-UHFFFAOYSA-L 0.000 description 6
- 229920000168 Microcrystalline cellulose Polymers 0.000 description 6
- 239000002202 Polyethylene glycol Substances 0.000 description 6
- UIIMBOGNXHQVGW-UHFFFAOYSA-M Sodium bicarbonate Chemical compound [Na+].OC([O-])=O UIIMBOGNXHQVGW-UHFFFAOYSA-M 0.000 description 6
- 229920002472 Starch Polymers 0.000 description 6
- 239000007844 bleaching agent Substances 0.000 description 6
- 238000007906 compression Methods 0.000 description 6
- 230000006835 compression Effects 0.000 description 6
- VTIIJXUACCWYHX-UHFFFAOYSA-L disodium;carboxylatooxy carbonate Chemical compound [Na+].[Na+].[O-]C(=O)OOC([O-])=O VTIIJXUACCWYHX-UHFFFAOYSA-L 0.000 description 6
- 239000002270 dispersing agent Substances 0.000 description 6
- 235000019813 microcrystalline cellulose Nutrition 0.000 description 6
- 239000008108 microcrystalline cellulose Substances 0.000 description 6
- 229940016286 microcrystalline cellulose Drugs 0.000 description 6
- 229920001515 polyalkylene glycol Polymers 0.000 description 6
- 229920001223 polyethylene glycol Polymers 0.000 description 6
- 235000013855 polyvinylpyrrolidone Nutrition 0.000 description 6
- 229920000036 polyvinylpyrrolidone Polymers 0.000 description 6
- 239000001267 polyvinylpyrrolidone Substances 0.000 description 6
- 229940045872 sodium percarbonate Drugs 0.000 description 6
- 235000019698 starch Nutrition 0.000 description 6
- 239000008107 starch Substances 0.000 description 6
- BVKZGUZCCUSVTD-UHFFFAOYSA-M Bicarbonate Chemical class OC([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-M 0.000 description 5
- KRKNYBCHXYNGOX-UHFFFAOYSA-K Citrate Chemical compound [O-]C(=O)CC(O)(CC([O-])=O)C([O-])=O KRKNYBCHXYNGOX-UHFFFAOYSA-K 0.000 description 5
- ABLZXFCXXLZCGV-UHFFFAOYSA-N Phosphorous acid Chemical class OP(O)=O ABLZXFCXXLZCGV-UHFFFAOYSA-N 0.000 description 5
- 239000001768 carboxy methyl cellulose Substances 0.000 description 5
- 239000008112 carboxymethyl-cellulose Substances 0.000 description 5
- 235000014113 dietary fatty acids Nutrition 0.000 description 5
- 239000000194 fatty acid Substances 0.000 description 5
- 229930195729 fatty acid Natural products 0.000 description 5
- HQKMJHAJHXVSDF-UHFFFAOYSA-L magnesium stearate Chemical class [Mg+2].CCCCCCCCCCCCCCCCCC([O-])=O.CCCCCCCCCCCCCCCCCC([O-])=O HQKMJHAJHXVSDF-UHFFFAOYSA-L 0.000 description 5
- 238000005406 washing Methods 0.000 description 5
- 239000010457 zeolite Substances 0.000 description 5
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 description 4
- 229920002153 Hydroxypropyl cellulose Polymers 0.000 description 4
- 150000007513 acids Chemical class 0.000 description 4
- 239000012190 activator Substances 0.000 description 4
- 239000000654 additive Substances 0.000 description 4
- 235000010443 alginic acid Nutrition 0.000 description 4
- 229920000615 alginic acid Polymers 0.000 description 4
- 235000012216 bentonite Nutrition 0.000 description 4
- 229920006184 cellulose methylcellulose Polymers 0.000 description 4
- 230000000694 effects Effects 0.000 description 4
- 150000004665 fatty acids Chemical class 0.000 description 4
- 235000010977 hydroxypropyl cellulose Nutrition 0.000 description 4
- 239000000126 substance Substances 0.000 description 4
- BJEPYKJPYRNKOW-REOHCLBHSA-N (S)-malic acid Chemical compound OC(=O)[C@@H](O)CC(O)=O BJEPYKJPYRNKOW-REOHCLBHSA-N 0.000 description 3
- FEWJPZIEWOKRBE-JCYAYHJZSA-N Dextrotartaric acid Chemical compound OC(=O)[C@H](O)[C@@H](O)C(O)=O FEWJPZIEWOKRBE-JCYAYHJZSA-N 0.000 description 3
- 239000004368 Modified starch Substances 0.000 description 3
- PMZURENOXWZQFD-UHFFFAOYSA-L Sodium Sulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=O PMZURENOXWZQFD-UHFFFAOYSA-L 0.000 description 3
- FEWJPZIEWOKRBE-UHFFFAOYSA-N Tartaric acid Natural products [H+].[H+].[O-]C(=O)C(O)C(O)C([O-])=O FEWJPZIEWOKRBE-UHFFFAOYSA-N 0.000 description 3
- 229910021536 Zeolite Inorganic materials 0.000 description 3
- 239000003513 alkali Substances 0.000 description 3
- 150000004996 alkyl benzenes Chemical class 0.000 description 3
- 125000000217 alkyl group Chemical group 0.000 description 3
- BJEPYKJPYRNKOW-UHFFFAOYSA-N alpha-hydroxysuccinic acid Natural products OC(=O)C(O)CC(O)=O BJEPYKJPYRNKOW-UHFFFAOYSA-N 0.000 description 3
- 230000015572 biosynthetic process Effects 0.000 description 3
- 239000013530 defoamer Substances 0.000 description 3
- HNPSIPDUKPIQMN-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Al]O[Al]=O HNPSIPDUKPIQMN-UHFFFAOYSA-N 0.000 description 3
- 150000002170 ethers Chemical class 0.000 description 3
- 239000000945 filler Substances 0.000 description 3
- KWIUHFFTVRNATP-UHFFFAOYSA-N glycine betaine Chemical compound C[N+](C)(C)CC([O-])=O KWIUHFFTVRNATP-UHFFFAOYSA-N 0.000 description 3
- 239000000391 magnesium silicate Substances 0.000 description 3
- 235000012243 magnesium silicates Nutrition 0.000 description 3
- 235000019359 magnesium stearate Nutrition 0.000 description 3
- 229910052943 magnesium sulfate Inorganic materials 0.000 description 3
- 235000019341 magnesium sulphate Nutrition 0.000 description 3
- 235000011090 malic acid Nutrition 0.000 description 3
- 239000001630 malic acid Substances 0.000 description 3
- 229920000609 methyl cellulose Polymers 0.000 description 3
- 235000010981 methylcellulose Nutrition 0.000 description 3
- 230000003287 optical effect Effects 0.000 description 3
- UEZVMMHDMIWARA-UHFFFAOYSA-M phosphonate Chemical compound [O-]P(=O)=O UEZVMMHDMIWARA-UHFFFAOYSA-M 0.000 description 3
- 239000004584 polyacrylic acid Substances 0.000 description 3
- 229920005646 polycarboxylate Polymers 0.000 description 3
- 229920000193 polymethacrylate Polymers 0.000 description 3
- 229910000030 sodium bicarbonate Inorganic materials 0.000 description 3
- 235000017557 sodium bicarbonate Nutrition 0.000 description 3
- 229910000029 sodium carbonate Inorganic materials 0.000 description 3
- 239000001509 sodium citrate Substances 0.000 description 3
- 159000000000 sodium salts Chemical class 0.000 description 3
- 229910052938 sodium sulfate Inorganic materials 0.000 description 3
- 235000011152 sodium sulphate Nutrition 0.000 description 3
- 235000019832 sodium triphosphate Nutrition 0.000 description 3
- 239000011975 tartaric acid Substances 0.000 description 3
- 235000002906 tartaric acid Nutrition 0.000 description 3
- XSVSPKKXQGNHMD-UHFFFAOYSA-N 5-bromo-3-methyl-1,2-thiazole Chemical compound CC=1C=C(Br)SN=1 XSVSPKKXQGNHMD-UHFFFAOYSA-N 0.000 description 2
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 2
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 description 2
- FBPFZTCFMRRESA-FSIIMWSLSA-N D-Glucitol Natural products OC[C@H](O)[C@H](O)[C@@H](O)[C@H](O)CO FBPFZTCFMRRESA-FSIIMWSLSA-N 0.000 description 2
- FBPFZTCFMRRESA-JGWLITMVSA-N D-glucitol Chemical compound OC[C@H](O)[C@@H](O)[C@H](O)[C@H](O)CO FBPFZTCFMRRESA-JGWLITMVSA-N 0.000 description 2
- 108010010803 Gelatin Proteins 0.000 description 2
- 229910019142 PO4 Inorganic materials 0.000 description 2
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 2
- 229920000388 Polyphosphate Polymers 0.000 description 2
