EP1781768B2 - Coated shaped detergent or cleaning agent body - Google Patents
Coated shaped detergent or cleaning agent body Download PDFInfo
- Publication number
- EP1781768B2 EP1781768B2 EP05769966.2A EP05769966A EP1781768B2 EP 1781768 B2 EP1781768 B2 EP 1781768B2 EP 05769966 A EP05769966 A EP 05769966A EP 1781768 B2 EP1781768 B2 EP 1781768B2
- Authority
- EP
- European Patent Office
- Prior art keywords
- coated
- shaped
- water
- coating
- coating agent
- 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.)
- Active
Links
- 239000012459 cleaning agent Substances 0.000 title claims abstract description 22
- 239000003599 detergent Substances 0.000 title description 31
- 239000011248 coating agent Substances 0.000 claims abstract description 89
- 238000000034 method Methods 0.000 claims abstract description 53
- 238000004519 manufacturing process Methods 0.000 claims abstract description 4
- 238000000576 coating method Methods 0.000 claims description 55
- 238000005406 washing Methods 0.000 claims description 26
- 238000005507 spraying Methods 0.000 claims description 23
- 229920002451 polyvinyl alcohol Polymers 0.000 claims description 17
- 239000004372 Polyvinyl alcohol Substances 0.000 claims description 15
- 239000000243 solution Substances 0.000 claims description 14
- 238000004140 cleaning Methods 0.000 claims description 13
- 229920000642 polymer Polymers 0.000 claims description 12
- 239000006185 dispersion Substances 0.000 claims description 11
- 238000007789 sealing Methods 0.000 claims description 11
- 229920003086 cellulose ether Polymers 0.000 claims description 7
- 229920000036 polyvinylpyrrolidone Polymers 0.000 claims description 7
- 235000013855 polyvinylpyrrolidone Nutrition 0.000 claims description 7
- 239000001267 polyvinylpyrrolidone Substances 0.000 claims description 6
- 229920000620 organic polymer Polymers 0.000 claims description 5
- 239000007864 aqueous solution Substances 0.000 claims description 3
- 238000011049 filling Methods 0.000 claims description 3
- 238000000465 moulding Methods 0.000 description 45
- 239000001993 wax Substances 0.000 description 36
- 239000000126 substance Substances 0.000 description 30
- 239000000463 material Substances 0.000 description 24
- 239000000203 mixture Substances 0.000 description 22
- 239000012188 paraffin wax Substances 0.000 description 18
- 235000019422 polyvinyl alcohol Nutrition 0.000 description 15
- 239000007921 spray Substances 0.000 description 12
- 238000001035 drying Methods 0.000 description 11
- 235000019271 petrolatum Nutrition 0.000 description 10
- -1 Hydroxybutyl Chemical group 0.000 description 9
- 235000019809 paraffin wax Nutrition 0.000 description 9
- 239000003795 chemical substances by application Substances 0.000 description 8
- 239000007788 liquid Substances 0.000 description 8
- 238000004806 packaging method and process Methods 0.000 description 8
- 229920001577 copolymer Polymers 0.000 description 7
- 239000004615 ingredient Substances 0.000 description 6
- 239000000155 melt Substances 0.000 description 6
- 229920000609 methyl cellulose Polymers 0.000 description 6
- 235000010981 methylcellulose Nutrition 0.000 description 6
- 239000001923 methylcellulose Substances 0.000 description 6
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 6
- 229920001479 Hydroxyethyl methyl cellulose Polymers 0.000 description 5
- 150000001298 alcohols Chemical class 0.000 description 5
- 229920002678 cellulose Polymers 0.000 description 5
- 239000001913 cellulose Substances 0.000 description 5
- 235000010980 cellulose Nutrition 0.000 description 5
- 239000003112 inhibitor Substances 0.000 description 5
- 238000002360 preparation method Methods 0.000 description 5
- 239000007787 solid Substances 0.000 description 5
- 229920003169 water-soluble polymer Polymers 0.000 description 5
- 229920002134 Carboxymethyl cellulose Polymers 0.000 description 4
- 229920002153 Hydroxypropyl cellulose Polymers 0.000 description 4
- 239000004166 Lanolin Substances 0.000 description 4
- 229920003171 Poly (ethylene oxide) Polymers 0.000 description 4
- 239000000470 constituent Substances 0.000 description 4
- 235000014113 dietary fatty acids Nutrition 0.000 description 4
- 238000004090 dissolution Methods 0.000 description 4
- 239000000194 fatty acid Substances 0.000 description 4
- 229930195729 fatty acid Natural products 0.000 description 4
- 239000012530 fluid Substances 0.000 description 4
- 239000001863 hydroxypropyl cellulose Substances 0.000 description 4
- 235000010977 hydroxypropyl cellulose Nutrition 0.000 description 4
- TYWMIZZBOVGFOV-UHFFFAOYSA-N tetracosan-1-ol Chemical compound CCCCCCCCCCCCCCCCCCCCCCCCO TYWMIZZBOVGFOV-UHFFFAOYSA-N 0.000 description 4
- 241000252185 Cobitidae Species 0.000 description 3
- 108010010803 Gelatin Proteins 0.000 description 3
- 150000003926 acrylamides Chemical class 0.000 description 3
- 239000013543 active substance Substances 0.000 description 3
- 238000007792 addition Methods 0.000 description 3
- 239000002585 base Substances 0.000 description 3
- 229910052799 carbon Inorganic materials 0.000 description 3
- 239000008199 coating composition Substances 0.000 description 3
- 150000002148 esters Chemical class 0.000 description 3
- 150000004665 fatty acids Chemical class 0.000 description 3
- 229920000159 gelatin Polymers 0.000 description 3
- 239000008273 gelatin Substances 0.000 description 3
- 235000019322 gelatine Nutrition 0.000 description 3
- 235000011852 gelatine desserts Nutrition 0.000 description 3
- 230000002209 hydrophobic effect Effects 0.000 description 3
- 235000019388 lanolin Nutrition 0.000 description 3
- 238000002844 melting Methods 0.000 description 3
- 230000008018 melting Effects 0.000 description 3
- 239000002904 solvent Substances 0.000 description 3
- DSEKYWAQQVUQTP-XEWMWGOFSA-N (2r,4r,4as,6as,6as,6br,8ar,12ar,14as,14bs)-2-hydroxy-4,4a,6a,6b,8a,11,11,14a-octamethyl-2,4,5,6,6a,7,8,9,10,12,12a,13,14,14b-tetradecahydro-1h-picen-3-one Chemical compound C([C@H]1[C@]2(C)CC[C@@]34C)C(C)(C)CC[C@]1(C)CC[C@]2(C)[C@H]4CC[C@@]1(C)[C@H]3C[C@@H](O)C(=O)[C@@H]1C DSEKYWAQQVUQTP-XEWMWGOFSA-N 0.000 description 2
- QNRATNLHPGXHMA-XZHTYLCXSA-N (r)-(6-ethoxyquinolin-4-yl)-[(2s,4s,5r)-5-ethyl-1-azabicyclo[2.2.2]octan-2-yl]methanol;hydrochloride Chemical compound Cl.C([C@H]([C@H](C1)CC)C2)CN1[C@@H]2[C@H](O)C1=CC=NC2=CC=C(OCC)C=C21 QNRATNLHPGXHMA-XZHTYLCXSA-N 0.000 description 2
- RPZANUYHRMRTTE-UHFFFAOYSA-N 2,3,4-trimethoxy-6-(methoxymethyl)-5-[3,4,5-trimethoxy-6-(methoxymethyl)oxan-2-yl]oxyoxane;1-[[3,4,5-tris(2-hydroxybutoxy)-6-[4,5,6-tris(2-hydroxybutoxy)-2-(2-hydroxybutoxymethyl)oxan-3-yl]oxyoxan-2-yl]methoxy]butan-2-ol Chemical compound COC1C(OC)C(OC)C(COC)OC1OC1C(OC)C(OC)C(OC)OC1COC.CCC(O)COC1C(OCC(O)CC)C(OCC(O)CC)C(COCC(O)CC)OC1OC1C(OCC(O)CC)C(OCC(O)CC)C(OCC(O)CC)OC1COCC(O)CC RPZANUYHRMRTTE-UHFFFAOYSA-N 0.000 description 2
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 description 2
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 2
- 229920000896 Ethulose Polymers 0.000 description 2
- 239000001856 Ethyl cellulose Substances 0.000 description 2
- 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 2
- 229920001800 Shellac Polymers 0.000 description 2
- 239000004164 Wax ester Substances 0.000 description 2
- 239000004480 active ingredient Substances 0.000 description 2
- WNLRTRBMVRJNCN-UHFFFAOYSA-N adipic acid Chemical compound OC(=O)CCCCC(O)=O WNLRTRBMVRJNCN-UHFFFAOYSA-N 0.000 description 2
- 150000001335 aliphatic alkanes Chemical class 0.000 description 2
- 238000013459 approach Methods 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 239000001768 carboxy methyl cellulose Substances 0.000 description 2
- 235000010948 carboxy methyl cellulose Nutrition 0.000 description 2
- 239000008112 carboxymethyl-cellulose Substances 0.000 description 2
- 150000001875 compounds Chemical class 0.000 description 2
- 238000011109 contamination Methods 0.000 description 2
- RKTYLMNFRDHKIL-UHFFFAOYSA-N copper;5,10,15,20-tetraphenylporphyrin-22,24-diide Chemical compound [Cu+2].C1=CC(C(=C2C=CC([N-]2)=C(C=2C=CC=CC=2)C=2C=CC(N=2)=C(C=2C=CC=CC=2)C2=CC=C3[N-]2)C=2C=CC=CC=2)=NC1=C3C1=CC=CC=C1 RKTYLMNFRDHKIL-UHFFFAOYSA-N 0.000 description 2
- 238000005260 corrosion Methods 0.000 description 2
- 230000007797 corrosion Effects 0.000 description 2
- 150000001924 cycloalkanes Chemical class 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 229920001249 ethyl cellulose Polymers 0.000 description 2
- 235000019325 ethyl cellulose Nutrition 0.000 description 2
- 150000002191 fatty alcohols Chemical class 0.000 description 2
- 239000011888 foil Substances 0.000 description 2
- 239000003205 fragrance Substances 0.000 description 2
- 150000004676 glycans Chemical class 0.000 description 2
- 239000008187 granular material Substances 0.000 description 2
- BXWNKGSJHAJOGX-UHFFFAOYSA-N hexadecan-1-ol Chemical compound CCCCCCCCCCCCCCCCO BXWNKGSJHAJOGX-UHFFFAOYSA-N 0.000 description 2
- 229920013819 hydroxyethyl ethylcellulose Polymers 0.000 description 2
- 229940039717 lanolin Drugs 0.000 description 2
- 239000004570 mortar (masonry) Substances 0.000 description 2
- 239000003791 organic solvent mixture Substances 0.000 description 2
- XNGIFLGASWRNHJ-UHFFFAOYSA-N phthalic acid Chemical compound OC(=O)C1=CC=CC=C1C(O)=O XNGIFLGASWRNHJ-UHFFFAOYSA-N 0.000 description 2
- 229920001515 polyalkylene glycol Polymers 0.000 description 2
- 229920001282 polysaccharide Polymers 0.000 description 2
- 239000005017 polysaccharide Substances 0.000 description 2
- 239000000843 powder Substances 0.000 description 2
- 239000004208 shellac Substances 0.000 description 2
- 235000013874 shellac Nutrition 0.000 description 2
- ZLGIYFNHBLSMPS-ATJNOEHPSA-N shellac Chemical compound OCCCCCC(O)C(O)CCCCCCCC(O)=O.C1C23[C@H](C(O)=O)CCC2[C@](C)(CO)[C@@H]1C(C(O)=O)=C[C@@H]3O ZLGIYFNHBLSMPS-ATJNOEHPSA-N 0.000 description 2
- 229940113147 shellac Drugs 0.000 description 2
- 238000003860 storage Methods 0.000 description 2
- 239000004094 surface-active agent Substances 0.000 description 2
- HLZKNKRTKFSKGZ-UHFFFAOYSA-N tetradecan-1-ol Chemical compound CCCCCCCCCCCCCCO HLZKNKRTKFSKGZ-UHFFFAOYSA-N 0.000 description 2
- REZQBEBOWJAQKS-UHFFFAOYSA-N triacontan-1-ol Chemical compound CCCCCCCCCCCCCCCCCCCCCCCCCCCCCCO REZQBEBOWJAQKS-UHFFFAOYSA-N 0.000 description 2
- 235000019386 wax ester Nutrition 0.000 description 2
- VYQDALBEQRZDPL-UHFFFAOYSA-N (2-hexadecanoyloxy-3-hydroxypropyl) octadecanoate Chemical compound CCCCCCCCCCCCCCCCCC(=O)OCC(CO)OC(=O)CCCCCCCCCCCCCCC VYQDALBEQRZDPL-UHFFFAOYSA-N 0.000 description 1
- XBZYWSMVVKYHQN-MYPRUECHSA-N (4as,6as,6br,8ar,9r,10s,12ar,12br,14bs)-10-hydroxy-2,2,6a,6b,9,12a-hexamethyl-9-[(sulfooxy)methyl]-1,2,3,4,4a,5,6,6a,6b,7,8,8a,9,10,11,12,12a,12b,13,14b-icosahydropicene-4a-carboxylic acid Chemical compound C1C[C@H](O)[C@@](C)(COS(O)(=O)=O)[C@@H]2CC[C@@]3(C)[C@]4(C)CC[C@@]5(C(O)=O)CCC(C)(C)C[C@H]5C4=CC[C@@H]3[C@]21C XBZYWSMVVKYHQN-MYPRUECHSA-N 0.000 description 1
- VBICKXHEKHSIBG-UHFFFAOYSA-N 1-monostearoylglycerol Chemical compound CCCCCCCCCCCCCCCCCC(=O)OCC(O)CO VBICKXHEKHSIBG-UHFFFAOYSA-N 0.000 description 1
- 229940094997 1-tetracosanol Drugs 0.000 description 1
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 description 1
- NIXOWILDQLNWCW-UHFFFAOYSA-N 2-Propenoic acid Natural products OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 1
- 241000640882 Condea Species 0.000 description 1
- VOWAEIGWURALJQ-UHFFFAOYSA-N Dicyclohexyl phthalate Chemical compound C=1C=CC=C(C(=O)OC2CCCCC2)C=1C(=O)OC1CCCCC1 VOWAEIGWURALJQ-UHFFFAOYSA-N 0.000 description 1
- 102000016942 Elastin Human genes 0.000 description 1
- 108010014258 Elastin Proteins 0.000 description 1
- 102000004190 Enzymes Human genes 0.000 description 1
- 108090000790 Enzymes Proteins 0.000 description 1
- IAYPIBMASNFSPL-UHFFFAOYSA-N Ethylene oxide Chemical compound C1CO1 IAYPIBMASNFSPL-UHFFFAOYSA-N 0.000 description 1
- 229920000881 Modified starch Polymers 0.000 description 1
- 240000007594 Oryza sativa Species 0.000 description 1
- 235000007164 Oryza sativa Nutrition 0.000 description 1
- 239000004264 Petrolatum Substances 0.000 description 1
- 229920002845 Poly(methacrylic acid) Polymers 0.000 description 1
- OFOBLEOULBTSOW-UHFFFAOYSA-N Propanedioic acid Natural products OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 0.000 description 1
- 240000000111 Saccharum officinarum Species 0.000 description 1
- 235000007201 Saccharum officinarum Nutrition 0.000 description 1
- 244000044822 Simmondsia californica Species 0.000 description 1
- 235000004433 Simmondsia californica Nutrition 0.000 description 1
- 229920002472 Starch Polymers 0.000 description 1
- 239000006096 absorbing agent Substances 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 150000007513 acids Chemical class 0.000 description 1
- 150000001252 acrylic acid derivatives Chemical class 0.000 description 1
- 150000001253 acrylic acids Chemical class 0.000 description 1
- 239000012190 activator Substances 0.000 description 1