- 239000004614 Process Aid Substances 0.000 description 2
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 2
- KDYFGRWQOYBRFD-UHFFFAOYSA-N Succinic acid Natural products OC(=O)CCC(O)=O KDYFGRWQOYBRFD-UHFFFAOYSA-N 0.000 description 2
- 150000001242 acetic acid derivatives Chemical class 0.000 description 2
- 229910052783 alkali metal Inorganic materials 0.000 description 2
- 150000001340 alkali metals Chemical class 0.000 description 2
- 150000008051 alkyl sulfates Chemical class 0.000 description 2
- 229910052782 aluminium Inorganic materials 0.000 description 2
- 150000001412 amines Chemical class 0.000 description 2
- SVPXDRXYRYOSEX-UHFFFAOYSA-N bentoquatam Chemical compound O.O=[Si]=O.O=[Al]O[Al]=O SVPXDRXYRYOSEX-UHFFFAOYSA-N 0.000 description 2
- QRUDEWIWKLJBPS-UHFFFAOYSA-N benzotriazole Chemical compound C1=CC=C2N[N][N]C2=C1 QRUDEWIWKLJBPS-UHFFFAOYSA-N 0.000 description 2
- 239000012964 benzotriazole Substances 0.000 description 2
- KDYFGRWQOYBRFD-NUQCWPJISA-N butanedioic acid Chemical compound O[14C](=O)CC[14C](O)=O KDYFGRWQOYBRFD-NUQCWPJISA-N 0.000 description 2
- 125000002057 carboxymethyl group Chemical group [H]OC(=O)C([H])([H])[*] 0.000 description 2
- 150000001860 citric acid derivatives Chemical class 0.000 description 2
- 235000011180 diphosphates Nutrition 0.000 description 2
- 238000004851 dishwashing Methods 0.000 description 2
- 238000006073 displacement reaction Methods 0.000 description 2
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- 235000011852 gelatine desserts Nutrition 0.000 description 2
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- SXLLDUPXUVRMEE-UHFFFAOYSA-N nonanediperoxoic acid Chemical compound OOC(=O)CCCCCCCC(=O)OO SXLLDUPXUVRMEE-UHFFFAOYSA-N 0.000 description 2
- 235000010987 pectin Nutrition 0.000 description 2
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- 150000004965 peroxy acids Chemical class 0.000 description 2
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 description 2
- 239000010452 phosphate Substances 0.000 description 2
- 239000001205 polyphosphate Substances 0.000 description 2
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- 235000017550 sodium carbonate Nutrition 0.000 description 2
- NLJMYIDDQXHKNR-UHFFFAOYSA-K sodium citrate Chemical compound O.O.[Na+].[Na+].[Na+].[O-]C(=O)CC(O)(CC([O-])=O)C([O-])=O NLJMYIDDQXHKNR-UHFFFAOYSA-K 0.000 description 2
- 239000012418 sodium perborate tetrahydrate Substances 0.000 description 2
- IBDSNZLUHYKHQP-UHFFFAOYSA-N sodium;3-oxidodioxaborirane;tetrahydrate Chemical compound O.O.O.O.[Na+].[O-]B1OO1 IBDSNZLUHYKHQP-UHFFFAOYSA-N 0.000 description 2
- 239000000600 sorbitol Substances 0.000 description 2
- 150000003871 sulfonates Chemical class 0.000 description 2
- 150000003467 sulfuric acid derivatives Chemical class 0.000 description 2
- SWMBOMMGMHMOHE-MHLULTLJSA-N (2r,3r,4r,5r)-hexane-1,2,3,4,5,6-hexol;(2r,3r,4r,5s)-hexane-1,2,3,4,5,6-hexol Chemical compound OC[C@H](O)[C@@H](O)[C@H](O)[C@H](O)CO.OC[C@@H](O)[C@@H](O)[C@H](O)[C@H](O)CO SWMBOMMGMHMOHE-MHLULTLJSA-N 0.000 description 1
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- FIDRAVVQGKNYQK-UHFFFAOYSA-N 1,2,3,4-tetrahydrotriazine Chemical compound C1NNNC=C1 FIDRAVVQGKNYQK-UHFFFAOYSA-N 0.000 description 1
- FHVDTGUDJYJELY-UHFFFAOYSA-N 6-{[2-carboxy-4,5-dihydroxy-6-(phosphanyloxy)oxan-3-yl]oxy}-4,5-dihydroxy-3-phosphanyloxane-2-carboxylic acid Chemical compound O1C(C(O)=O)C(P)C(O)C(O)C1OC1C(C(O)=O)OC(OP)C(O)C1O FHVDTGUDJYJELY-UHFFFAOYSA-N 0.000 description 1
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- 229940050410 gluconate Drugs 0.000 description 1
- 150000002334 glycols Chemical class 0.000 description 1
- QAOWNCQODCNURD-UHFFFAOYSA-M hydrogensulfate Chemical compound OS([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-M 0.000 description 1
- 150000002462 imidazolines Chemical class 0.000 description 1
- 238000007654 immersion Methods 0.000 description 1
- 239000003456 ion exchange resin Substances 0.000 description 1
- 229920003303 ion-exchange polymer Polymers 0.000 description 1
- 239000004337 magnesium citrate Substances 0.000 description 1
- 229960005336 magnesium citrate Drugs 0.000 description 1
- 235000002538 magnesium citrate Nutrition 0.000 description 1
- 239000000594 mannitol Substances 0.000 description 1
- 235000010355 mannitol Nutrition 0.000 description 1
- 230000007246 mechanism Effects 0.000 description 1
- 229920003145 methacrylic acid copolymer Polymers 0.000 description 1
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 1
- 150000007524 organic acids Chemical class 0.000 description 1
- 235000005985 organic acids Nutrition 0.000 description 1
- 150000002894 organic compounds Chemical class 0.000 description 1
- 150000004967 organic peroxy acids Chemical class 0.000 description 1
- 229920000620 organic polymer Polymers 0.000 description 1
- 238000004806 packaging method and process Methods 0.000 description 1
- 239000012188 paraffin wax Substances 0.000 description 1
- WXZMFSXDPGVJKK-UHFFFAOYSA-N pentaerythritol Chemical compound OCC(CO)(CO)CO WXZMFSXDPGVJKK-UHFFFAOYSA-N 0.000 description 1
- 239000002304 perfume Substances 0.000 description 1
- 239000000546 pharmaceutical excipient Substances 0.000 description 1
- 229940124531 pharmaceutical excipient Drugs 0.000 description 1
- 150000003014 phosphoric acid esters Chemical class 0.000 description 1
- 229920003023 plastic Polymers 0.000 description 1
- 239000004033 plastic Substances 0.000 description 1
- 229920000058 polyacrylate Polymers 0.000 description 1
- 229920005862 polyol Polymers 0.000 description 1
- 150000003077 polyols Chemical class 0.000 description 1
- 229920001451 polypropylene glycol Polymers 0.000 description 1
- 238000003825 pressing Methods 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- 150000003856 quaternary ammonium compounds Chemical class 0.000 description 1
- 238000009490 roller compaction Methods 0.000 description 1
- 238000005096 rolling process Methods 0.000 description 1
- 235000012239 silicon dioxide Nutrition 0.000 description 1
- 239000000377 silicon dioxide Substances 0.000 description 1
- 229910021647 smectite Inorganic materials 0.000 description 1
- 239000000344 soap Substances 0.000 description 1
- 229960001922 sodium perborate Drugs 0.000 description 1
- 229940080313 sodium starch Drugs 0.000 description 1
- 229920003109 sodium starch glycolate Polymers 0.000 description 1
- MWNQXXOSWHCCOZ-UHFFFAOYSA-L sodium;oxido carbonate Chemical compound [Na+].[O-]OC([O-])=O MWNQXXOSWHCCOZ-UHFFFAOYSA-L 0.000 description 1
- YKLJGMBLPUQQOI-UHFFFAOYSA-M sodium;oxidooxy(oxo)borane Chemical compound [Na+].[O-]OB=O YKLJGMBLPUQQOI-UHFFFAOYSA-M 0.000 description 1
- 239000002689 soil Substances 0.000 description 1
- 238000001179 sorption measurement Methods 0.000 description 1
- 238000001694 spray drying Methods 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
- 150000003445 sucroses Chemical class 0.000 description 1
- 230000002522 swelling effect Effects 0.000 description 1
- 229920005613 synthetic organic polymer Polymers 0.000 description 1
- 239000007885 tablet disintegrant Substances 0.000 description 1
- 229920001897 terpolymer Polymers 0.000 description 1
- 235000019818 tetrasodium diphosphate Nutrition 0.000 description 1
- 239000004753 textile Substances 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
- 238000009736 wetting Methods 0.000 description 1
- 239000004711 α-olefin Substances 0.000 description 1
Images
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
- C11D17/00—Detergent materials or soaps characterised by their shape or physical properties
- C11D17/0047—Detergents in the form of bars or tablets
- C11D17/0065—Solid detergents containing builders
- C11D17/0073—Tablets
-
- 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
- C11D17/06—Powder; Flakes; Free-flowing mixtures; Sheets
-
- 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
- C11D3/16—Organic compounds
- C11D3/20—Organic compounds containing oxygen
- C11D3/22—Carbohydrates or derivatives thereof
- C11D3/222—Natural or synthetic polysaccharides, e.g. cellulose, starch, gum, alginic acid or cyclodextrin
-
- 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
- C11D3/16—Organic compounds
- C11D3/37—Polymers
- C11D3/3746—Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds
- C11D3/3757—(Co)polymerised carboxylic acids, -anhydrides, -esters in solid and liquid compositions
- C11D3/3761—(Co)polymerised carboxylic acids, -anhydrides, -esters in solid and liquid compositions in solid compositions
Definitions
- the invention is directed to granules that are particularly good at water records and forwards inside, which in some cases increases the volume takes place, so that the granules as disintegrants for pressed moldings, such as tablets.
- Disintegrants for tablets or granules are auxiliary substances that disintegrate tablets or granules in contact with liquids, in particular Influence water positively.
- the decay of Tablets in large parts and then a disintegration into smaller ones Particles are caused and accelerated.
- inorganic and organic disintegrants for tablets are Substances known, for example inorganic substances such as bentonites, also persalts, acetates, alkali carbonates / hydrogen carbonates and citric acid.
- organic compounds include starch, modified Starch and starch degradation products, cellulose, cellulose ethers, such as Methyl cellulose hydroxypropyl cellulose and carboxymethyl cellulose, poly (meth) acrylates, Polyvinyl pyrrolidone and cross-linked polyvinyl pyrrolidone, Alginates, gelatin and pectins.
- an explosive granulate and its use in washing or cleaning-active moldings such as tablets, known a high adsorption capacity for water and a grain size distribution in which at least 90% by weight has a particle size of at least 0.2 mm and a maximum of 3 mm.
- the granules preferably contain 25-100% by weight of disintegrants, such as starch, starch derivatives, cellulose, cellulose derivatives, Alginic acid, carboxylmethylamylopectin, polyacrylic acid, polyvinylpyrrolidone and polyvinyl polypyrrolidone.
- disintegrants such as starch, starch derivatives, cellulose, cellulose derivatives, Alginic acid, carboxylmethylamylopectin, polyacrylic acid, polyvinylpyrrolidone and polyvinyl polypyrrolidone.
- Citric acid is used as a disintegrant or citrates, bicarbonates and carbonates, bisulfate and percarbonate, microcrystalline Cellulose, sugar, sorbitol or swellable layered silicates called the type of bentonite or smectite.
- the explosives are used in quantities of 1 to 25% by weight as a single raw material or as a compound.
- DE-A-44 04 279 describes the following disintegrants for washing or cleaning tablets: starch, starch derivatives, cellulose, cellulose derivatives, microcrystalline cellulose, salts of polymeric polyacrylates or polymethacrylates, methyl celluloses, hydroxypropyl celluloses or methyl hydroxypropyl celluloses. Acetates or percarbonates are also mentioned as disintegrants.
- the application amounts are up to 15% by weight. Since water-soluble silicates are used as builders, a combination of poly (meth) acrylates and nonionic cellulose ethers can Amounts of 1% by weight lead to very good results.
- Detergent tablets are known from EP-A-522 766 which contain disintegrants which function according to four different mechanisms: swelling, porosity / capillary action, deformation and chemical reaction.
- Starch, starch derivatives, carboxymethyl starch, sodium starch glycolates, cellulose and cellulose derivatives, carboxymethyl cellulose, crosslinked modified cellulose, microcrystalline cellulose and various organic polymers such as polyethylene glycol, and crosslinked polyvinypyrrolidones and inorganic swelling agents such as bentonites are described. Combinations of organic acids and bicarbonates of the carbonates of alkali metals are also mentioned.
- EP 0 628 627 A1 describes a water-soluble, water-softening agent Builder in the form of a tablet. Combinations are used as explosives from citric acid and / or partially neutralized polymers and carbonate and / or bicarbonate or an insoluble polyvinylpyrrolidone.
- detergent tablets are described as disintegrants Starch derivatives, cellulose compounds, polyvinylpyrrolidone compounds, polyvinylpolypyrrolidone compounds, Bentonite compounds, alginate gelatin and may contain pectins.
- a polyfunctional organic carboxylic acid such as maleic acid Malic acid citric acid or tartaric acid together with carbonates or Bicarbonates recommended.
- 95/06 109 is a method for producing detergent granules known high density from anhydrous material.
- the agglomerates are free fluent and have a high content of detergent substances.
- the object of the invention is to swell quickly and strongly in water
- To create granules so that it can be used as a disintegrant for molded articles is suitable to promote their decay on contact with water.
- This task is solved by a compacted explosive granulate for pressed molded articles containing non-water-soluble, water-swellable high-purity cellulose and / or cellulose derivatives and finely divided polymers or copolymers of (meth) acrylic acid or mixtures of these polymers or copolymers and one or more liquid nonionic and / or anionic and / or amphoteric surfactant (s) used for gel formation or thickening incline with water, the weight ratio of the combined in Water-swellable cellulose / cellulose derivatives and the polymers / copolymers of (meth) acrylic acid: liquid surfactant (s) is from 100: 1 to 10: 1.
- the anisotropic cellulose was aligned by the compression or cellulose derivatives.
- the water-swellable, high-purity cellulose becomes microcrystalline in form Structure used, the super-molecular structural elements Have the shape of fibrils, in the longitudinal direction of which crystalline and can alternate amorphous areas. Have proven to be particularly suitable Fibrils of native cellulose with a maximum length of 300 ⁇ m have been proven. Both microcrystalline and amorphous fine cellulose can be used and mixtures thereof can be used.