- 239000011149 active material Substances 0.000 description 1
- 235000011037 adipic acid Nutrition 0.000 description 1
- 239000001361 adipic acid Substances 0.000 description 1
- 229920000615 alginic acid Polymers 0.000 description 1
- 235000010443 alginic acid Nutrition 0.000 description 1
- 150000001338 aliphatic hydrocarbons Chemical class 0.000 description 1
- 229910052783 alkali metal Inorganic materials 0.000 description 1
- 239000012164 animal wax Substances 0.000 description 1
- 239000012753 anti-shrinkage agent Substances 0.000 description 1
- 239000004599 antimicrobial Substances 0.000 description 1
- 239000003963 antioxidant agent Substances 0.000 description 1
- 239000002216 antistatic agent Substances 0.000 description 1
- 238000000889 atomisation Methods 0.000 description 1
- 235000013871 bee wax Nutrition 0.000 description 1
- 239000012166 beeswax Substances 0.000 description 1
- 239000011230 binding agent Substances 0.000 description 1
- 239000007844 bleaching agent Substances 0.000 description 1
- 239000004204 candelilla wax Substances 0.000 description 1
- 235000013868 candelilla wax Nutrition 0.000 description 1
- 229940073532 candelilla wax Drugs 0.000 description 1
- 125000004432 carbon atom Chemical group C* 0.000 description 1
- 150000001735 carboxylic acids Chemical class 0.000 description 1
- 239000004203 carnauba wax Substances 0.000 description 1
- 235000013869 carnauba wax Nutrition 0.000 description 1
- 239000000969 carrier Substances 0.000 description 1
- 229960000541 cetyl alcohol Drugs 0.000 description 1
- 238000005056 compaction Methods 0.000 description 1
- 230000006835 compression Effects 0.000 description 1
- 238000007906 compression Methods 0.000 description 1
- 239000012141 concentrate Substances 0.000 description 1
- 239000007799 cork Substances 0.000 description 1
- 238000004132 cross linking Methods 0.000 description 1
- 230000006378 damage Effects 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 230000003111 delayed effect Effects 0.000 description 1
- 238000000280 densification Methods 0.000 description 1
- 230000001419 dependent effect Effects 0.000 description 1
- 150000001991 dicarboxylic acids Chemical class 0.000 description 1
- 239000002270 dispersing agent Substances 0.000 description 1
- QLVARBCGUNCRTA-LOYHVIPDSA-N ditetradecyl (2r,3r)-2,3-dihydroxybutanedioate Chemical compound CCCCCCCCCCCCCCOC(=O)[C@H](O)[C@@H](O)C(=O)OCCCCCCCCCCCCCC QLVARBCGUNCRTA-LOYHVIPDSA-N 0.000 description 1
- 239000000975 dye Substances 0.000 description 1
- 239000003792 electrolyte Substances 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 230000002349 favourable effect Effects 0.000 description 1
- 239000000945 filler Substances 0.000 description 1
- 238000011010 flushing procedure Methods 0.000 description 1
- 239000006260 foam Substances 0.000 description 1
- 239000000417 fungicide Substances 0.000 description 1
- 230000002070 germicidal effect Effects 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- 150000002334 glycols Chemical class 0.000 description 1
- 229920000578 graft copolymer Polymers 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- IUJAMGNYPWYUPM-UHFFFAOYSA-N hentriacontane Chemical compound CCCCCCCCCCCCCCCCCCCCCCCCCCCCCCC IUJAMGNYPWYUPM-UHFFFAOYSA-N 0.000 description 1
- 230000007062 hydrolysis Effects 0.000 description 1
- 238000006460 hydrolysis reaction Methods 0.000 description 1
- 238000010348 incorporation Methods 0.000 description 1
- 238000010409 ironing Methods 0.000 description 1
- 230000001788 irregular Effects 0.000 description 1
- 239000012182 japan wax Substances 0.000 description 1
- VZCYOOQTPOCHFL-UPHRSURJSA-N maleic acid Chemical compound OC(=O)\C=C/C(O)=O VZCYOOQTPOCHFL-UPHRSURJSA-N 0.000 description 1
- 239000011976 maleic acid Substances 0.000 description 1
- 239000011159 matrix material Substances 0.000 description 1
- 239000012184 mineral wax Substances 0.000 description 1
- 235000019426 modified starch Nutrition 0.000 description 1
- 239000012170 montan wax Substances 0.000 description 1
- 229940043348 myristyl alcohol Drugs 0.000 description 1
- 239000003921 oil Substances 0.000 description 1
- 230000003287 optical effect Effects 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- 239000012168 ouricury wax Substances 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 239000002304 perfume Substances 0.000 description 1
- 229940066842 petrolatum Drugs 0.000 description 1
- 229920003023 plastic Polymers 0.000 description 1
- 239000004033 plastic Substances 0.000 description 1
- 229920002432 poly(vinyl methyl ether) polymer Polymers 0.000 description 1
- 229920001281 polyalkylene Polymers 0.000 description 1
- 229920001223 polyethylene glycol Polymers 0.000 description 1
- 238000006116 polymerization reaction Methods 0.000 description 1
- 238000003825 pressing Methods 0.000 description 1
- 108090000623 proteins and genes Proteins 0.000 description 1
- 102000004169 proteins and genes Human genes 0.000 description 1
- 230000005855 radiation Effects 0.000 description 1
- 235000009566 rice Nutrition 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 229920006395 saturated elastomer Polymers 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 239000012176 shellac wax Substances 0.000 description 1
- 229920002545 silicone oil Polymers 0.000 description 1
- 239000012748 slip agent Substances 0.000 description 1
- 239000012177 spermaceti Substances 0.000 description 1
- 229940084106 spermaceti Drugs 0.000 description 1
- 239000008107 starch Substances 0.000 description 1
- 235000019698 starch Nutrition 0.000 description 1
- 230000008961 swelling Effects 0.000 description 1
- 238000012549 training Methods 0.000 description 1
- VZCYOOQTPOCHFL-UHFFFAOYSA-N trans-butenedioic acid Natural products OC(=O)C=CC(O)=O VZCYOOQTPOCHFL-UHFFFAOYSA-N 0.000 description 1
- 238000012546 transfer Methods 0.000 description 1
- 239000012178 vegetable wax Substances 0.000 description 1
- 229920003176 water-insoluble polymer Polymers 0.000 description 1
- 238000004018 waxing Methods 0.000 description 1
- 238000005303 weighing Methods 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
- 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
- C11D17/0082—Coated 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
- C11D17/0047—Detergents in the form of bars or tablets
- C11D17/0065—Solid detergents containing builders
- C11D17/0073—Tablets
- C11D17/0078—Multilayered tablets
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
- Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
- Y10T428/00—Stock material or miscellaneous articles
- Y10T428/27—Web or sheet containing structurally defined element or component, the element or component having a specified weight per unit area [e.g., gms/sq cm, lbs/sq ft, etc.]
- Y10T428/273—Web or sheet containing structurally defined element or component, the element or component having a specified weight per unit area [e.g., gms/sq cm, lbs/sq ft, etc.] of coating
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
- Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
- Y10T428/00—Stock material or miscellaneous articles
- Y10T428/27—Web or sheet containing structurally defined element or component, the element or component having a specified weight per unit area [e.g., gms/sq cm, lbs/sq ft, etc.]
- Y10T428/273—Web or sheet containing structurally defined element or component, the element or component having a specified weight per unit area [e.g., gms/sq cm, lbs/sq ft, etc.] of coating
- Y10T428/277—Cellulosic substrate
Definitions
- the present invention relates to coated detergent tablets and to processes for their production.
- the present application relates to shaped bodies which have a cavity in the form of a depression or a through hole and whose surface coverage of the coated molding surface with the coating agent is between 0.2 and 50 mg / cm 2 .
- Detergents or cleaners are now available to the consumer in a variety of forms.
- this offer also includes, for example, detergent concentrates in the form of extruded or tabletted compositions.
- These fixed, concentrated or compressed forms of supply are characterized by a reduced volume per dosing unit and thus reduce the costs for packaging and transport.
- the washing or cleaning agent tablets additionally meet the consumer's desire for simple dosing. The corresponding means are comprehensively described in the prior art.
- tableted detergents or cleaners are more difficult to dissolve than conventional powdered or liquid detergents or cleaners due to the high densification of their constituents. This can cause problems. Delayed disintegration / dissolution of the ingredients can result in reduced cleaning performance, incomplete flushing of the media through the dispenser compartment, and the formation of stains and encrustations.
- This object has been achieved by a coating method for detergent tablets, in which the tablet surface is coated with a surface coverage of between 0.2 and 50 mg / cm 2 .
- the coating compositions can be used as pure substances, for example in the form of their melts, but also as dispersions or solutions.
- organic solvents are also suitable as dispersants, with aqueous dispersions or aqueous solutions being particularly preferred.
- These dispersions or solutions, in particular the aqueous dispersions or solutions preferably have a weight fraction of the coating agent below 80% by weight, preferably below 65% by weight, more preferably below 50% by weight and in particular below 40% by weight, in each case based on the total weight of the dispersion or solution.
- the application of the molding with the coating agent is carried out by spraying.
- spraying all known to those skilled in the art for this purpose are suitable.
- the spraying is preferably carried out by means of single-fluid or high-pressure spray nozzles, two-component spray nozzles or three-component spray nozzles.
- a high melt pressure 5-15 MPa
- spraying in dual-fluid spray nozzles takes place by means of a stream of compressed air (at 0.15-0.3 MPa).
- the spraying with two-component spray nozzles is more favorable, especially with regard to possible blockages of the nozzle, but more expensive due to the high consumption of compressed air.
- three-component spray nozzles which, in addition to the stream of compressed air for atomization, are intended to prevent a further air-guiding system which prevents blockages and droplet formation at the nozzle.
- the use of two-component spray nozzles preferably two-component spray nozzles with a fluid bore of between 1 and 6 mm, in particular between 3 and 5 mm, is particularly preferred.
- the droplet diameter of the sprayed-on coating material or of the sprayed coating dispersion or solution is preferably between 1 and 100 ⁇ m, particularly preferably between 2 and 80 ⁇ m, very particularly preferably between 4 and 70 ⁇ m and in particular between 8 and 60 ⁇ m.
- the temperature of the sprayed coating material is preferably between 20 and 90 ° C, preferably between 25 and 60 ° C, more preferably between 30 and 55 ° C and in particular between 40 and 50 ° C.
- a surface load of the shaped body surface by spraying the sprayed liquid between 0.1 and 200 mg / (cm 2 s), preferably between 0.2 and 100 mg when spraying the molded body / (cm 2 s), more preferably between 0.4 and 50 mg / (m 2 s), and in particular between 0.8 and 20 mg / (cm 2 s).
- a surface load of the shaped body surface by spraying the sprayed liquid between 0.1 and 200 mg / (cm 2 s), preferably between 0.2 and 100 mg when spraying the molded body / (cm 2 s), more preferably between 0.4 and 50 mg / (m 2 s), and in particular between 0.8 and 20 mg / (cm 2 s).
- the coating composition to the molding is preferably completed in less than 10 minutes, preferably less than 5 minutes, more preferably less than 2 minutes, most preferably less than 1 minute, and most preferably less than 0.5 minutes.
- the sprayed washing or cleaning agent shaped body is preferably dried after spraying.
- the drying can be carried out, for example, thermally and / or by the action of a vacuum. In the case of thermal drying, methods using hot air or heat radiation are preferred. Drying temperatures are preferably between 35 and 90 ° C, preferably between 40 and 80 ° C and in particular between 50 and 70 ° C.
- the drying of the moldings is usually not complete, that is, not all of the amount of solvent applied by the spraying is removed by the drying.
- Polyvinyl alcohols of a certain molecular weight range are preferably used as the coating material, it being preferred according to the invention that the film material comprises a polyvinyl alcohol whose molecular weight is in the range from 10,000 to 100,000 gmol -1 , preferably from 11,000 to 90,000 gmol -1 , particularly preferably from 12,000 to 80,000 gmol -1 and in particular from 13,000 to 70,000 gmol -1 .