- the finely divided cellulose preferably has bulk densities of 40 g / l up to 300 g / l, very particularly preferably from 65 g / l to 170 g / l. Become already used granulated types, their bulk density is higher and can be from 350 g / l to 550 g / l.
- the bulk weights of the cellulose derivatives can range from 50 g / l to 1000 g / l, preferably in the range of 100 g / l and 800 g / l.
- the particle size of the finely divided cellulose can be between 30 ⁇ m and 300 ⁇ m, preferably between 30 ⁇ m and 200 ⁇ m, in the case of granulated types the average particle size is between 350 ⁇ m and 800 ⁇ m.
- the particle size of the finely divided Cellulose derivatives can be between 30 ⁇ m and 1000 ⁇ m.
- cellulose derivatives that are swellable in water such as cellulose ethers and cellulose esters and mixed modifications the same can also be used.
- Suitable cellulose ethers are e.g. Methyl cellulose, hydroxypropyl cellulose and carboxymethyl cellulose, as well modified carboxymethyl cellulose.
- Granules are present.
- finely divided polymers of (meth) acrylic acid or copolymers of (Meth) acrylic acid or salts thereof or mixtures of such polymers or copolymers or salts thereof with high water absorption contained in the granulate Linear ones have proven to be particularly suitable Polymers of (meth) acrylic acid, copolymers of (meth) acrylic acid or salts the same with weight average molecular weights of 5,000 to 70,000 and cross-linked polymers of (meth) acrylic acid, copolymers of (Meth) acrylic acid or salts thereof with weight average molecular weights proven from 1,000,000 to 5,000,000.
- the copolymers are concerned it is preferably a copolymer of (meth) acrylic acid and maleic acid or maleic anhydride, for example 40 to 90% by weight (Meth) acrylic acid and 60 to 10% by weight of maleic acid or maleic anhydride contain, whose relative molar mass, based on free acids, between 3,000 and 100,000, preferably 3,000 to 70,000 and very particularly preferred Is 5,000 to 50,000.
- Ter- and quattropolymeric polycarboxylates have also proven to be very suitable proven, made from (meth) acrylic acid, maleic acid and vinyl alcohol or vinyl alcohol derivatives, or those of (meth) acrylic acid, ethylenically unsaturated sulfonic acids and sugar derivatives, or such (Meth) acrylic acid, maleic acid, vinyl alcohol derivatives and sulfonic acid groups Monomers
- Salt formation is preferably carried out with cations of alkali metals, Ammonia and amines, or their mixtures.
- the finely divided polymers / copolymers of (meth) acrylic acid or salts preferably have the same of the cross-linked derivatives described above an average particle size of 45 ⁇ m to 150 ⁇ m. Most notably particle sizes from 45 ⁇ m to 90 ⁇ m are preferred.
- Particles with average particle sizes over 150 ⁇ m show a good one Explosive effects, but are too large after swelling, become when washing filtered off and are visually as particles on the textile after washing visible.
- Cellulose / cellulose derivatives are made with polymers / copolymers from (Meth) acrylic acid or salts thereof combined in the granulate, the weight ratio can be from 100: 0.5 to 100: 30, preferably from 100: 1 to 100: 20, a weight ratio of is very particularly preferred 100: 1 to 100: 10, the most favorable is a weight ratio of 100: 3.
- the granulate contains one or more other essential constituents liquid, water-forming or thickening surfactants from the group of nonionic, anionic or amphoteric surfactants.
- the nonionic surfactants are selected from alkyl polyglucosides, fatty acid alkylolamides, Fatty acid polyethylene glycol esters, fatty amine oxethylates, Fatty alcohol ethoxylates with 3-15 mol ethylene oxide or propylene oxide, Fatty acid glycerides, sorbitan esters, sucrose esters, e.g. Sucrose palmitate, Pentaerythritol partial esters, which can also be ethoxylated, as well as alkylphenol polyethylene glycol ethers and phenol poly - ethylene glycol ethers (if they can be used in the respective country)
- the anionic surfactants are selected from alkyl sulfates, linear and branched alkylbenzenesulfonates, alkylglycerol ethers, fatty alcohol polyethylene glycol ether sulfates, Paraffin sulfonates, alpha olefin sulfonates, Sulfosuccinates, phosphoric acid esters and fatty alcohol ether carboxylates.
- amphoteric surfactants are selected from coconut fatty acid amidopropyl betaine, modified imidazolines and fatty acid amide derivatives with betaine structure.
- the quantitative ratio of cellulose / cellulose derivatives and / or polymers / copolymers of (meth) acrylic acid or salts thereof: surfactant can from 100: 1 to 10: 1. Quantities of 100: 2 are preferred up to 100: 5
- the gel-forming or water-thickening surfactants can be anionic, be amphoteric or nonionic, particularly preferred are nonionic Surfactants.
- liquid Surfactants initially in direct contact with the cellulose / cellulose derivatives to bring and attach to it and then the finely divided polymers / Copolymers of (meth) acrylic acid or its salts in the mixture to be introduced in such a way that the polymer particles on the fibrils of the cellulose be liable.
- the mixture of the granulate components according to the invention, cellulose / cellulose derivatives and polymers / copolymers of (meth) acrylic acid and nonionic surfactants are then granulated using conventional methods.
- mixers from Vomm, Lödige, Schugi, Eirich, Henschel or Fukae can be used.
- the final compression is essential.
- Compacting under Pressure can be applied in various ways.
- Compaction on rolling mills has proven to be particularly suitable whose rollers run at different speeds, so that the pressure on the granules in the nip is still due to friction is added. This leads to the formation of a scale-like structure and alignment of the anisotropic cellulose / cellulose derivatives in the granulate.
- This orientation can be one of the reasons for the particularly cheap source kinetic behavior of this embodiment of the invention Be granules.
- the compression of the granules should preferably be such that the compression Granules a bulk density of 100 g / l to 800 g / l, preferred from 200 g / l to 600 g / l, very particularly preferably from 300 g / l to 500 g / l having.
- the disintegrant granules according to the invention are in the moldings in Contain amounts of 0.5 wt.% To 10 wt.%, Preferably 2 wt.% To 7 % By weight and particularly preferably 3% by weight to 6% by weight.
- the specific water absorption capacity of the granules according to the invention can be determined gravimetrically as follows: A defined amount of granules (eg 2.00 g) is sealed in a thin paper bag, such as a tea bag, and immersed in a vessel with an excess of water. After 3 minutes of immersion, the bag is removed from the water and hung for 10 minutes to drain. The bag is weighed and the water absorption is determined from the weight difference of a wet bag with and without granules. Distilled water or water with a defined hardness can be used for the determination.
- a defined amount of granules eg 2.00 g
- a thin paper bag such as a tea bag
- the water absorption which can be determined in this way is preferably 500 until 2000 %
- the compacted granulate according to the invention is distinguished by a special one Swelling kinetics, the expansion changes depending on the Time is not linear and should reach a certain level after the shortest possible time to reach.
- the increase in volume after 5 seconds is preferably 55% by volume to 225% by volume, the increase in volume being greater with higher compaction, ie higher bulk density.
- the increase in volume is preferably 75% by volume to 270% by volume, the increase in volume likewise increasing with increasing bulk density.
- the volume increases after 5 seconds contact with water from 55 vol.% to 100 vol.% and after 10 seconds from 75 vol.% to 130 vol.%.
- a bulk density of 400 g / l to 500 g / l the volume increase of 200 after 5 seconds Vol.% To 225 vol.% And after 10 seconds from 230 vol.% To 270 vol.%.
- Figure 1 shows a diagram for the swelling kinetics of known explosives and granules according to the invention.
- Table 1 contains the corresponding measured values. Swelling kinetics of different materials Bulk density [g / l] 70 90 90 300 300 450 450 Cellulose V 1 M1 V2 M2 V3 M3 Time [sec] Way [mm] Way [mm] Way [mm] Way [mm] Way [mm] Way [mm] Way [mm] Way [mm] 0 0 0 0 0 1 0.10 0.20 0.25 0.30 0.50 0.80 1.20 2nd 0.20 0.40 0.40 0.60 1.05 1.20 1.80 3rd 0.30 0.60 0.65 0.90 1.35 1.50 2.20 4th 0.35 0.70 0.80 1.00 1.58 1.60 2.40 5 0.40 0.85 0.95 1.10 1.75 1.70 2.50 6 0.42 1.00 1.15 1.15 1.83 1.72 2.58 7 0.44 1.10 1.25 1.20 1.93 1.80 2.65 8th 0.46 1.20 1.40 1.25 2.00 1.82 2.70 9 0.48 1.35 1.55 1.40 2.05 1.82 2.72 10th 0.48 1.40 1.65 1.50 2.15 1.85 2.
- composition of the samples V1 to V3 is as in Table 3, example 2.1.
- composition of the samples M1 to M3 is as in Table 3, example. 2.3: Does not fall under the scope of protection; but supports the concept of the present invention. Volume expansion in vol.% Cellulose V1 M1 V2 M2 V3 M3 Bulk density in g / l 70 90 90 300 300 450 450 Volume increase after 5 sec vol.% 5 14 16 55 100 200 225 after 10 sec vol.% 6 23 28 75 130 230 270
- Formulation V1 has the composition of Example 2.1 in undensified form.
- Formulation M1 has the composition of Example 2.3 in undensified form.
- V2, M2 denote samples that were compressed to a bulk density of 300 g / l after mixing in a roller press.
- V3 and M3 refer to samples which, after mixing, were compressed to a bulk density of 450 g / l using a roller press.
- the increase in volume after 5 seconds is preferably at least 95%, particularly preferred> 150%.
- Another object of the invention is a method for manufacturing a compacted granulate that is insoluble in water but swellable high-purity cellulose and / or cellulose derivatives and finely divided polymers / copolymers of (meth) acrylic acid or its salts and one or more contains liquid surfactants by mixing high-purity cellulose / cellulose derivative with the surfactant (s) according to the invention and mixing the polymers / copolymers, granulating and then compressing the Granules aligned with anisotropic cellulose / cellulose derivatives.
- the first step of the process involves a mixing and granulating process, in the pre-compounds produced by agglomeration processes become. These precompounds form a free-flowing and coarse-grained Goods that have a certain degree of moisture.
- the next step will be these precompounds are mechanically compressed.
- the products can be between two pressure areas in roller compressors, e.g. B. smooth or profiled, compressed become. If certain sliding properties are available, the Compression in extruders or flat die presses to form dies.
- the compactate is ejected as a strand. Compression methods in Matrices with stamps or pillow rollers produce compact forms such as tablets or briquettes. Roller compactors, Extruders, roller or cube presses, but also granulating presses be used. Below are the coarse, densified particles crushed, e.g. Suitable for mills, shredders or roller mills are.
- the granulate according to the invention takes this quickly in contact with water with volume increase and is therefore suitable as a so-called Disintegrant for pressed moldings so that they quickly disintegrate in water.
- the invention includes the use of the compacted granules as Disintegrants for pressed molded articles, for example tablets, cubes, Bullets and the like.
- disintegrant for detergent formulations is particularly preferred, Detergent formulations, stain salts, water softeners in tablet or cube form.
- Detergent tablets and detergent tablets for different Purposes, in the sanitary area or for dishwashers are generally known.
- Such moldings must have sufficient stability and strength to enable handling, packaging and storage however, quickly disintegrate on contact with water, so that the components can have the desired effect.
- the pressed moldings often contain so-called Disintegrants that due to the swelling behavior and the increase in volume Remove the cohesion of the shaped bodies and accelerate the disintegration.
- Detergent formulations usually contain builders, bleaches and bleach activators, surfactants, tabletting aids, disintegrants and other common additives and auxiliaries.
- Fillers can also form part of the builder system such as alkali carbonates, bicarbonates e.g. Sodium carbonate or sodium hydrogen carbonate, Sesquiocarbonates, sodium sulfate, magnesium sulfate, or citrate, citric acid, succinic acid, tartaric acid and malic acid his.
- Cobuilders and dispersants are often used as auxiliary builders. Such cobuilders or dispersants can be polyacrylic acids and their sodium salts.
- Copolymers of (meth) acrylic acid and maleic acid terpolymers and Quattropolymers of (meth) acrylic acid, maleic acid, vinyl alcohol and sulfo groups Vinyl compounds can be used.
- Ter- and quattropolymeric polycarboxylates are also particularly preferred, made from (meth) acrylic acid, maleic acid and vinyl alcohol or Vinyl alcohol derivatives (as described in DE 43 00 772 C2) or those from (meth) acrylic acid, 2-alkylallylsulfonic acid and sugar derivatives (as described in DE 42 21 381 C1) or those made from (meth) acrylic acid, Maleic acid, vinyl alcohol derivatives and monomers with sulfonic acid groups (described in DE 19 516 957 A).
- polyethylene glycol and / or polypropylene glycol with a Suitable molecular weight from 900 to 30,000, as well as carboxylated polysaccharides, Polyaspartates and polyglutamate.
- Customary bleaching agents are sodium perborate tetrahydrate and sodium perborate monohydrate, sodium percarbonate, peroxypyrophosphates, citrate perhydrates, as well as H 2 O 2 -producing peracidic salts, peracids such as perbenzoates, peroxyphthalates, diperazelaic acid and diperdodecanedioic acids.
- the bleach content in tablets is preferably 10-60% by weight and in particular 15-50% by weight.
- activators can be incorporated.
- Suitable bleach activators are the N-acyl and O-acyl compounds forming with H 2 O 2 organic peracids, preferably N, N'-tetraacylated diamines, carboxylic acid anhydrides and esters of polyols such as glucose pentaacetate. Acetylated mixtures of sorbitol and mannitol can also be used.
- bleach activators are N, N, N ', N'-tetraacetylethylene diamine (TAED), 1,5-diacetyl-2,4-dioxo-hexahydro-1,2,5-triazine (DADHT) and acetylated sorbitol mannitol Mixtures (SORMAN).
- TAED N, N, N ', N'-tetraacetylethylene diamine
- DADHT 1,5-diacetyl-2,4-dioxo-hexahydro-1,2,5-triazine
- SORMAN acetylated sorbitol mannitol Mixtures
- cationic surfactants can also be present in detergent formulations, for example quaternary ammonium compounds with C 8 -C 16 N-alkyl or N-alkenyl groups and N-substituents such as methyl, hydroxyethyl or hydroxypropyl groups.
- Polyalkylene glycols and magnesium stearates come as tableting aids into consideration.
- Examples of other common detergent additives and auxiliaries are Enzymes, magnesium silicates, aluminum aluminates, benzotriazole, glycerin, Magnesium stearate, polyalkylene glycols, hexametaphosphate, phosphonates, bentonites, Soil release polymers, carboxymethyl celluloses.
- Dishwashing tablets as an educational form of detergent formulations usually contain polyphosphates, pyrophosphates, Metaphosphates or phosphonates, layered silicates, amorphous silicates, amorphous disilicates and zeolites, as well as fillers such as sodium carbonate, Sodium sulfate, magnesium sulfate, sodium hydrogen carbonate, citrate as well Citric acid, succinic acid, tartaric acid and malic acid. Frequently are also used as auxiliary builders, cobuilders and dispersants. Such Cobuilders or dispersants can be polyacrylic acids or copolymers with polyacrylic acid and its sodium salts.
- Customary bleaching agents are sodium perborate tetrahydrate and sodium perborate monohydrate, sodium percarbonate, peroxypyrophosphates, citrate perhydrates, as well as H 2 O 2 -producing peracidic salts, peracids such as perbenzoates, peroxyphthalates, diperazelaic acid and diperdodecanedioic acids.
- the content in the tablets is preferably 10-60% by weight and in particular 15-50% by weight.
- Low-foaming non-ionic surfactants of the polyalkylene glycol and alkyl polyglucoside type are also used.