- Coating materials which comprise a polymer from the group starch and starch derivatives, cellulose and cellulose derivatives, in particular methyl cellulose and mixtures thereof, are preferred within the scope of the process according to the invention.
- the inventive method is suitable for simple as well as repeated coating of the shaped body.
- a method characterized in that the coating agent is applied to the molding by the moldings is sprayed several times with a solution or a dispersion of the coating composition, according to the invention are preferred.
- a "multiple" or “repeated” coating of the shaped body takes place in such a way that the shaped body is dried at least superficially between the individual coating steps.
- the coating steps are consequently interrupted by a drying step but at least by a waiting time, which preferably exceeds at least one minute, preferably at least two minutes and in particular at least three minutes. Drying steps which are carried out under more severe conditions, that is to say at elevated temperature and / or higher vacuum, can preferably be reduced to at least 10 seconds, particularly preferably at least 30 seconds, preferably at least 40 seconds and in particular to at least 50 seconds.
- the surface coverage of the moldings after this repeated coating is preferably between 0.2 and 100 mg / cm 2 , preferably between 1 and 80 mg / cm 2 , more preferably between 10 and 70 mg / cm 2 and in particular between 20 and 60 mg / cm 2 .
- LCST substances are substances that have better solubility at low temperatures than at higher temperatures. They are also referred to as substances with lower critical demixing temperature. These substances are usually polymers. Depending on the conditions of use, the lower critical demixing temperature should be between room temperature and the temperature of the heat treatment, for example between 20 ° C, preferably 30 ° C and 100 ° C, in particular between 30 ° C and 50 ° C.
- the LCST substances are preferably selected from alkylated and / or hydroxyalkylated polysaccharides, cellulose ethers, polyisopropylacrylamide, copolymers of polyisopropylacrylamide and blends of these substances.
- LCST substances are cellulose ethers and mixtures of cellulose ethers with carboxymethylcellulose (CMC).
- CMC carboxymethylcellulose
- Other polymers which exhibit a lower critical demixing temperature in water and which are also suitable are polymers of mono- or di-N-alkylated acrylamides, copolymers of mono- or di-N-substituted acrylamides with acrylates and / or acrylic acids or mixtures of interconnected networks of the above (co) polymers.
- polyethylene oxide or copolymers thereof such as ethylene oxide / propylene oxide copolymers and graft copolymers of alkylated acrylamides with polyethylene oxide, polymethacrylic acid, polyvinyl alcohol and copolymers thereof, polyvinyl methyl ether, certain proteins such as poly (VATGVV), a repeating unit in the natural protein elastin, and certain alginates.
- LCST low critical demixing temperature
- waxing is meant a number of natural or artificially derived substances which generally melt above 35 ° C without decomposition and are already slightly above the melting point, relatively low viscosity and non-stringy. They show a strong temperature-dependent consistency and solubility. According to their origin, the waxes are divided into three groups, the natural waxes, chemically modified waxes and the synthetic waxes.
- Synthetic waxes are generally understood as meaning polyalkylene waxes or polyalkylene glycol waxes. Also suitable as coating materials are compounds from other classes of substances which fulfill the stated requirements with regard to the softening point. Suitable synthetic compounds have, for example, higher esters of phthalic acid, in particular dicyclohexyl phthalate, which is commercially available under the name Unimoll ® 66 (Bayer AG), proved. Also suitable are synthetic waxes made of lower carboxylic acids and fatty alcohols, such as dimyristyl tartrate, sold under the name Cosmacol ® ETLP (Condea) is available. Conversely, synthetic or partially synthetic esters of lower alcohols can be used with fatty acids from natural sources. This class of substances includes, for example, Tegin® 90 (Goldschmidt), a glycerol monostearate palmitate. Shellac, for example shellac KPS three-ring SP (Kalkhoff GmbH) can be used as further substance.
- Wax alcohols are higher molecular weight, water-insoluble fatty alcohols having generally about 22 to 40 carbon atoms.
- the wax alcohols are present, for example, in the form of wax esters of higher molecular weight fatty acids (wax acids) as the main constituent of many natural waxes.
- wax alcohols are lignoceryl alcohol (1-tetracosanol), cetyl alcohol, myristyl alcohol or melissyl alcohol.
- Paraffin is the term for a solid or liquid mixture of purified, saturated aliphatic hydrocarbons (paraffins). This is readily soluble in ether and chloroform but not soluble in water. Both liquid paraffins and paraffin melts can be used in the context of the present invention.
- paraffin waxes have the advantage over the other natural waxes mentioned that the use of preferred washing or cleaning agent shaped bodies coated with paraffin waxes in an alkaline cleaning agent environment does not result in hydrolysis of the waxes (as for example in the case of wax esters), since paraffin wax contains no hydrolyzable groups.
- Paraffin waxes consist mainly of alkanes and low levels of iso- and cycloalkanes.
- the paraffin to be used according to the invention preferably has substantially no constituents with a melting point of more than 70 ° C., more preferably of more than 60 ° C.
- Preferred coating materials contain at least one paraffin wax with a melting range from 40 ° C to 60 ° C.
- Paraffin waxes applied in the form of their melts preferably solidify within 10 minutes, preferably within 5 minutes and especially within 2 minutes.
- hydrophobic substances as a coating material is preferred in the present invention, since these substances improve the storage behavior of the laundry detergent or cleaner moldings according to the invention at high humidities.
- the increased moisture resistance of the coated body makes it possible to dispense after application of a hydrophobic substance to a seal with a water-soluble or water-dispersible film.
- this is only a preferred embodiment of the method according to the invention.
- it may be preferable to apply a film to the hydrophobic-coated molded body.
- the film can be fused at least proportionately with the coating, loosely, that enclose the body, or contain an air cushion, so that the molded body is additionally protected from mechanical effects.
- the shaped bodies are coated twice, three times or four times, it being possible in each case for the coating processes to use the same or different coating materials.
- coating materials from the group of water-soluble polymers (for example PVA, PVP, gelatin or LCST polymers) and the water-insoluble waxes and the paraffins.
- the table below gives an overview of a number of particularly preferred sequences of these coating materials.
- the coating marked as the first layer corresponds to the layer first applied to the shaped body.
- the slash (I) takes on the meaning of a "and / or" -link.
- the coating materials can be mixed with active ingredients and active ingredients. Dyes, fragrances or bitter substances are preferably added to the coating materials.
- the spatial form of the detergent tablets is not subject to any restriction.
- Examples are room bodies with a polygonal base area, whereby the body represents a continuation of the polygonal floor space in the room.
- Preferred examples of the polygonal body are prismatic bodies.
- Examples of the prismatic body are trigonal prisms, rhombic prisms, orthorhombic prisms, tetragonal prisms, pentagonal prisms, hexagonal prisms, or octagonal prisms. Particularly preferred is a cuboid shape.
- Examples of other suitable polygonal bodies are trigonal, tetragonal, rhombic, orthorhombic, hexagonal or octagonal pyramids and dipyramids.
- the body may also be a hybrid of various geometric bodies. Preference is furthermore given to moldings with an oval or round base surface, wherein the body preferably again represents a continuation of the base surface in the room.
- the volume of the detergent tablets is preferably between 12 and 30 ml, preferably between 15 and 25 ml and in particular between 17 and 22 ml.
- the weight of the tablets is preferably between 10 and 25 g.
- Such detergent tablets are particularly suitable as dosing units for single use.
- the dosage of these moldings is usually done via the metering chambers of washing machines or dishwashers.
- the spatial form of the molding can therefore of course be adapted to any irregular shapes of dosing / Ein Hughesschitzn different washing machines and dishwashers.
- a cuboid shape of the washing or cleaning agent shaped body is preferred insofar as this makes it possible to fill in the usual cuboid insufflation chambers or dishwashers best in terms of volume.
- cuboid-shaped detergents or cleaning agents can be stored very well in a space-saving manner.
- the detergent tablets may have a cavity in the form of a through hole.
- the openings of this hole may be located in adjacent side surfaces and / or in opposite side surfaces of the shaped body. If the openings of the hole are located on mutually opposite sides of the shaped body, the corresponding shaped bodies are also referred to as ring shaped bodies or ring tablets.
- the tablets in the context of the present invention also multi-phase, in particular multi-layered, ausgestalten.
- the moldings can be made in a predetermined spatial form and predetermined size.
- the training as a blackboard the bar or bar shape, cubes, cuboids and corresponding space elements with flat side surfaces and in particular cylindrical configurations with circular or oval cross-section.
- This last embodiment covers the presentation form of the tablet up to compact cylinder pieces with a ratio of height to diameter above 1.
- ⁇ is the diametrical fracture stress (DFS) in Pa
- P is the force in N which results in the pressure applied to the molded article causing the breakage of the molded article
- D is the molded article diameter in meters and t the height of the moldings.
- the stability and hardness of the processed shaped bodies can be improved by the method according to the invention without impairing their decay and dissolution properties.
- the molded body after coating with constant dissolution behavior characterized by an increased breaking strength.
- preferred processes according to the invention are characterized in that the coating in step b) takes place on the outer surfaces of the molded body with the cavity, but not within the cavity.
- the coating of the molding is repeated in this process variant, preferably twice, three or four times.
- the substances or mixtures of substances filled in the cavity can be fixed in the cavity in different ways.
- the substances or substance mixtures are present in a water-soluble or water-dispersible packaging, for example a deep-drawn bag or an injection-molded container, which at least partially fills the cavity and in turn with the molding by adhesion or a mechanical connection, for example a detent, Snap, plug or clamp connection is connected.
- the cavity is preferably filled to at least 70% by volume, preferably at least 80% by volume, more preferably at least 90% by volume and in particular at least 95% by volume of its volume.
- a water-soluble or water-dispersible film is sealed onto the coated surface of the shaped body, the sealing being effected by heat sealing.
- the sealed foil can perform a number of different functions.
- such a film is suitable for fixing the substances or substance mixtures filled in the cavity of the shaped body in this cavity.
- the breaking strength and / or storage stability of the shaped body can be further increased by means of these films.
- Preferred film materials used are, in particular, the water-soluble polymers mentioned above from the group (optionally acetalized) polyvinyl alcohol (PVAL), polyvinylpyrrolidone, polyethylene oxide, gelatin, cellulose, and derivatives thereof and mixtures thereof.
- a further subject of the present application is a coated washing or cleaning agent shaped article, characterized in that the surface coverage of the coated molding surface with the coating agent is between 0.2 and 50 mg / cm 2 and the water-soluble or water-dispersible film is sealed onto the coated surface, characterized in that the shaped body comprises a coated surface and a water-soluble or water-dispersible film, wherein the coating and the water-soluble or water-dispersible film are at least partially fused together and the coating agent was sprayed onto the shaped body.
- preferred coated detergent tablets have a surface coverage of the coated shaped body surface with the coating agent between 0.4 and 40 mg / cm 2 , preferably between 0.8 and 30 mg / cm 2 and in particular between 1 and 20 mg / cm 2 ,
- the coating agent is preferably a water-soluble organic polymer, preferably a polymer from the group consisting of polyvinyl alcohol, polyvinylpyrrolidone and cellulose ethers.
- the fracture hardness of the coated detergent tablets is preferably above 60 N, preferably above 80 N, particularly preferably above 100 N and in particular above 110 N.
- the shaped bodies preferably have a cavity in the form of a depression or a through hole, wherein those shaped bodies which are coated on the outer surfaces but not within the cavity are particularly preferred.
- the cavity of the shaped bodies according to the invention is preferably filled.
- compositions according to the invention or the compositions prepared by the process according to the invention described above contain washing and cleaning substances, preferably washing and cleaning substances from the group of builders, surfactants, polymers, bleaches, bleach activators, enzymes, glass corrosion inhibitors, corrosion inhibitors, disintegration aids , Fragrances and perfume carriers.
- the agents are therefore usually water-soluble or water-dispersible.
- the detergents and cleaners can contain further ingredients which further improve the performance and / or aesthetic properties of these compositions.
- Preferred agents contain one or more of the group of electrolytes, pH adjusters, fluorescers, hydrotopes, foam inhibitors, silicone oils, anti redeposition agents, optical brighteners, grayness inhibitors, anti-shrinkage agents, anti-crease agents, color transfer inhibitors, antimicrobial agents, germicides, fungicides, antioxidants, antistatic agents, ironing aids , Phobic and impregnating agents, swelling and anti-slip agents and UV absorbers.
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- Moulds For Moulding Plastics Or The Like (AREA)
Abstract
Description
Die vorliegende Erfindung betrifft beschichtete Wasch- oder Reinigungsmittelformkörper sowie Verfahren zu deren Herstellung. Insbesondere betrifft die vorliegende Anmeldung Formkörper, die eine Kavität in Form einer Mulde oder eines durchgehenden Loches aufweisen und deren Oberflächenbedeckung der beschichteten Formkörperoberfläche mit dem Beschichtungsmittel zwischen 0,2 und 50 mg/cm2 beträgt.The present invention relates to coated detergent tablets and to processes for their production. In particular, the present application relates to shaped bodies which have a cavity in the form of a depression or a through hole and whose surface coverage of the coated molding surface with the coating agent is between 0.2 and 50 mg / cm 2 .
Wasch- oder Reinigungsmittel sind heute für den Verbraucher in vielfältigen Angebotsformen erhältlich. Neben Waschpulvern und -granulaten umfasst dieses Angebot beispielsweise auch Reinigungsmittelkonzentrate in Form extrudierter oder tablettierter Zusammensetzungen. Diese festen, konzentrierten bzw. verdichteten Angebotsformen zeichnen sich durch ein verringertes Volumen pro Dosiereinheit aus und senken damit die Kosten für Verpackung und Transport. Insbesondere die Wasch- oder Reinigungsmitteltabletten erfüllen dabei zusätzlich den Wunsch des Verbrauchers nach einfacher Dosierung. Die entsprechenden Mittel sind im Stand der Technik umfassend beschrieben.Detergents or cleaners are now available to the consumer in a variety of forms. In addition to washing powders and granules, this offer also includes, for example, detergent concentrates in the form of extruded or tabletted compositions. These fixed, concentrated or compressed forms of supply are characterized by a reduced volume per dosing unit and thus reduce the costs for packaging and transport. In particular, the washing or cleaning agent tablets additionally meet the consumer's desire for simple dosing. The corresponding means are comprehensively described in the prior art.