- Examples of other common detergent additives and auxiliaries are here too enzymes, magnesium silicates, aluminum aluminates, benzotriazole, Glycerin, magnesium stearate, polyalkylene glycols, hexametaphosphate as well Phosphonates.
- Water softening tablets usually consist of builders such as Layered silicates, amorphous silicates, amorphous disilicates and zeolites, as well as fillers such as sodium carbonate, sodium sulfate, magnesium sulfate, Sodium bicarbonate, citrate and citric acid. Often called Auxiliary builders cobuilders and dispersants also used. Such cobuilders or dispersants can be polyacrylic acids or copolymers with polyacrylic acid and their sodium salts.
- Low-foaming non-ionic surfactants of the polyalkylene glycol and alkyl polyglucoside type are also used.
- Examples of other common detergent additives and auxiliaries are Magnesium silicates, polyalkylene glycols and phosphonates.
- disintegrant compositions according to the teaching of the invention (all amounts in% by weight) .
- Detergent tablet containing phosphate strength of the tablet and its Disintegration time using the granules of the above examples:
- Phosphate-containing detergent tablets with the composition described in Table 3 were examined for their disintegration time and strength.
- Table 5 shows the strength and disintegration time of the individual detergent tablets when using the different disintegrants: Disintegrant composition according to example Disintegration time in sec Strength in N 2.1 35 62 2.2 28 61 2.3 25th 63 2.4 28 70 2.5 22 53 2.6 19th 64 2.7 21 63 2.8 29 58
- Phosphate-free detergent tablet strength of the tablet and its disintegration time using one of the granules of the aforementioned examples:
- Amorphous disilicate 36 30th Fatty alcohol ethoxylate 2nd 7 Fatty alcohol sulfate 11 15 Linear alkyl benzene sulphonate 4th 2nd Sodium percarbonate 16 16 TAED 4th 4th Acrylate-maleate copolymer - 3rd soda 7 4th Sodium citrate 5 5 Microcrystalline cellulose (200 ⁇ m) 4th 4th Defoamer, optical brightener, CMC, phosphonate 5 4th Enzyme mix 1 1 Disintegrant preparation according to example 2.3 5 5 5 Recipe Disintegration time in sec Strength in N a) 40 68 b) 15 48
- Example 11 Pressed molded articles with the intended use as
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Abstract
Description
Mengen von 1 Gew.% zu sehr guten Ergebnissen führen.
Ebenso genannt werden Kombinationen aus organischen Säuren und Bicarbonaten der Carbonate von Alkalimetallen.
Eine definierte Granulatmenge (z.B. 2.00 g) wird in einen dünnen Papierbeutel, wie einem Teebeutel eingeschweißt und in ein Gefäß mit einem Überschuß an Wasser getaucht. Nach 3 Minuten Eintauchzeit wird der Beutel aus dem Wasser herausgenommen und 10 Minuten zum Abtropfen aufgehängt. Der Beutel wird gewogen und aus der Gewichtsdifferenz eines nassen Beutels mit und ohne Granulat die Wasseraufnahme bestimmt. Für die Bestimmung kann destilliertes Wasser oder Wasser mit definierter Härte verwendet werden.
Nach 10 Sekunden beträgt die Volumenzunahme vorzugsweise 75 Vol.% bis 270 Vol.%, wobei ebenfalls die Volumenzunahme mit steigendem Schüttgewicht zunimmt.
Quellkinetik verschiedener Materialien | |||||||
Schüttdichte [g/l] | 70 | 90 | 90 | 300 | 300 | 450 | 450 |
Cellulose | V 1 | M1 | V2 | M2 | V3 | M3 | |
Zeit [Sec] | Weg [mm] | Weg [mm] | Weg [mm] | Weg [mm] | Weg [mm] | Weg [mm] | Weg [mm] |
0 | 0 | 0 | 0 | 0 | 0 | 0 | 0 |
1 | 0,10 | 0,20 | 0,25 | 0,30 | 0,50 | 0,80 | 1,20 |
2 | 0,20 | 0,40 | 0,40 | 0,60 | 1,05 | 1,20 | 1,80 |
3 | 0,30 | 0,60 | 0,65 | 0,90 | 1,35 | 1,50 | 2,20 |
4 | 0,35 | 0,70 | 0,80 | 1,00 | 1,58 | 1,60 | 2,40 |
5 | 0,40 | 0,85 | 0,95 | 1,10 | 1,75 | 1,70 | 2,50 |
6 | 0,42 | 1,00 | 1,15 | 1,15 | 1,83 | 1,72 | 2,58 |
7 | 0,44 | 1,10 | 1,25 | 1,20 | 1,93 | 1,80 | 2,65 |
8 | 0,46 | 1,20 | 1,40 | 1,25 | 2,00 | 1,82 | 2,70 |
9 | 0,48 | 1,35 | 1,55 | 1,40 | 2.05 | 1,82 | 2,72 |
10 | 0,48 | 1,40 | 1,65 | 1,50 | 2,15 | 1,85 | 2,75 |
11 | 0,49 | 1,45 | 1,75 | 1,60 | 2,20 | 1,90 | 2,80 |
12 | 0,50 | 1,50 | 1,80 | 1,65 | 2,25 | 1,92 | 2,83 |
Volumenausdehnung in Vol.% | |||||||
Cellulose | V1 | M1 | V2 | M2 | V3 | M3 | |
Schüttdichte in g/l | 70 | 90 | 90 | 300 | 300 | 450 | 450 |
Volumenzunahme | |||||||
nach 5 Sec Vol.% | 5 | 14 | 16 | 55 | 100 | 200 | 225 |
nach 10 Sec Vol.% | 6 | 23 | 28 | 75 | 130 | 230 | 270 |
Mit V2, M2 sind Proben bezeichnet, die nach dem Mischen in einer Walzenpresse auf ein Schüttgewicht von 300 g/l verdichtet wurden. Mit V3 und M3 sind Proben bezeichnet, die nach dem Mischen auf ein Schüttgewicht von 450 g/l mittels Walzenpresse verdichtet wurden.
Der Gehalt an Bleichmitteln in Tabletten beträgt vorzugsweise 10-60 Gew.% und insbesondere 15-50 Gew.%.
Beispiele für Sprengmittelzusammensetzungen entsprechend der Lehre der Erfindung (alle Mengen in Gew.%) . | ||||||||
Beispiel | 2.1 Vergleich | 2.2 Vergleich | 2.3 | 2.4 | 2.5 | 2.6 | 2.7 | 2.8 |
Bestandteil: | ||||||||
Cellulose | 85 | 50 | 80 | 48 | 85 | 94 | 88 | 65 |
Lineares PAA | 15 | 5 | 10 | 5 | 8 | - | 9 | 7 |
Vernetztes PPA | - | - | - | - | 5 | 4 | - | - |
CMC | - | - | - | - | - | - | 1 | - |
Mikrokristalline | - | - | - | - | - | - | - | 26 |
Cellulose | ||||||||
Nio-Tensid | - | - | 10 | 5 | 2 | 2 | 2 | 2 |
Wasser ad 100% | - | 45 | - | 42 | - | - | - | - |
Zusammensetzung Waschmitteltablette: | |
Rohstoff | Einsatzmenge in % |
Natriumtripolyphosphat | 35 |
Natriumpercarbonat | 19 |
TAED | 4 |
Fettalkoholsulfat | 14 |
Lineares Alkylbenzolsulphonat | 4 |
Soda | 8 |
Entschäumer, optischer Aufheller, CMC, Phosphonat | 6 |
Mikrokristalline Cellulose (200 µm) | 2 |
Enzymmix | 1 |
Fettalkoholethoxilat (C12/14, EO=4,7) | 2 |
Sprengmittelzubereitung gemäß Beispielen 2.1 bis 2.8 | 5 |
Sprengmittelzusammensetzung entspr. Beispiel | Zerfallszeit in sec | Festigkeit in N |
2.1 | 35 | 62 |
2.2 | 28 | 61 |
2.3 | 25 | 63 |
2.4 | 28 | 70 |
2.5 | 22 | 53 |
2.6 | 19 | 64 |
2.7 | 21 | 63 |
2.8 | 29 | 58 |
Rohstoff | Einsatzmenge in % | |
a) | b) | |
Zeolith P | 39 | 35 |
Fettalkoholethoxilat (C12/14, E0=4,7) | 4 | 7 |
Natriumpercarbonat | 16 | 16 |
TAED | 4 | 4 |
Fettalkoholsulfat | 10 | 11 |
Lineares Alkylbenzolsulphonat | 3 | 3 |
Soda | 4 | 4 |
Entschäumer, optischer Aufheller, CMC, Phosphonat | 5 | 5 |
Enzymmix | 1 | 1 |
Mikrokristalline Cellulose (200 µm) | 4 | 4 |
Sprengmittelzubereitung gemäß Beispiel 2.3 | 5 | 5 |
Natriumcitrat | 5 | 5 |
Rezeptur | Zerfallszeit in sec | Festigkeit in N |
a) | 40 | 57 |
b) | 60 | 51 |
Rohstoff | Einsatzmenge in % | |
a) | b) | |
Amorphes Disilikat | 36 | 30 |
Fettalkoholethoxilat | 2 | 7 |
Fettalkoholsulfat | 11 | 15 |
Lineares Alkylbenzolsulphonat | 4 | 2 |
Natriumpercarbonat | 16 | 16 |
TAED | 4 | 4 |
Acrylat-Maleat-Copolymer | - | 3 |
Soda | 7 | 4 |
Natriumcitrat | 5 | 5 |
Mikrokristalline Cellulose (200 µm) | 4 | 4 |
Entschäumer, optischer Aufheller, CMC, Phosphonat | 5 | 4 |
Enzymmix | 1 | 1 |
Sprengmittelzubereitung gemäß Beispiel 2.3 | 5 | 5 |
Rezeptur | Zerfallszeit in sec | Festigkeit in N |
a) | 40 | 68 |
b) | 15 | 48 |
Rohstoff | Einsatzmenge in % |
Soda -Disiklikat Cogranulat | 20 |
Soda | 41 |
Nichtionisches Tensid | 4 |
TAED | 7 |
Enzymmix | 1 |
Natriumpercarbonat | 24 |
Sprengmittelzubereitung gemäß Beispiel 2.4 | 3 |
Rohstoff | Einsatzmenge in % |
Zeolith | 15 |
Natriumhydrogencarbonat | 32 |
Zitronensäure | 20 |
Polycarboxylat | 17 |
Schichtsilikat | 8 |
Prozeßhilfsmittel | 5 |
Sprengmittelzubereitung gemäß Beispiel 2.5 | 3 |
Rohstoff | Einsatzmenge in % |
Soda-Silikat Cogranulat | 20 |
Tripolyphosphat | 35 |
Soda | 20 |
Natriumperborat | 12 |
TAED | 4 |
Enzymmix | 2 |
Prozeßhilfsmittel | 3 |
Parfum, Farbstoffe | 2 |
Sprengmittelzubereitung gemäß Beispiel 2.7 | 2 |
Physikalische Parameter | Fleckensalz gemäß Zusammensetzung a) | Wasserenthärter gemäß Zusammensetzung b) | Maschinengeschirr-Reiniger gemäß Zusammensetzung c) |
Festigkeit in N | 188 | 210 | 186 |
Zerfallszeit ohne Sprengmittel | 224 s | 147 s | 240 s |
Zerfallszeit mit Sprengmittel | 100 s | 73 s | 70 s |
Claims (21)
- Verdichtetes Sprengmittelgranulat für gepreßte Formkörper, enthaltend nichtwasserlösliche, in Wasser quellbare hochreine Cellulose und/oder Cellulosederivate und feinteilige Polymere / Copolymere von (Meth)acrylsäure oder Salzen derselben und ein oder mehrere flüssige, mit Wasser gelbildende oder verdickende nicht ionische und/oder anionische und/oder amphotere Tenside, wobei das Gewichtsverhältnis der kombinierten in Wasser quellbaren Cellulose/Cellulosederivate und Polymere/Copolymere von (Meth)acrylsäure : flüssigen Tensid(en) von 100:1 bis 10:1 beträgt.
- Granulat nach Anspruch 1, dadurch gekennzeichnet, daß durch das Verdichten eine Ausrichtung der anisotropen Cellulose bzw. Cellulosederivate erzeugt wird.
- Granulat nach einem der Ansprüche 1 oder 2, dadurch gekennzeichnet, daß in Wasser quellbare Cellulose/Cellulosederivate und feinteilige Polymere / Copolymere von (Meth)acrylsäure in einem Gewichtsverhältnis von 100:0,5 bis 100:30, vorzugsweise von 100:1 bis 100:20, ganz besonders bevorzugt in einem Gewichtsverhältnis von 100:1 bis 100:10 vorhanden sind.
- Granulat nach einem der Ansprüche 1 bis 3, dadurch gekennzeichnet, daß die Schüttdichte von 100 g/l bis 800 g/l beträgt, vorzugsweise 200 g/l bis 600 g/l und besonders bevorzugt 300 g/l bis 500 g/l.
- Granulat nach einem der Ansprüche 1 bis 4, dadurch gekennzeichnet, daß die spezifische Wasseraufnahme 500 bis 2.000 Gew.% beträgt.
- Granulat nach einem der Ansprüche 1 bis 5, dadurch gekennzeichnet, daß es eine nichtlineare Quellkinetik aufweist.
- Granulat nach einem der Ansprüche 1 bis 6, dadurch gekennzeichnet, daß die feinteiligen Polymere/Copolymere von (Meth)acrylsäure ausgewählt sind aus linearen Polymeren/Copolymeren von (Meth)acrylsäure, quervernetzten Polymeren/Copolymeren von (Meth)acrylsäure, Copolymeren von (Meth)acrylsäure und Malein-säure, ter- und quattropolymeren Copolymeren, hergestellt aus (Meth)acrylsäure, Maleinsäure und Vinylalkohol oder Vinylalkoholderivaten, oder solchen aus (Meth)acrylsäure, ethylenisch ungesättigter Sulfonsäure und Zuckerderivaten, oder solchen aus (Meth)acrylsäure, Maleinsäure oder Maleinsäureanhydrid, Vinylalkoholderivaten und sulfonsäuregruppenhaltigen Monomeren, und Mischungen derselben.
- Granulat nach einem der Ansprüche 1 bis 7, dadurch gekennzeichnet, daß die feinteilige Cellulose eine mittlere Teilchengröße zwischen 30 µm und 300 µm hat/haben und/oder ein Schüttgewicht von 40 g/l bis 300 g/l, bevorzugt von 65 g/l bis 170 g/l aufweist.
- Granulat nach einem der Ansprüche 1 bis 8, dadurch gekennzeichnet, daß die Cellulosederivate ausgewählt sind aus Cellulosesethern, Celluloseestern oder gemischten Modifizierungen derselben.
- Granulat nach Anspruch 9, dadurch gekennzeichnet, daß die Cellulosederivate eine mittlere Teilchengröße zwischen 30 µm und 1000 µm haben und/oder ein Schüttgewicht von 50 g/l bis 1000 g/l, bevorzugt von 100 g/l bis 800 g/l aufweisen.
- Granulat nach einem der Ansprüche 1 bis 10, dadurch gekennzeichnet, daß das/die flüssige(n) anionische(n) und/oder nichtionische(n) Tensid(e) ausgewählt sind aus Fettalkoholethoxylaten mit 3 bis 15 Mol Ethylenoxid, Anionics vom Typ Fettalkoholsulfat und linearen Alkylbenzolsulfonaten, sowie Alkylethersulfaten und Mischungen derselben.