Tablettierte Wasch- oder Reinigungsmittel sind aufgrund der hohen Verdichtung ihrer Bestandteile jedoch schwerer löslich als herkömmliche pulverförmige oder flüssige Wasch- oder Reinigungsmittel.
Hieraus können sich Probleme ergeben. Die verzögerte Desintegration / Lösung der Bestandteile kann eine verminderte Reinigungsleistung, ein unvollständiges Einspülen der Mittel durch die Einspülkammer, sowie die Bildung von Flecken und Verkrustungen zur Folge haben.However, tableted detergents or cleaners are more difficult to dissolve than conventional powdered or liquid detergents or cleaners due to the high densification of their constituents.
This can cause problems. Delayed disintegration / dissolution of the ingredients can result in reduced cleaning performance, incomplete flushing of the media through the dispenser compartment, and the formation of stains and encrustations.
Es können zwar hinreichend bruchstabile, d.h. harte Wasch- und Reinigungsmittelformkörper hergestellt werden, oft sind diese aber den Belastungen bei Verpackung, Transport und Handhabung, d.h. Fall- und Reibebeanspruchungen, nicht ausreichend gewachsen, so dass Kantenbruch- und Abrieberscheinungen das Erscheinungsbild des Formkörpers beeinträchtigen oder gar zu einer völligen Zerstörung der Formkörperstruktur führen.Although it can be sufficiently fracture-resistant, i. hard detergent tablets are often produced, but these are often the stresses in packaging, transport and handling, i. Falling and rubbing stresses, not sufficiently grown, so that Kantenbruch- and Abrieberscheinungen affect the appearance of the molding or even lead to a complete destruction of the molding structure.
Trotz der zahlreichen Veröffentlichungen auf dem Gebiet der Wasch- oder Reinigungsmittel besteht weiterhin ein Bedürfnis nach Verbesserung der Reinigungsleistung dieser Mittel, insbesondere unter Beibehaltung oder Verringerung der pro Wasch- oder Reinigungsgang eingesetzten Mengen an wasch- oder reinigungsaktiven Substanzen.
Im Zuge der Diskussion zum Umweltschutz und zur Einsparung von Ressourcen besteht zudem ein Bedürfnis die Menge der zur Verpackung und Konfektionierung dieser Mittel eingesetzten nicht wasch- oder reinigungsaktiven Materialien (z.B. wasserlösliche oder nicht-wasserlösliche Polymerfilme der Umverpackung) zu reduzieren.Despite the numerous publications in the field of detergents or cleaning agents, there remains a need for improving the cleaning performance of these agents, in particular while maintaining or reducing the amounts of washing or cleaning substances used per washing or cleaning cycle.
In the course of the discussion on environmental protection and the saving of resources, there is also a need to reduce the amount of non-washing or cleaning-active materials used for packaging and packaging these agents (eg water-soluble or non-water-soluble polymer films of the outer packaging).
Zur Überwindung der Dichotomie zwischen Härte, d.h. Transport- und Handhabungsstabilität, und leichtem Zerfall der Formkörper sind im Stand der Technik viele Lösungsansätze entwickelt worden. Ein insbesondere aus der Pharmazie bekannter und auf das Gebiet der Wasch- und Reinigungsmittelformkörper ausgedehnter Ansatz ist die Inkorporation bestimmter Desintegrationshilfsmittel, die den Zutritt von Wasser erleichtern oder bei Zutritt von Wasser quellen bzw. gasentwickelnd oder in anderer Form desintegrierend wirken. Andere Lösungsvorschläge aus der Patentliteratur beschreiben die Verpressung von Vorgemischen bestimmter Teilchengrößen, die Trennung einzelner Inhaltsstoffe von bestimmten anderen Inhaltsstoffen sowie die Beschichtung einzelner Inhaltsstoffe oder des gesamten Formkörpers mit Bindemitteln.To overcome the dichotomy between hardness, i. Transport and handling stability, and easy disintegration of the moldings, many approaches have been developed in the prior art. An approach known in particular from the pharmaceutical industry and extended to the field of detergent tablets is the incorporation of certain disintegration aids which facilitate the ingress of water or which swell or become gas-evolved or otherwise disintegrate upon the ingress of water. Other proposed solutions from the patent literature describe the compression of premixes of certain particle sizes, the separation of individual ingredients of certain other ingredients and the coating of individual ingredients or the entire molded article with binders.
Die Beschichtung von Wasch- und Reinigungsmittelformkörpern ist Gegenstand einiger Patentanmeldungen.The coating of detergent tablets is the subject of some patent applications.
So beschreiben die europäischen Patentanmeldungen
Beschichtete Waschmitteltabletten sind auch Gegenstand der europäischen Patentanmeldung
Wasch- oder reinigungsaktive Zubereitungen in Form beschichteter Muldentabletten werden in den Druckschriften
Die im Stand der Technik offenbarten Lösungsvorschläge nutzen dabei Beschichtungsmaterialien, welche im späteren Wasch- oder Reinigungsvorgang teilweise nur zögerlich lösbar sind und zum Teil durch den Zusatz von Desintegrationshilfsmitteln überhaupt erst desintegrierbar gemacht werden müssen. Auf diese Weise steht entweder am Anfang des Reinigungsganges keine oder nicht genügen Aktivsubstanz in der Flotte zur Verfügung, oder eine Dosierbarkeit über Einspülkammern von Haushaltswaschmaschinen ist nicht ohne zusätzliche Kosten gegeben.The proposed solutions disclosed in the prior art use coating materials which are only partially releasable in the later washing or cleaning process and in some cases have to be made disintegratable by the addition of disintegration auxiliaries. In this way, either no or insufficient active substance is available in the liquor at the beginning of the cleaning cycle, or a metering via Einspülkammern of household washing machines is not given without additional costs.
Die internationale Anmeldung
Aufgabe der vorliegenden Anmeldung war daher die Bereitstellung von Wasch- oder Reinigungsmittelformkörpern, welcher sich gegenüber den bekannten Formkörpern des Standes der Technik bei gleicher oder vergleichbarer Bruchhärte durch eine deutlich verbesserte Löslichkeit auszeichnen. Die Formkörper sollten insbesondere eine verbesserte Kaltwasserlöslichkeit aufweisen. Vorzugsweise sollten die resultierenden beschichteten Formkörper ohne weitere Verpackungsmittel, insbesondere ohne weitere Umverpackungen aus wasserunlöslichen Polymerfolien lager- und transportfähig sein.The object of the present application was therefore to provide laundry detergent or cleaning product tablets, which are distinguished by a significantly improved solubility with respect to the known shaped articles of the prior art with the same or comparable breakage hardness. The moldings should in particular have improved cold water solubility. Preferably, the resulting coated moldings should be storable and transportable without further packaging, in particular without further outer packaging of water-insoluble polymer films.
Gelöst wurde diese Aufgabe durch ein Beschichtungsverfahren für Wasch- oder Reinigungsmittelformkörper, bei welchem die Formkörperoberfläche mit einer Oberflächenbedeckung zwischen 0,2 und 50 mg/cm2 beschichtet wird.This object has been achieved by a coating method for detergent tablets, in which the tablet surface is coated with a surface coverage of between 0.2 and 50 mg / cm 2 .
Verfahren zur Herstellung eines Wasch- oder Reinigungsmittelformkörpers, umfassend die Schritte
- a) Bereitstellen eines Formkörpers, der eine Kavität in Form einer Mulde oder eines durchgehenden Loches aufweist;
- b) Aufbringen eines Beschichtungsmittels auf die Oberfläche des Formkörpers, so dass die Oberflächenbedeckung der beschichteten Formkörperoberfläche mit dem Beschichtungsmittel zwischen 0,2 und 50 mg/cm2 beträgt;
- c) Aufsiegeln einer wasserlöslichen oder wasserdispergierbaren Folie auf die beschichtete Oberfläche des Formkörpers durch Heißsiegelung,
- a) providing a shaped body having a cavity in the form of a trough or a through hole;
- b) applying a coating agent to the surface of the molding so that the surface coverage of the coated molding surface with the coating agent is between 0.2 and 50 mg / cm 2 ;
- c) sealing a water-soluble or water-dispersible film on the coated surface of the molded article by heat sealing,
Erfindungsgemäß bevorzugte Verfahren zeichnen sich dadurch aus, dass die Oberflächenbedeckung des Formkörpers zwischen 0,4 und 40 mg/cm2, vorzugsweise zwischen 0,8 und 30 mg/cm2 und insbesondere zwischen 1 und 20 mg/cm2 beträgt. Der Gewichtsanteil der Beschichtung am Gesamtgewicht des beschichteten Formkörpers beträgt vorzugsweise weniger als 2 Gew.-%, bevorzugt weniger als 1 Gew.-%, besonders bevorzugt weniger als 0,7 Gew.-% und insbesondere weniger als 0,4 Gew.-%.Preferred processes according to the invention are characterized in that the surface coverage of the shaped body is between 0.4 and 40 mg / cm 2 , preferably between 0.8 and 30 mg / cm 2 and in particular between 1 and 20 mg / cm 2 . The proportion by weight of the coating in the total weight of the coated shaped body is preferably less than 2% by weight, preferably less than 1% by weight, more preferably less than 0.7% by weight and in particular less than 0.4% by weight. ,
In dem erfindungsgemäßen Verfahren können die Beschichtungsmittel als Reinsubstanzen, beispiels-weise in Form ihrer Schmelzen, aber auch als Dispersionen oder Lösungen eingesetzt werden. Als Dispersionsmittel sind dabei neben Wasser auch organische Lösungsmittel geeignet, wobei wässrige Dispersionen oder wässrige Lösungen besonders bevorzugt werden. Diese Dispersionen oder Lösungen, insbesondere die wässrigen Dispersionen oder Lösungen weisen dabei vorzugsweise einem Gewichtsanteil des Beschichtungsmittel unterhalb 80 Gew.%, bevorzugt unterhalb 65 Gew.-%, besonders bevorzugt unterhalb 50 Gew.-% und insbesondere unterhalb 40 Gew.-%, jeweils bezogen auf das Gesamtgewicht der Dispersion oder der Lösung, auf.In the process according to the invention, the coating compositions can be used as pure substances, for example in the form of their melts, but also as dispersions or solutions. In addition to water, organic solvents are also suitable as dispersants, with aqueous dispersions or aqueous solutions being particularly preferred. These dispersions or solutions, in particular the aqueous dispersions or solutions, preferably have a weight fraction of the coating agent below 80% by weight, preferably below 65% by weight, more preferably below 50% by weight and in particular below 40% by weight, in each case based on the total weight of the dispersion or solution.
Die Beaufschlagung des Formkörpers mit dem Beschichtungsmittel erfolgt durch Besprühen. Zum Besprühen der Formkörper eignen sich alle dem Fachmann zu diesem Zweck bekannten Vorrichtungen. Das Besprühen erfolgt vorzugsweise mittels Einstoff- bzw. Hochdrucksprühdüsen, Zweistoffsprühdüsen oder Dreistoffsprühdüsen. Zum Versprühen mit Einstoffsprühdüsen ist die Anwendung eines hohen Massedruckes (5-15 MPa) erforderlich, während das Versprühen in Zweistoffsprühdüsen mit Hilfe eines Pressluftstromes (bei 0,15-0,3 MPa) erfolgt. Die Versprühung mit Zweistoffsprühdüsen ist besonders im Hinblick auf eventuelle Verstopfungen der Düse günstiger, aber durch den hohen Pressluftverbrauch aufwendiger. Einsetzbar sind weiterhin auch Dreistoffsprühdüsen, welche neben dem Pressluftstrom zur Zerstäubung ein weiteres Luftführungssystem, das Verstopfungen und Tropfenbildung an der Düse verhindern soll. Im Rahmen des erfindungsgemäßen Verfahrens wird der Einsatz von Zweistoffsprühdüsen, vorzugsweise Zweistoffsprühdüsen mit einer Flüssigkeitsbohrung zwischen 1 und 6 mm, insbesondere zwischen 3 und 5 mm besonders bevorzugt.The application of the molding with the coating agent is carried out by spraying. For spraying the moldings, all known to those skilled in the art for this purpose are suitable. The spraying is preferably carried out by means of single-fluid or high-pressure spray nozzles, two-component spray nozzles or three-component spray nozzles. For spraying with single-fluid spray nozzles, the application of a high melt pressure (5-15 MPa) is required, while spraying in dual-fluid spray nozzles takes place by means of a stream of compressed air (at 0.15-0.3 MPa). The spraying with two-component spray nozzles is more favorable, especially with regard to possible blockages of the nozzle, but more expensive due to the high consumption of compressed air. It is also possible to use three-component spray nozzles which, in addition to the stream of compressed air for atomization, are intended to prevent a further air-guiding system which prevents blockages and droplet formation at the nozzle. In the context of the method according to the invention, the use of two-component spray nozzles, preferably two-component spray nozzles with a fluid bore of between 1 and 6 mm, in particular between 3 and 5 mm, is particularly preferred.
Die Düsen im Prozessraum können von oben nach unten oder von unten nach oben sprühen. Besonders bevorzugt werden Verfahren, bei denen die Sprühvorrichtung in die die Prozesskammer begrenzenden Seitenwände integriert und dort fixiert ist. Besonders bevorzugt sind solche Verfahren, bei denen in der Prozesskammer zwei oder mehr Sprühvorrichtungen eingesetzt werden, wobei sich mindestens zwei der Sprühvorrichtungen hinsichtlich ihrer Orientierung, das heißt hinsichtlich ihrer Sprührichtung unterscheiden.The nozzles in the process room can spray from top to bottom or from bottom to top. Particularly preferred are methods in which the spray device is integrated into the process chamber limiting side walls and fixed there. Particularly preferred are those methods in which two or more spraying devices are used in the process chamber, wherein at least two of the spraying devices differ with regard to their orientation, that is, with regard to their spraying direction.
In einer bevorzugten Ausführungsform des erfindungsgemäßen Verfahrens werden der Formkörper und die Sprühvorrichtung während des Sprühvorgangs relativ zueinander bewegt. Diese Bewegung kann sowohl durch eine Bewegung des Formkörpers als auch durch eine Bewegung der Sprühvorrichtung oder durch die Bewegung von Formkörper und Sprühvorrichtung realisiert werden. Besonders bevorzugt sind solche Verfahren, bei denen die Sprühvorrichtung in wenigstens eine Raumrichtung, vorzugsweise in zwei oder drei Raumrichtungen bewegt wird. Werden gleichzeitig auch die Formkörper bewegt, so kann die Bewegungsrichtung der Sprühvorrichtung der Bewegungsrichtung der Formkörper beispielsweise entgegenlaufen oder mit dieser übereinstimmen. Auch eine Bewegung der Sprühvorrichtung orthogonal zur Bewegungsrichtung der Formkörper kann ausgeführt werden. Die Formkörper können kontinuierlich und diskontinuierlich in und durch den Prozessraum der Sprühvorrichtung bewegt werden.In a preferred embodiment of the method according to the invention, the shaped body and the spraying device are moved relative to one another during the spraying process. This movement can be realized both by a movement of the shaped body and by a movement of the spraying device or by the movement of the shaped body and spraying device. Particularly preferred are those methods in which the spraying device is moved in at least one spatial direction, preferably in two or three spatial directions. If, at the same time, the shaped bodies are also moved, the direction of movement of the spraying device can, for example, run counter to or coincide with the direction of movement of the shaped bodies. Also, a movement of the spraying device orthogonal to the direction of movement of the moldings can be carried out. The moldings can be moved continuously and discontinuously into and through the process space of the spray device.
Der Tropfendurchmesser des aufgesprühten Beschichtungsmaterials, bzw. der aufgesprühten Beschichtungsdispersion oder -lösung beträgt vorzugsweise zwischen 1 und 100 µm, besonders bevorzugt zwischen 2 und 80 µm, ganz besonders bevorzugt zwischen 4 und 70 µm und insbesondere zwischen 8 und 60 µm. Die Temperatur des aufgesprühten Beschichtungsmaterials beträgt vorzugsweise zwischen 20 und 90°C, bevorzugt zwischen 25 und 60°C, besonders bevorzugt zwischen 30 und 55°C und insbesondere zwischen 40 und 50°C.The droplet diameter of the sprayed-on coating material or of the sprayed coating dispersion or solution is preferably between 1 and 100 μm, particularly preferably between 2 and 80 μm, very particularly preferably between 4 and 70 μm and in particular between 8 and 60 μm. The temperature of the sprayed coating material is preferably between 20 and 90 ° C, preferably between 25 and 60 ° C, more preferably between 30 and 55 ° C and in particular between 40 and 50 ° C.
Die Vorteile des erfindungsgemäßen Verfahrens lassen sich insbesondere durch solche bevorzugten Verfahrensvarianten realisieren, bei denen beim Besprühen der Formkörper eine Flächenbelastung der Formkörperoberfläche durch die versprühte Flüssigkeit zwischen 0,1 und 200 mg/(cm2s), vorzugsweise zwischen 0,2 und 100 mg/(cm2s), besonders bevorzugt zwischen 0,4 und 50 mg/(m2s) und insbesondere zwischen 0,8 und 20 mg/(cm2s) beträgt. Der Auftrag des Beschichtungsmittels auf den Formkörper ist vorzugsweise in weniger als 10 Minuten, bevorzugt in weniger als 5 Minuten, besonders bevorzugt in weniger als 2 Minuten, ganz besonders bevorzugt in weniger als 1 Minute und insbesondere in weniger als 0,5 Minuten abgeschlossen.The advantages of the process according to the invention can be realized in particular by those preferred process variants in which a surface load of the shaped body surface by spraying the sprayed liquid between 0.1 and 200 mg / (cm 2 s), preferably between 0.2 and 100 mg when spraying the molded body / (cm 2 s), more preferably between 0.4 and 50 mg / (m 2 s), and in particular between 0.8 and 20 mg / (cm 2 s). Of the Application of the coating composition to the molding is preferably completed in less than 10 minutes, preferably less than 5 minutes, more preferably less than 2 minutes, most preferably less than 1 minute, and most preferably less than 0.5 minutes.
Während des Sprühvorgangs liegen die Wasch- oder Reinigungsmittelformkörper vorzugsweise vereinzelt vor, das heißt ohne unmittelbaren Kontakt zueinander vor. Das erfindungsgemäße Verfahren unterscheidet sich damit von solchen Beschichtungsverfahren, bei denen geordnete oder ungeordnete Stapel oder Haufen von Formkörpern, beispielsweise in Trommelcoatern oder Dragierkesseln beschichtet werden.During the spraying process, the detergent tablets are preferably present in isolated form, that is to say without direct contact with one another. The process according to the invention thus differs from those coating processes in which ordered or unordered stacks or piles of shaped articles, for example in drum coaters or coating pans, are coated.
Der besprühte Wasch- oder Reinigungsmittelformkörper wird nach dem Besprühen vorzugsweise getrocknet. Die Trocknung kann beispielsweise thermisch und/oder durch Einwirkung eines Vakuums erfolgen. Bei der thermischen Trocknung sind Verfahren unter Einsatz von Heißluft oder Wärmestrahlung bevorzugt. Trocknungstemperaturen betragen vorzugsweise zwischen 35 und 90°C, vorzugsweise zwischen 40 und 80°C und insbesondere zwischen 50 und 70°C. Die Trocknung der Formkörper erfolgt in der Regel nicht vollständig, das heißt, nicht die gesamte durch das Besprühen aufgebrachte Lösungsmittelmenge wird durch die Trocknung entfernt.The sprayed washing or cleaning agent shaped body is preferably dried after spraying. The drying can be carried out, for example, thermally and / or by the action of a vacuum. In the case of thermal drying, methods using hot air or heat radiation are preferred. Drying temperatures are preferably between 35 and 90 ° C, preferably between 40 and 80 ° C and in particular between 50 and 70 ° C. The drying of the moldings is usually not complete, that is, not all of the amount of solvent applied by the spraying is removed by the drying.
Besonders bevorzugt sind Verfahren in denen weniger als 50% der aufgebrachten Lösungsmittelmenge im Trocknungsschritt verdampft werden. Dieser verdampfte Anteil kann durch Verwiegung des unbeschichteten Formkörpers, des nassen Formkörpers vor Trocknung und des getrockneten Formkörpers, d.h. aus der vor und nach Trocknung gemessenen Gewichtszunahme des Formkörpers ermittelt werden.Particularly preferred are processes in which less than 50% of the applied amount of solvent is evaporated in the drying step. This evaporated portion can be obtained by weighing the uncoated body, the wet body before drying, and the dried body, i. be determined from the measured before and after drying weight increase of the molding.
Besonders bevorzugt sind erfindungsgemäße Verfahren, bei denen im Anschluss an das Besprühen der Formkörper auf einen Trocknungsschritt verzichtet wird.Particular preference is given to processes according to the invention in which a drying step is dispensed with after spraying the shaped bodies.
Als Beschichtungsmittel werden vorzugsweise wasserlösliche organische Polymere eingesetzt. In einer bevorzugten Verfahrensvariante umfasst das Beschichtungsmaterial ein oder mehrere wasserlösliche(s) Polymer(e), vorzugsweise ein Material aus der Gruppe (gegebenenfalls acetalisierter) Polyvinylalkohol (PVAL), Polyvinylpyrrolidon, Polyethylenoxid, Gelatine, Cellulose, und deren Derivate und deren Mischungen.The coating agents used are preferably water-soluble organic polymers. In a preferred process variant, the coating material comprises one or more water-soluble polymer (s), preferably a material from the group (optionally acetalized) polyvinyl alcohol (PVAL), polyvinylpyrrolidone, polyethylene oxide, gelatin, cellulose, and derivatives thereof and mixtures thereof.
Vorzugsweise werden als Beschichtungsmaterial Polyvinylalkohole eines bestimmten Molekulargewichtsbereichs eingesetzt, wobei erfindungsgemäß bevorzugt ist, dass das Folienmaterial einen Polyvinylalkohol umfasst, dessen Molekulargewicht im Bereich von 10.000 bis 100.000 gmol-1, vorzugsweise von 11.000 bis 90.000 gmol-1, besonders bevorzugt von 12.000 bis 80.000 gmol-1 und insbesondere von 13.000 bis 70.000 gmol-1 liegt.Polyvinyl alcohols of a certain molecular weight range are preferably used as the coating material, it being preferred according to the invention that the film material comprises a polyvinyl alcohol whose molecular weight is in the range from 10,000 to 100,000 gmol -1 , preferably from 11,000 to 90,000 gmol -1 , particularly preferably from 12,000 to 80,000 gmol -1 and in particular from 13,000 to 70,000 gmol -1 .
Der Polymerisationsgrad solcher bevorzugten Polyvinylalkohole liegt zwischen ungefähr 200 bis ungefähr 2100, vorzugsweise zwischen ungefähr 220 bis ungefähr 1890, besonders bevorzugt zwischen ungefähr 240 bis ungefähr 1680 und insbesondere zwischen ungefähr 260 bis ungefähr 1500.The degree of polymerization of such preferred polyvinyl alcohols is between about 200 to about 2100, preferably between about 220 to about 1890, more preferably between about 240 to about 1680, and most preferably between about 260 to about 1500.
Bevorzugt sind im Rahmen des erfindungsgemäßen Verfahrens Beschichtungsmaterialien, welche ein Polymer aus der Gruppe Stärke und Stärkederivate, Cellulose und Cellulosederivate, insbesondere Methylcellulose und Mischungen hieraus umfassen.Coating materials which comprise a polymer from the group starch and starch derivatives, cellulose and cellulose derivatives, in particular methyl cellulose and mixtures thereof, are preferred within the scope of the process according to the invention.
Besonders bevorzugt werden solche erfindungsgemäßen Verfahren, bei denen als Beschichtungsmittel ein wasserlösliches organisches Polymer, vorzugsweise ein Polymer aus der Gruppe Polyvinylalkohol, Polyvinylpyrrolidon und Celluloseether eingesetzt wird. Selbstverständlich auch Mischungen verschiedener Substanzen in Form ihrer Schmelzen, Lösungen oder Dispersionen als Beschichtungsmaterialien eingesetzt werden.Particular preference is given to processes according to the invention in which the coating agent used is a water-soluble organic polymer, preferably a polymer from the group consisting of polyvinyl alcohol, polyvinylpyrrolidone and cellulose ether. Of course, mixtures of various substances in the form of their melts, solutions or dispersions are used as coating materials.
Das erfindungsgemäße Verfahren eignet sich zur einfachen wie zur wiederholten Beschichtung der Formkörper. Verfahren, dadurch gekennzeichnet, dass das Beschichtungsmittel auf den Formkörper aufgebracht wird, indem der Formkörper mehrfach mit einer Lösung oder einer Dispersion des Beschichtungsmittels besprüht wird, sind erfindungsgemäß bevorzugt. Eine "mehrfache" oder "wiederholte" Beschichtung des Formkörpers erfolgt dabei derart, dass der Formkörper zwischen den einzelnen Beschichtungsschritten wenigstens oberflächlich getrocknet wird. Die Beschichtungsschritte werden folglich durch einen Trocknungsschritt mindestens jedoch durch eine Wartezeit, welche vorzugsweise mindestens eine Minute, bevorzugt mindestens zwei Minuten und insbesondere mindestens drei Minuten übersteigt, unterbrochen. Trocknungsschritte, die bei drastischeren Bedingungen durchgeführt werden, das heißt bei erhöhter Temperatur und/oder stärkerem Vakuum, können bevorzugt auf mindestens 10 Sekunden, besonders bevorzugt mindestens 30 Sekunden, vorzugsweise mindestens 40 Sekunden und insbesondere auf mindestens 50 Sekunden verringert werden.The inventive method is suitable for simple as well as repeated coating of the shaped body. A method, characterized in that the coating agent is applied to the molding by the moldings is sprayed several times with a solution or a dispersion of the coating composition, according to the invention are preferred. A "multiple" or "repeated" coating of the shaped body takes place in such a way that the shaped body is dried at least superficially between the individual coating steps. The coating steps are consequently interrupted by a drying step but at least by a waiting time, which preferably exceeds at least one minute, preferably at least two minutes and in particular at least three minutes. Drying steps which are carried out under more severe conditions, that is to say at elevated temperature and / or higher vacuum, can preferably be reduced to at least 10 seconds, particularly preferably at least 30 seconds, preferably at least 40 seconds and in particular to at least 50 seconds.
Die Oberflächenbedeckung der Formkörper nach dieser wiederholten Beschichtung beträgt vorzugsweise zwischen 0,2 und 100 mg/cm2, vorzugsweise zwischen 1 und 80 mg/cm2, besonders bevorzugt zwischen 10 und 70 mg/cm2 und insbesondere zwischen 20 und 60 mg/cm2.The surface coverage of the moldings after this repeated coating is preferably between 0.2 and 100 mg / cm 2 , preferably between 1 and 80 mg / cm 2 , more preferably between 10 and 70 mg / cm 2 and in particular between 20 and 60 mg / cm 2 .
Ein weiterer Gegenstand der vorliegenden Anmeldung ist daher ein Verfahren zur Herstellung eines Wasch- oder Reinigungsmittelformkörpers, umfassend die Schritte
- a) Bereitstellen eines Formkörpers, der eine Kavität in Form einer Mulde oder eines durchgehenden Loches aufweist;
- b) Wiederholtes Aufbringen eines Beschichtungsmittels auf die Oberfläche des Formkörpers, so dass die Oberflächenbedeckung der beschichteten Formkörperoberfläche mit dem Beschichtungsmittel bei jedem Beschichtungsvorgang zwischen 0,2 und 50 mg/cm2 beträgt;
- c) Aufsiegeln einer wasserlöslichen oder wasserdispergierbaren Folie auf die beschichtete Oberfläche des Formkörpers durch Heißsiegelung.