- Verfahren zum Herstellen eines verdichteten Sprengmittelgranulats nach einem der Ansprüche 1 bis 11 durch Mischen der hochreinen Cellulose/Cellulosederivate mit dem (den) nichtionischen, anionischen und amphoteren Tensid(en) und Einmischen des (der) feinteiligen Polymere/Copolymere von (Meth)acrylsäure oder Salzen derselben, wobei das Gewichtsverhältnis der kombinierten in Wasser quellbaren Cellulose/Cellulosederivate und Polymere/Copolymere von (Meth)acrylsäure : flüssigen Tensid(en) von 100:1 bis 10:1 beträgt und Granulieren und anschließendes Verdichten des Granulats.
- Verfahren nach Anspruch 12, wobei das Verdichten des Granulats unter Ausrichtung anisotroper Cellulose/Cellulosederivate erfolgt.
- Verfahren nach Anspruch 12 oder 13, dadurch gekennzeichnet, daß das Verdichten mittels Walzen unter Friktion derselben erfolgt.
- Verfahren nach Anspruch 12 oder 13, dadurch gekennzeichnet, daß das Verdichten mittels Walzenkompaktors, Walzen- oder Würfelpressen oder Extrudern erfolgt.
- Verwendung des Sprengmittelgranulats nach einem der Ansprüche 1 bis 11, wobei das Sprengmittelgranulat in den gepreßten Formkörpern in Mengen von 0,5 Gew.% bis 10 Gew.%, vorzugsweise 2 Gew.% bis 7 Gew.% und besonders bevorzugt 3 Gew.% bis 6 Gew.% eingesetzt wird als Sprengmittel für gepresste Formkörper.
- Verwendung nach Anspruch 16 als Sprengmittel für Waschmitteltabletten.
- Verwendung nach Anspruch 16 als Sprengmittel für Reinigungsmitteltabletten.
- Verwendung nach Anspruch 18 als Sprengmittel für Reinigungsmitteltabletten für Geschirrspüler.
- Verwendung nach Anspruch 16 als Sprengmittel für Wasserenthärtungstabletten.
- Verwendung nach Anspruch 16 als Sprengmittel für Fleckensalztabletten.
Priority Applications (11)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
DK98121397T DK1004656T3 (da) | 1998-11-11 | 1998-11-11 | Komprimeret granulat, fremstillingsfremgangsmåde og anvendelse som sprængemiddel til pressede formlegemer |
ES98121397T ES2153229T3 (es) | 1998-11-11 | 1998-11-11 | Granulado densificado, procedimiento para su fabricacion y su utilizacion como agente desintegrador para cuerpos moldeados por compactacion. |
AT98121397T ATE198348T1 (de) | 1998-11-11 | 1998-11-11 | Verdichtetes granulat, herstellungsverfahren und verwendung als sprengmittel für gepresste formkörper |
EP98121397A EP1004656B1 (de) | 1998-11-11 | 1998-11-11 | Verdichtetes Granulat, Herstellungsverfahren und Verwendung als Sprengmittel für gepresste Formkörper |
PT79100995T PT1004656E (pt) | 1998-11-11 | 1998-11-11 | Processo de fabrico e utilizacao de granulado compactado como desintegrante em corpos moldados por prensagem |
DE59800410T DE59800410D1 (de) | 1998-11-11 | 1998-11-11 | Verdichtetes Granulat, Herstellungsverfahren und Verwendung als Sprengmittel für gepresste Formkörper |
HU9903991A HU228025B1 (en) | 1998-11-11 | 1999-11-01 | Caulked granulate, process for producing it and its use as a material for promoting decomposition |
TR1999/02772A TR199902772A2 (xx) | 1998-11-11 | 1999-11-10 | S�k��t�r�lm�� gran�l, �retimi ve sulama maddesi olarak kullan�m� |
CZ19993977A CZ290160B6 (cs) | 1998-11-11 | 1999-11-10 | Zhutněný granulát, způsob jeho výroby a jeho pouľití jako bubřidla pro lisovaná tvarová tělesa |
PL336514A PL191104B1 (pl) | 1998-11-11 | 1999-11-10 | Zgęszczony granulat substancji rozsadzającej, sposób jego wytwarzania i zastosowanie zgęszczonego granulatu substancji rozsadzającej |
US09/438,657 US6232285B1 (en) | 1998-11-11 | 1999-11-12 | Compacted granulate, process for making same and use as disintegrating agent for pressed detergent tablets, cleaning agent tablets for dishwashers, water softening tablets and scouring salt tablets |
Applications Claiming Priority (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
EP98121397A EP1004656B1 (de) | 1998-11-11 | 1998-11-11 | Verdichtetes Granulat, Herstellungsverfahren und Verwendung als Sprengmittel für gepresste Formkörper |
Publications (2)
Publication Number | Publication Date |
---|---|
EP1004656A1 EP1004656A1 (de) | 2000-05-31 |
EP1004656B1 true EP1004656B1 (de) | 2000-12-27 |
Family
ID=8232957
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
EP98121397A Expired - Lifetime EP1004656B1 (de) | 1998-11-11 | 1998-11-11 | Verdichtetes Granulat, Herstellungsverfahren und Verwendung als Sprengmittel für gepresste Formkörper |
Country Status (11)
Country | Link |
---|---|
US (1) | US6232285B1 (de) |
EP (1) | EP1004656B1 (de) |
AT (1) | ATE198348T1 (de) |
CZ (1) | CZ290160B6 (de) |
DE (1) | DE59800410D1 (de) |
DK (1) | DK1004656T3 (de) |
ES (1) | ES2153229T3 (de) |
HU (1) | HU228025B1 (de) |
PL (1) | PL191104B1 (de) |
PT (1) | PT1004656E (de) |
TR (1) | TR199902772A2 (de) |
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1998
- 1998-11-11 PT PT79100995T patent/PT1004656E/pt unknown
- 1998-11-11 ES ES98121397T patent/ES2153229T3/es not_active Expired - Lifetime
- 1998-11-11 DE DE59800410T patent/DE59800410D1/de not_active Expired - Lifetime
- 1998-11-11 DK DK98121397T patent/DK1004656T3/da active
- 1998-11-11 AT AT98121397T patent/ATE198348T1/de active
- 1998-11-11 EP EP98121397A patent/EP1004656B1/de not_active Expired - Lifetime
-
1999
- 1999-11-01 HU HU9903991A patent/HU228025B1/hu unknown
- 1999-11-10 CZ CZ19993977A patent/CZ290160B6/cs not_active IP Right Cessation
- 1999-11-10 PL PL336514A patent/PL191104B1/pl unknown
- 1999-11-10 TR TR1999/02772A patent/TR199902772A2/xx unknown
- 1999-11-12 US US09/438,657 patent/US6232285B1/en not_active Expired - Lifetime
Cited By (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
DE102004020010A1 (de) * | 2004-04-21 | 2005-11-17 | Henkel Kgaa | Verfahren zur Herstellung von Polymer-Granulaten |
Also Published As
Publication number | Publication date |
---|---|
PT1004656E (pt) | 2001-04-30 |
ES2153229T3 (es) | 2001-02-16 |
HUP9903991A3 (en) | 2000-09-28 |
HUP9903991A2 (hu) | 2000-08-28 |
PL336514A1 (en) | 2000-05-22 |
CZ397799A3 (cs) | 2000-08-16 |
DE59800410D1 (de) | 2001-02-01 |
PL191104B1 (pl) | 2006-03-31 |
US6232285B1 (en) | 2001-05-15 |
DK1004656T3 (da) | 2001-02-05 |
HU228025B1 (en) | 2012-08-28 |
TR199902772A3 (tr) | 2000-06-21 |
CZ290160B6 (cs) | 2002-06-12 |
HU9903991D0 (en) | 2000-01-28 |
ATE198348T1 (de) | 2001-01-15 |
EP1004656A1 (de) | 2000-05-31 |
TR199902772A2 (xx) | 2000-06-21 |
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