- a) providing a shaped body having a cavity in the form of a trough or a through hole;
- b) Repeated application of a coating agent to the surface of the molded article such that the surface coverage of the coated molded article surface with the coating agent at each coating operation is between 0.2 and 50 mg / cm 2 ;
- c) sealing a water-soluble or water-dispersible film on the coated surface of the molding by heat sealing.
Bevorzugt werden insbesondere solche erfindungsgemäßen Verfahren, bei denen der Formkörper zweifach, dreifach oder vierfach beschichtet wird. Wird die Beschichtung mehrfach wiederholt, so können sich je nach Anwendungsgebiet der Wasch- oder Reinigungsmittelformkörper in den einzelnen Beschichtungsgängen auch unterschiedliche Beschichtungsmittel eingesetzt werden. Derartige Verfahren, bei denen unterschiedliche Beschichtungsmaterialien eingesetzt werden, sind erfindungsgemäß besonders bevorzugt.
Weitere Beschichtungsmaterialien, die sich in Kombination mit den besonders bevorzugten wasserlöslichen Polymeren, beispielsweise in Form einer geschmolzenen, gelösten oder dispergierten Mischung, oder als zweites oder drittes Beschichtungsmaterial bei einer wiederholten Beschichtung der Formkörper eignen sind
- a) die LCST Subtanzen
- b) die Wachse
- c) die Paraffine
Other coating materials which are suitable in combination with the particularly preferred water-soluble polymers, for example in the form of a molten, dissolved or dispersed mixture, or as a second or third coating material in a repeated coating of the moldings
- a) the LCST subtances
- b) the waxes
- c) the paraffins
Bei LCST-Substanzen handelt sich um Substanzen, die bei niedrigen Temperaturen eine bessere Löslichkeit aufweisen als bei höheren Temperaturen. Sie werden auch als Substanzen mit unterer kritischer Entmischungstemperatur bezeichnet. Diese Substanzen sind in der Regel Polymere. Je nach Anwendungsbedingungen sollte die untere kritische Entmischungstemperatur zwischen Raumtemperatur und der Temperatur der Wärmebehandlung, zum Beispiel zwischen 20°C, vorzugsweise 30°C und 100°C liegen, insbesondere zwischen 30°C und 50°C. Die LCST-Substanzen sind vorzugsweise ausgewählt aus alkylierten und/oder hydroxyalkylierten Polysacchariden, Celluloseethern, Polyisopropylacrylamid, Copolymeren des Polyisopropylacrylamids sowie Blends dieser Substanzen.LCST substances are substances that have better solubility at low temperatures than at higher temperatures. They are also referred to as substances with lower critical demixing temperature. These substances are usually polymers. Depending on the conditions of use, the lower critical demixing temperature should be between room temperature and the temperature of the heat treatment, for example between 20 ° C, preferably 30 ° C and 100 ° C, in particular between 30 ° C and 50 ° C. The LCST substances are preferably selected from alkylated and / or hydroxyalkylated polysaccharides, cellulose ethers, polyisopropylacrylamide, copolymers of polyisopropylacrylamide and blends of these substances.
Beispiele für alkylierte und/oder hydroxyalkylierte Polysaccharide sind Methylhydroxypropylmethyl-cellulose (MHPC), Ethyl(hydroxyethyl)cellulose (EHEC), Hydroxypropylcellulose (HPC), Methylcellulose (MC), Ethylcellulose (EC), Carboxymethylcellulose (CMC), Carboxymethylmethylcellulose (CMMC), Hydroxybutylcellulose (HBC), Hydroxybutylmethylcellulose (HBMC), Hydrdoxyethylcellulose (HEC), Hydroxyethylcarboxymethylcellulose (HECMC), Hydroxyethylethylcellulose (HEEC), Hydroxypropylcellulose (HPC), Hydroxypropylcarboxymethylcellulose (HPCMC), Hydroxyethylmethylcellulose (HEMC), Methylhydroxyethylcellulose (MHEC), Methylhydroxyethylpropylcellulose (MHEPC), Methylcellulose (MC) und Propylcellulose (PC) und deren Gemische, wobei Carboxymethylcellulose, Methylcellulose, Methylhydroxyethylcellulose und Methylhydroxyproplcellulose sowie die Alkalisalze der CMC und die leicht ethoxylierte MC oder Gemische der voranstehenden bevorzugt sind.Examples of alkylated and / or hydroxyalkylated polysaccharides are methylhydroxypropylmethylcellulose (MHPC), ethyl (hydroxyethyl) cellulose (EHEC), hydroxypropylcellulose (HPC), methylcellulose (MC), ethylcellulose (EC), carboxymethylcellulose (CMC), carboxymethylmethylcellulose (CMMC), Hydroxybutyl cellulose (HBC), hydroxybutylmethylcellulose (HBMC), hydrdoxyethylcellulose (HEC), hydroxyethylcarboxymethylcellulose (HECMC), hydroxyethylethylcellulose (HEEC), hydroxypropylcellulose (HPC), hydroxypropylcarboxymethylcellulose (HPCMC), hydroxyethylmethylcellulose (HEMC), methylhydroxyethylcellulose (MHEC), methylhydroxyethylpropylcellulose (MHEPC), Methylcellulose (MC) and propylcellulose (PC) and mixtures thereof, with carboxymethylcellulose, methylcellulose, methylhydroxyethylcellulose and methylhydroxypropellulose, as well as the alkali metal salts of CMC and the slightly ethoxylated MC or mixtures of the foregoing, being preferred.
Weitere Beispiele für LCST-Substanzen sind Cellulosether sowie Gemische von Celluloseethern mit Carboxymethylcellulose (CMC). Weitere Polymere, die eine untere kritische Entmischungstemperatur in Wasser zeigen und die ebenfalls geeignet sind, sind Polymere von Mono- oder Di-N-alkylierten Acrylamiden, Copolymere von Mono- oder Di-N-substituierten Acrylamiden mit Acrylaten und/oder Acrylsäuren oder Gemische von miteinander verschlungenen Netzwerken der oben genannten (Co)Polymere. Geeignet sind außerdem Polyethylenoxid oder Copolymere davon, wie Ethylenoxid/Propylenoxidcopolymere und Pfropfcopolymere von alkylierten Acrylamiden mit Polyethylenoxid, Polymethacrylsäure, Polyvinylalkohol und Copolymere davon, Polyvinylmethylether, bestimmte Proteine wie Poly(VATGVV), eine sich wiederholende Einheit in dem natürlichen Protein Elastin und bestimmte Alginate. Gemische aus diesen Polymeren mit Salzen oder Tensiden können ebenfalls als LCST-Substanz verwendet werden. Durch derartige Zusätze oder durch den Vernetzungsgrad der Polymere kann die LCST (untere kritische Entmischungstemperatur) entsprechend modifiziert werden.Further examples of LCST substances are cellulose ethers and mixtures of cellulose ethers with carboxymethylcellulose (CMC). Other polymers which exhibit a lower critical demixing temperature in water and which are also suitable are polymers of mono- or di-N-alkylated acrylamides, copolymers of mono- or di-N-substituted acrylamides with acrylates and / or acrylic acids or mixtures of interconnected networks of the above (co) polymers. Also suitable are polyethylene oxide or copolymers thereof, such as ethylene oxide / propylene oxide copolymers and graft copolymers of alkylated acrylamides with polyethylene oxide, polymethacrylic acid, polyvinyl alcohol and copolymers thereof, polyvinyl methyl ether, certain proteins such as poly (VATGVV), a repeating unit in the natural protein elastin, and certain alginates. Mixtures of these polymers with salts or surfactants can also be used as the LCST substance. By such additions or by the degree of crosslinking of the polymers, the LCST (lower critical demixing temperature) can be modified accordingly.
Unter "Wachsen" wird eine Reihe natürlicher oder künstlich gewonnener Stoffe verstanden, die in der Regel über 35°C ohne Zersetzung schmelzen und schon wenig oberhalb des Schmelzpunktes verhält-nismäßig niedrigviskos und nicht fadenziehend sind. Sie weisen eine stark temperaturabhängige Kon-sistenz und Löslichkeit auf. Nach ihrer Herkunft teilt man die Wachse in drei Gruppen ein, die natürlichen Wachse, chemisch modifizierte Wachse und die synthetischen Wachse.By "waxing" is meant a number of natural or artificially derived substances which generally melt above 35 ° C without decomposition and are already slightly above the melting point, relatively low viscosity and non-stringy. They show a strong temperature-dependent consistency and solubility. According to their origin, the waxes are divided into three groups, the natural waxes, chemically modified waxes and the synthetic waxes.
Zu den natürlichen Wachsen zählen beispielsweise pflanzliche Wachse wie Candelillawachs, Camauba-wachs, Japanwachs, Espartograswachs, Korkwachs, Guarumawachs, Reiskeimölwachs, Zuckerrohr-wachs, Ouricurywachs, oder Montanwachs, tierische Wachse wie Bienenwachs, Schellackwachs, Walrat, Lanolin (Wollwachs), oder Bürzelfett, Mineralwachse wie Ceresin oder Ozokerit (Erdwachs), oder petro-chemische Wachse wie Petrolatum, Paraffinwachse oder Mikrowachse.The natural waxes include, for example, vegetable waxes such as candelilla wax, carnauba wax, Japan wax, Espartograswachs, cork wax, guaruma wax, rice germ oil wax, sugarcane wax, ouricury wax, or montan wax, animal waxes such as beeswax, shellac wax, spermaceti, lanolin (wool wax), or raffia fat Mineral waxes such as ceresin or ozokerite (groundwax) or petrochemical waxes such as petrolatum, paraffin waxes or microwaxes.
Zu den chemisch modifizierten Wachsen zählen beispielsweise Hartwachse wie Montanesterwachse, Sassolwachse oder hydrierte Jojobawachse.The chemically modified waxes include, for example, hard waxes such as montan ester waxes, Sassol waxes or hydrogenated jojoba waxes.
Unter synthetischen Wachsen werden in der Regel Polyalkylenwachse oder Polyalkylenglycolwachse verstanden. Als Beschichtungsmaterialien einsetzbar sind auch Verbindungen aus anderen Stoffklassen, die die genannten Erfordernisse hinsichtlich des Erweichungspunkts erfüllen. Als geeignete synthetische Verbindungen haben sich beispielsweise höhere Ester der Phthalsäure, insbesondere Dicyclohexyl-phthalat, das kommerziell unter dem Namen Unimoll® 66 (Bayer AG) erhältlich ist, erwiesen. Geeignet sind auch synthetisch hergestellte Wachse aus niederen Carbonsäuren und Fettalkoholen, beispielsweise Dimyristyl Tartrat, das unter dem Namen Cosmacol® ETLP (Condea) erhältlich ist. Umgekehrt sind auch synthetische oder teilsynthetische Ester aus niederen Alkoholen mit Fettsäuren aus nativen Quellen einsetzbar. In diese Stoffklasse fällt beispielsweise das Tegin® 90 (Goldschmidt), ein Glycerinmonostearat-palmitat. Auch Schellack, beispielsweise Schellack-KPS-Dreiring-SP (Kalkhoff GmbH) ist als weitere Substanz einsetzbar.Synthetic waxes are generally understood as meaning polyalkylene waxes or polyalkylene glycol waxes. Also suitable as coating materials are compounds from other classes of substances which fulfill the stated requirements with regard to the softening point. Suitable synthetic compounds have, for example, higher esters of phthalic acid, in particular dicyclohexyl phthalate, which is commercially available under the name Unimoll ® 66 (Bayer AG), proved. Also suitable are synthetic waxes made of lower carboxylic acids and fatty alcohols, such as dimyristyl tartrate, sold under the name Cosmacol ® ETLP (Condea) is available. Conversely, synthetic or partially synthetic esters of lower alcohols can be used with fatty acids from natural sources. This class of substances includes, for example, Tegin® 90 (Goldschmidt), a glycerol monostearate palmitate. Shellac, for example shellac KPS three-ring SP (Kalkhoff GmbH) can be used as further substance.
Ebenfalls zu den Wachsen im Rahmen der vorliegenden Erfindung werden beispielsweise die sogenannten Wachsalkohole gerechnet. Wachsalkohole sind höhermolekulare, wasserunlösliche Fettalkohole mit in der Regel etwa 22 bis 40 Kohlenstoffatomen. Die Wachsalkohole kommen beispielsweise in Form von Wachsestem höhermolekularer Fettsäuren (Wachssäuren) als Hauptbestandteil vieler natürlicher Wachse vor. Beispiele für Wachsalkohole sind Lignocerylalkohol (1-Tetracosanol), Cetylalkohol, Myristyl-alkohol oder Melissylalkohol. Die Beschichtung kann gegebenenfalls auch Wollwachsalkohole enthalten, worunter man Triterpenoid- und Steroidalkohole, beispielsweise Lanolin, versteht, das beispielsweise unter der Handelsbezeichnung Argowax® (Pamentier & Co) erhältlich ist. Ebenfalls zumindest anteilig als Bestandteil der Beschichtung einsetzbar sind im Rahmen der vorliegenden Erfindung Fettsäureglycerin-ester oder Fettsäurealkanolamide aber gegebenenfalls auch wasserunlösliche oder nur wenig wasser-lösliche Polyalkylenglycolverbindungen.Likewise to the waxes in the context of the present invention, for example, the so-called wax alcohols are calculated. Wax alcohols are higher molecular weight, water-insoluble fatty alcohols having generally about 22 to 40 carbon atoms. The wax alcohols are present, for example, in the form of wax esters of higher molecular weight fatty acids (wax acids) as the main constituent of many natural waxes. Examples of wax alcohols are lignoceryl alcohol (1-tetracosanol), cetyl alcohol, myristyl alcohol or melissyl alcohol. The coating can optionally also contain wool wax alcohols which are understood to be understood triterpenoid and steroid alcohols, for example lanolin, available, for example, under the trade designation Argowax ® (Pamentier & Co). In the context of the present invention, fatty acid glycerol esters or fatty acid alkanolamides but optionally also water-insoluble or only slightly water-soluble polyalkylene glycol compounds may also be used as part of the coating in the context of the present invention.
Paraffin ist die Bezeichnung für ein festes oder flüssiges Gemisch gereinigter, gesättigter aliphatischer Kohlenwasserstoffe (Paraffine). Dieses ist in Ether und Chloroform leichtlöslich in Wasser jedoch nicht löslich. Im Rahmen der vorliegenden Erfindung können sowohl flüssige Paraffine, als auch Paraffin-Schmelzen eingesetzt werden.Paraffin is the term for a solid or liquid mixture of purified, saturated aliphatic hydrocarbons (paraffins). This is readily soluble in ether and chloroform but not soluble in water. Both liquid paraffins and paraffin melts can be used in the context of the present invention.
Aufgrund ihrer Lösungseigenschaften werden die flüssigen und festen Paraffine bevorzugt als Lösung oder Dispersion in einem organischen Lösungsmittel oder Lösungsmittelgemisch eingesetzt. Doch auch die Verwendung der Paraffine ohne Zusatz von Lösungsmittel in Form der Schmelzen oder Flüssigkeiten ist möglich.Because of their solubility properties, the liquid and solid paraffins are preferably used as a solution or dispersion in an organic solvent or solvent mixture. However, the use of paraffins without the addition of solvent in the form of melts or liquids is possible.
Paraffinwachse weisen gegenüber den anderen genannten, natürlichen Wachsen im Rahmen der vorlie-genden Erfindung den Vorteil auf, dass bei einem Einsatz bevorzugter, mit Paraffinwachsen beschichte-ten Wasch- oder Reinigungsmittelformkörper in einer alkalischen Reinigungsmittelumgebung keine Hy-drolyse der Wachse stattfindet (wie sie beispielsweise bei den Wachsestem zu erwarten ist), da Paraffinwachs keine hydrolisierbaren Gruppen enthält.In the context of the present invention, paraffin waxes have the advantage over the other natural waxes mentioned that the use of preferred washing or cleaning agent shaped bodies coated with paraffin waxes in an alkaline cleaning agent environment does not result in hydrolysis of the waxes (as for example in the case of wax esters), since paraffin wax contains no hydrolyzable groups.
Paraffinwachse bestehen hauptsächlich aus Alkanen sowie niedrigen Anteilen an Iso- und Cycloalkanen. Das erfindungsgemäß einzusetzende Paraffin weist bevorzugt im wesentlichen keine Bestandteile mit einem Schmelzpunkt von mehr als 70°C, besonders bevorzugt von mehr als 60°C auf.
Bevorzugte Beschichtungsmaterialien, enthalten mindestens einen Paraffinwachs mit einem Schmelzbereich von 40°C bis 60°C.Paraffin waxes consist mainly of alkanes and low levels of iso- and cycloalkanes. The paraffin to be used according to the invention preferably has substantially no constituents with a melting point of more than 70 ° C., more preferably of more than 60 ° C.
Preferred coating materials contain at least one paraffin wax with a melting range from 40 ° C to 60 ° C.
Vorzugsweise ist der Gehalt des eingesetzten Paraffinwachses an bei Umgebungstemperatur (in der Regel etwa 10 bis etwa 30°C) festen Alkanen, Isoalkanen und Cycloalkanen möglichst hoch. Je mehr feste Wachsbestandteile in einem Wachs bei Raumtemperatur vorhanden sind, desto brauchbarer ist es im Rahmen der vorliegenden Erfindung.Preferably, the content of the paraffin wax used at ambient temperature (usually about 10 to about 30 ° C) solid alkanes, isoalkanes and cycloalkanes as high as possible. The more solid wax constituents in a wax at room temperature, the more useful it is within the scope of the present invention.
In Form ihrer Schmelzen aufgebrachte Paraffinwachse erstarren vorzugsweise innerhalb von 10 Minuten, bevorzugt innerhalb von 5 Minuten und insbesondere innerhalb von 2 Minuten.Paraffin waxes applied in the form of their melts preferably solidify within 10 minutes, preferably within 5 minutes and especially within 2 minutes.
Die Verwendung von hydrophoben Stoffen als Beschichtungsmaterial ist in der vorliegenden Erfindung bevorzugt, da diese Stoffe das Lagerverhalten der erfindungsgemäßen Wasch- oder Reinigungsmittel-formkörper bei hohen Luftfeuchten verbessern. Die erhöhte Feuchtigkeitsresistenz der beschichteten Körper ermöglicht es, nach Auftragung eines hydrophoben Stoffes auf eine Versiegelung mit einer wasserlöslichen oder wasserdispergierbaren Folie zu verzichten. Dies ist jedoch nur eine bevorzugte Ausführungsform des erfindungsgemäßen Verfahrens. Andererseits kann es bevorzugt sein, eine Folie auf den hydrophob-beschichteten Formkörper aufzubringen. Dabei kann die Folie wenigstens anteils-weise mit der Beschichtung verschmolzen werden, lose aufliegen, das heißt den Körper umschließen, oder auch ein Luftpolster enthalten, so dass der Formkörper zusätzlich vor mechanischen Einwirkungen geschützt wird.The use of hydrophobic substances as a coating material is preferred in the present invention, since these substances improve the storage behavior of the laundry detergent or cleaner moldings according to the invention at high humidities. The increased moisture resistance of the coated body makes it possible to dispense after application of a hydrophobic substance to a seal with a water-soluble or water-dispersible film. However, this is only a preferred embodiment of the method according to the invention. On the other hand, it may be preferable to apply a film to the hydrophobic-coated molded body. In this case, the film can be fused at least proportionately with the coating, loosely, that enclose the body, or contain an air cushion, so that the molded body is additionally protected from mechanical effects.
In einer bevorzugten Ausführungsform des erfindungsgemäßen Verfahrens werden die Formkörper zweifach, dreifach oder vierfach beschichtet, wobei bei den Beschichtungsvorgängen jeweils die gleichen oder unterschiedliche Beschichtungsmaterialien eingesetzt werden können. Grundsätzlich wird im Rahmen der vorliegenden Anmeldung zwischen Beschichtungsmaterien aus der Gruppe der wasserlöslichen Polymere (z.B. PVA, PVP, Gelatine oder LCST Polymere) und der wasserunlöslichen Wachse sowie den Paraffinen unterschieden. Die nachfolgende Tabelle gibt eine Überblick über eine Reihe besonders bevorzugter Abfolgen dieser Beschichtungsmaterialien. Die als 1. Schicht gekennzeichnete Beschichtung entspricht dabei der zuerst auf den Formkörper aufgebrachten Schicht.
Innerhalb der folgenden Tabelle übernimmt der Schrägstrich (I) die Bedeutung einer "und/oder"-Verknüpfung.
Within the following table, the slash (I) takes on the meaning of a "and / or" -link.
Den Beschichtungsmaterialien können Wirk- und Aktivstoffe beigemischt sein. Bevorzugt werden den Beschichtungsmaterialien Farbstoffe, Duftstoffe oder Bitterstoffe zugesetzt.The coating materials can be mixed with active ingredients and active ingredients. Dyes, fragrances or bitter substances are preferably added to the coating materials.
Die Raumform der Wasch- oder Reinigungsmittelformkörper unterliegt keiner Beschränkung. Beispiele sind Raumkörper mit mehreckiger Grundfläche, wobei der Körper eine Fortsetzung der mehreckigen Grundfläche im Raum darstellt. Bevorzugte Beispiele der Körper mit mehreckiger Grundfläche sind prismenförmige Körper. Beispiele des prismenförmigen Körpers sind trigonale Prismen, rhombische Prismen, orthorhombische Prismen, tetragonale Prismen, pentagonale Prismen, hexagonale Prismen oder oktagonale Prismen. Besonders bevorzugt ist eine Quaderform. Beispiele für weitere geeignete mehreckige Körper sind trigonale, tetragonale, rhombische, orthorhombische, hexagonale oder oktagonale Pyramiden und Dipyramiden. Gemäß der vorliegenden Erfindung kann der Körper auch eine Mischform verschiedener geometrischer Körper sein. Weiterhin bevorzugt sind Formkörper mit ovaler oder runder Grundfläche, wobei der Körper vorzugsweise wiederum eine Fortsetzung der Grundfläche im Raum darstellt.The spatial form of the detergent tablets is not subject to any restriction. Examples are room bodies with a polygonal base area, whereby the body represents a continuation of the polygonal floor space in the room. Preferred examples of the polygonal body are prismatic bodies. Examples of the prismatic body are trigonal prisms, rhombic prisms, orthorhombic prisms, tetragonal prisms, pentagonal prisms, hexagonal prisms, or octagonal prisms. Particularly preferred is a cuboid shape. Examples of other suitable polygonal bodies are trigonal, tetragonal, rhombic, orthorhombic, hexagonal or octagonal pyramids and dipyramids. According to the present invention, the body may also be a hybrid of various geometric bodies. Preference is furthermore given to moldings with an oval or round base surface, wherein the body preferably again represents a continuation of the base surface in the room.
Das Volumen der Wasch- oder Reinigungsmittelformkörper beträgt vorzugsweise zwischen 12 und 30 ml, bevorzugt zwischen 15 und 25 ml und insbesondere zwischen 17 und 22 ml. Das Gewicht der Formkörper beträgt vorzugsweise zwischen 10 und 25 g. Derartige Wasch- oder Reinigungsmittelformkörper eignen sich insbesondere als Dosiereinheiten für die einmalige Anwendung. Die Dosierung dieser Formkörper erfolgt dabei in der Regel über die Dosierkammern von Wasch- oder Geschirrspülmaschinen. Die Raumform des Formkörpers kann daher selbstverständlich auch an beliebige unregelmäßige Formen von Dosierfächern/Einspülkammern verschiedener Waschmaschinen und Geschirrspülmaschinen angepasst werden. Eine Quaderform des Wasch- oder Reinigungsmittelformkörpers ist dabei insofern bevorzugt, als hierdurch übliche quaderförmige Einspülkammern oder Geschirrspülmaschinen bezüglich des Volumens am besten ausgefüllt werden können. Zudem lassen sich quaderförmig proportionierte Wasch- oder Reinigungsmittel sehr gut platzsparend lagern.The volume of the detergent tablets is preferably between 12 and 30 ml, preferably between 15 and 25 ml and in particular between 17 and 22 ml. The weight of the tablets is preferably between 10 and 25 g. Such detergent tablets are particularly suitable as dosing units for single use. The dosage of these moldings is usually done via the metering chambers of washing machines or dishwashers. The spatial form of the molding can therefore of course be adapted to any irregular shapes of dosing / Einspülkammern different washing machines and dishwashers. A cuboid shape of the washing or cleaning agent shaped body is preferred insofar as this makes it possible to fill in the usual cuboid insufflation chambers or dishwashers best in terms of volume. In addition, cuboid-shaped detergents or cleaning agents can be stored very well in a space-saving manner.
Einsetzbar sind weiterhin insbesondere auch Formkörper mit konvexen oder konkaven Seitenflächen. Eine bevorzugte Ausführungsform eines Formkörpers mit einer konkaven Seitenfläche ist der Muldenformkörper. Das Muldenvolumen dieser Formkörper entspricht dabei vorzugsweise mindestens 10 Vol.-%, vorzugsweise mindestens 20 Vol.-% und insbesondere mindestens 40 Vol.-% des Formkörpervolumens (ohne die Mulde).In particular moldings with convex or concave side surfaces can also be used. A preferred embodiment of a shaped body with a concave side surface is the molded body. The well volume of these shaped bodies preferably corresponds to at least 10% by volume, preferably at least 20% by volume and in particular at least 40% by volume of the molding volume (without the depression).
Alternativ zu einer Mulde können die Wasch- und Reinigungsmittelformkörper eine Kavität in Form eines durchgehenden Loches aufweisen. Die Öffnungen dieses Loches können sich in angrenzenden Seitenflächen und/oder in gegenüberliegenden Seitenflächen des Formkörpers befinden. Befinden sich die Öffnungen des Loches auf einander gegenüberliegenden Seiten des Formkörpers, so bezeichnet man die entsprechenden Formkörper auch als Ringformkörper oder Ringtabletten.As an alternative to a trough, the detergent tablets may have a cavity in the form of a through hole. The openings of this hole may be located in adjacent side surfaces and / or in opposite side surfaces of the shaped body. If the openings of the hole are located on mutually opposite sides of the shaped body, the corresponding shaped bodies are also referred to as ring shaped bodies or ring tablets.
Bei den in dem erfindungsgemäßen Verfahren eingesetzten Formkörpern kann es sich beispielsweise um Gießkörper, (Strang)-Extrudate oder Kompaktate handeln. Mit besonderem Vorzug werden als Formkörper Tabletten eingesetzt. Zur Herstellung von Tabletten werden partikelförmige Vorgemische in einer sogenannten Matrize zwischen zwei Stempeln zu einem festen Komprimat verdichtet. Dieser Vorgang, der im folgenden kurz als Tablettierung bezeichnet wird, gliedert sich in vier Abschnitte: Dosierung, Verdichtung, plastische Verformung und Ausstoßen.The moldings used in the process according to the invention may be, for example, cast bodies, (extruded) extrudates or compactates. With particular preference tablets are used as tablets. To produce tablets, particulate premixes are compacted in a so-called matrix between two punches to form a solid compressed product. This process, hereinafter referred to as tabletting, is divided into four sections: dosing, compaction, plastic deformation and ejection.
Selbstverständlich lassen sich die Tabletten im Rahmen der vorliegenden Erfindung ebenfalls mehr-phasig, insbesondere mehrschichtig, ausgestalten. Die Formkörper können dabei in vorbestimmter Raumform und vorbestimmter Größe gefertigt werden. Als Raumform kommen praktisch alle sinnvoll handhabbaren Ausgestaltungen in Betracht, beispielsweise also die Ausbildung als Tafel, die Stab- bzw. Barrenform, Würfel, Quader und entsprechende Raumelemente mit ebenen Seitenflächen sowie insbesondere zylinderförmige Ausgestaltungen mit kreisförmigem oder ovalem Querschnitt. Diese letzte Ausgestaltung erfasst dabei die Darbietungsform von der Tablette bis zu kompakten Zylinderstücken mit einem Verhältnis von Höhe zu Durchmesser oberhalb 1.Of course, the tablets in the context of the present invention also multi-phase, in particular multi-layered, ausgestalten. The moldings can be made in a predetermined spatial form and predetermined size. As a form of space practically all useful manageable configurations come into consideration, for example, the training as a blackboard, the bar or bar shape, cubes, cuboids and corresponding space elements with flat side surfaces and in particular cylindrical configurations with circular or oval cross-section. This last embodiment covers the presentation form of the tablet up to compact cylinder pieces with a ratio of height to diameter above 1.
Nach dem Verpressen weisen die Wasch- und Reinigungsmittelformkörper eine hohe Stabilität auf. Die Bruchfestigkeit zylinderförmiger Formkörper kann über die Messgröße der diametralen Bruchbeanspruchung erfasst werden. Diese ist bestimmbar nach
Hierin steht σ für die diametrale Bruchbeanspruchung (diametral fracture stress, DFS) in Pa, P ist die Kraft in N, die zu dem auf den Formkörper ausgeübten Druck führt, der den Bruch des Formkörpers verursacht, D ist der Formkörperdurchmesser in Meter und t ist die Höhe der Formkörper.Herein, σ is the diametrical fracture stress (DFS) in Pa, P is the force in N which results in the pressure applied to the molded article causing the breakage of the molded article, D is the molded article diameter in meters and t the height of the moldings.
Wie eingangs ausgeführt kann durch das erfindungsgemäße Verfahren die Stabilität und Bruchhärte der verarbeiteten Formkörper verbessert werden, ohne deren Zerfalls- und Auflösungseigenschaften zu beeinträchtigen. Mit anderen Worten zeichnen sich der Formkörper nach der Beschichtung bei gleichbleibendem Auflösungsverhalten durch eine erhöhte Bruchfestigkeit aus. Besonders deutlich wird dieser unerwartete Effekt bei Einsatz der zuvor beschriebenen Formkörper, welche eine Kavität in Form einer Mulde oder eines durchgehenden Loches aufweisen und zwar insbesondere dann, wenn die Beschichtung in Schritt b) auf den Außenflächen des Formkörpers, nicht jedoch innerhalb der Kavität aufgebracht wird. Bei großtechnischen Prozessen ist eine geringe "Kontamination" der Flächen innerhalb der Kavität unter gewissen Umständen nicht zu vermeiden. Diese "Kontamination" sollte jedoch vorzugsweise weniger als 10 Gew.-%, vorzugsweise weniger als 5 Gew.-% und insbesondere weniger als 3 Gew.-% der Gesamtmenge des aufgetragenen Beschichtungsmittels betragen.As stated at the outset, the stability and hardness of the processed shaped bodies can be improved by the method according to the invention without impairing their decay and dissolution properties. In other words, the molded body after coating with constant dissolution behavior characterized by an increased breaking strength. This unexpected effect becomes particularly clear when using the above-described shaped bodies which have a cavity in the form of a depression or a through hole, in particular if the coating in step b) is applied to the outer surfaces of the molding but not within the cavity , In large-scale processes, a low "contamination" of the surfaces within the cavity can not be avoided under certain circumstances. However, this "contamination" should preferably be less than 10% by weight, preferably less than 5% by weight and in particular less than 3% by weight of the total amount of coating agent applied.
Bevorzugte erfindungsgemäße Verfahren sind demnach dadurch gekennzeichnet, dass die Beschichtung in Schritt b) auf den Außenflächen des Formkörpers mit der Kavität, nicht jedoch innerhalb der Kavität erfolgt.Accordingly, preferred processes according to the invention are characterized in that the coating in step b) takes place on the outer surfaces of the molded body with the cavity, but not within the cavity.
Ein bevorzugter Gegenstand der vorliegenden Anmeldung ist daher ein Verfahren zur Herstellung eines Wasch- oder Reinigungsmittelformkörpers, umfassend die Schritte
- a) Bereitstellen eines Formkörpers, vorzugsweise einer Tablette, welche eine Kavität in Form einer Mulde oder eines durchgehenden Loches aufweist;
- b) Aufbringen eines Beschichtungsmittels auf die Oberfläche des Formkörpers, so dass die Oberflächenbedeckung der beschichteten Formkörperoberfläche mit dem Beschichtungsmittel zwischen 0,2 und 50 mg/cm2 beträgt, wobei die Beschichtung auf den Außenflächen des Formkörpers, nicht jedoch innerhalb der Kavität aufgebracht wird;
- c) Aufsiegeln einer wasserlöslichen oder wasserdispergierbaren Folie auf die beschichtete Oberfläche des Formkörpers durch Heißsiegelung.
- a) providing a shaped body, preferably a tablet, which has a cavity in the form of a trough or a through hole;
- b) applying a coating agent to the surface of the molding so that the surface coverage of the coated molding surface with the coating agent is between 0.2 and 50 mg / cm 2 , the coating being applied to the exterior surfaces of the molding but not within the cavity;
- c) sealing a water-soluble or water-dispersible film on the coated surface of the molding by heat sealing.
Mit besonderem Vorzug wird die Beschichtung des Formkörpers auch in dieser Verfahrensvariante wiederholt, vorzugsweise zweifach, dreifach oder vierfach, vorgenommen.With particular preference, the coating of the molding is repeated in this process variant, preferably twice, three or four times.
Die Kavität der zuvor beschriebenen Mulden- oder Ringformkörper werden in einer bevorzugten Verfahrensvariante mit einer wasch- oder reinigungsaktiven Substanz oder einem wasch- oder reinigungsaktiven Substanzgemisch befüllt. Als Füllmaterialien werden a) partikelförmige Zusammensetzungen aus der Gruppe der Pulver, Granulate oder Extrudate oder b) flüssige oder gelförmige Zubereitungen bevorzugt. Als flüssige Zubereitungen können beispielsweise Lösungen oder Schmelzen eingefüllt werden. Die Befüllung der Kavität kann vor oder nach dem Aufbringen des Beschichtungsmaterials, aber auch zwischen zwei Beschichtungsgängen erfolgen. Bevorzugt werden Verfahren, bei denen die Befüllung nach dem Beschichten des Formkörpers erfolgt.In a preferred process variant, the cavity of the above-described troughed or ring-shaped bodies is filled with a washing- or cleaning-active substance or a washing or cleaning-active substance mixture. As filler materials, preference is given to a) particulate compositions from the group of powders, granules or extrudates or b) liquid or gelatinous preparations. As liquid preparations, for example, solutions or melts can be filled. The filling of the cavity can be carried out before or after the application of the coating material, but also between two coating courses. Preference is given to processes in which the filling takes place after the coating of the shaped body.
Die in die Kavität gefüllten Substanzen oder Substanzgemische können auf unterschiedliche Weise in der Kavität fixiert werden. In einer ersten bevorzugten Ausführungsform werden die Substanzen oder Substanzgemische in der Kavität durch Adhäsion fixiert. In einer weiteren bevorzugten Ausführungsform liegen die Substanzen oder Substanzgemische in einer wasserlöslichen oder wasserdispergierbaren Verpackung, beispielsweise einem tiefgezogenen Beutel oder einem spritzgegossenen Behälter vor, welcher die Kavität wenigstens anteilsweise ausfüllt und seinerseits mit dem Formkörper durch Adhäsion oder eine mechanische Verbindung, beispielsweise eine Rast-, Schnapp-, Steck- oder Klemmverbindung verbunden ist.The substances or mixtures of substances filled in the cavity can be fixed in the cavity in different ways. In a first preferred embodiment, the substances or substance mixtures fixed in the cavity by adhesion. In a further preferred embodiment, the substances or substance mixtures are present in a water-soluble or water-dispersible packaging, for example a deep-drawn bag or an injection-molded container, which at least partially fills the cavity and in turn with the molding by adhesion or a mechanical connection, for example a detent, Snap, plug or clamp connection is connected.
Die Kavität wird vorzugsweise zu mindestens 70 Vol.-%, bevorzugt mindestens 80 Vol.-%, besonders bevorzugt mindestens 90 Vol.-% und insbesondere mindestens 95 Vol.-% ihres Volumens befüllt.The cavity is preferably filled to at least 70% by volume, preferably at least 80% by volume, more preferably at least 90% by volume and in particular at least 95% by volume of its volume.
In dem erfindungsgemäßen Verfahren wird nach dem Beschichten eine wasserlösliche oder wasserdispergierbare Folie auf die beschichtete Oberfläche des Formkörpers aufgesiegelt, wobei die Siegelung durch Heißsiegelung erfolgt.In the process according to the invention, after coating, a water-soluble or water-dispersible film is sealed onto the coated surface of the shaped body, the sealing being effected by heat sealing.
Die aufgesiegelte Folie kann eine Reihe unterschiedlicher Funktionen übernehmen. Beispielsweise ist eine solche Folie geeignet, die in die Kavität des Formkörpers eingefüllten Substanzen oder Substanzgemische in dieser Kavität zu fixieren. Weiterhin kann mittels dieser Folien die Bruchfestigkeit und/oder Lagerstabilität des Formkörpers weiter erhöht werden. Als bevorzugte Folienmaterialien werden insbesondere die weiter oben genannten wasserlöslichen Polymere aus der Gruppe (gegebenenfalls acetalisierter) Polyvinylalkohol (PVAL), Polyvinylpyrrolidon, Polyethylenoxid, Gelatine, Cellulose, und deren Derivate und deren Mischungen eingesetzt.The sealed foil can perform a number of different functions. For example, such a film is suitable for fixing the substances or substance mixtures filled in the cavity of the shaped body in this cavity. Furthermore, the breaking strength and / or storage stability of the shaped body can be further increased by means of these films. Preferred film materials used are, in particular, the water-soluble polymers mentioned above from the group (optionally acetalized) polyvinyl alcohol (PVAL), polyvinylpyrrolidone, polyethylene oxide, gelatin, cellulose, and derivatives thereof and mixtures thereof.
Überraschenderweise wurde festgestellt, dass sich die Siegelung der vorgenannten Folien auf den erfindungsgemäß beschichteten Formkörpern gegenüber Siegelungen auf herkömmlichen Formkörpern durch eine erhöhte Festigkeit und Dichtigkeit auszeichnen.It has surprisingly been found that the sealing of the abovementioned films on the moldings coated according to the invention over seals on conventional moldings is distinguished by increased strength and imperviousness.
Ein weiterer Gegenstand der vorliegenden Anmeldung ist ein beschichteter Wasch- oder Reinigungsmittelformkörper, dadurch gekennzeichnet, dass die Oberflächenbedeckung der beschichteten Formkörperoberfläche mit dem Beschichtungsmittel zwischen 0,2 und 50 mg/cm2 beträgt und auf die beschichtete Oberfläche eine wasserlösliche oder wasserdispergierbare Folie aufgesiegelt ist, dadurch gekennzeichnet, dass der Formkörper eine beschichtete Oberfläche sowie eine wasserlösliche oder wasserdispergierbare Folie umfasst, wobei die Beschichtung und die wasserlösliche oder wasserdispergierbare Folie wenigstens anteilsweise miteinander verschmolzen sind und das Beschichtungsmittel auf den Formkörper aufgesprüht wurde.A further subject of the present application is a coated washing or cleaning agent shaped article, characterized in that the surface coverage of the coated molding surface with the coating agent is between 0.2 and 50 mg / cm 2 and the water-soluble or water-dispersible film is sealed onto the coated surface, characterized in that the shaped body comprises a coated surface and a water-soluble or water-dispersible film, wherein the coating and the water-soluble or water-dispersible film are at least partially fused together and the coating agent was sprayed onto the shaped body.
Bezüglich der bevorzugten Ausführungsformen für diese Formkörper gelten mutatis mutandis die zuvor für das erfindungsgemäße Verfahren gemachten Angaben.With regard to the preferred embodiments of these moldings mutatis mutandis apply the information previously given for the inventive method.
Insbesondere weisen bevorzugte beschichtete Wasch- oder Reinigungsmittelformkörper nach eine Oberflächenbedeckung der beschichteten Formkörperoberfläche mit dem Beschichtungsmittel zwischen 0,4 und 40 mg/cm2, vorzugsweise zwischen 0,8 und 30 mg/cm2 und insbesondere zwischen 1 und 20 mg/cm2 auf.In particular, preferred coated detergent tablets have a surface coverage of the coated shaped body surface with the coating agent between 0.4 and 40 mg / cm 2 , preferably between 0.8 and 30 mg / cm 2 and in particular between 1 and 20 mg / cm 2 ,
Bei dem Beschichtungsmittel handelt es sich vorzugsweise um ein wasserlösliches organisches Polymer, vorzugsweise um ein Polymer aus der Gruppe Polyvinylalkohol, Polyvinylpyrrolidon und Celluloseether handelt.The coating agent is preferably a water-soluble organic polymer, preferably a polymer from the group consisting of polyvinyl alcohol, polyvinylpyrrolidone and cellulose ethers.
Die Bruchhärte der beschichteten Wasch- oder Reinigungsmittelformkörper liegt vorzugsweise oberhalb 60 N, bevorzugt oberhalb 80 N, besonders bevorzugt oberhalb 100 N und insbesondere oberhalb 110 N.The fracture hardness of the coated detergent tablets is preferably above 60 N, preferably above 80 N, particularly preferably above 100 N and in particular above 110 N.
Die Formkörper weisen vorzugsweise eine Kavität in Form einer Mulde oder eines durchgehenden Loches auf, wobei solche Formkörper besonders bevorzugt sind, die auf den Außenflächen, nicht jedoch innerhalb der Kavität beschichtet ist.The shaped bodies preferably have a cavity in the form of a depression or a through hole, wherein those shaped bodies which are coated on the outer surfaces but not within the cavity are particularly preferred.
Die Kavität der erfindungsgemäßen Formkörper ist vorzugsweise befüllt.The cavity of the shaped bodies according to the invention is preferably filled.
Erfindungsgemäße Wasch- oder Reinigungsmittelformkörper sind dadurch gekennzeichnet, dass der Formkörper eine beschichtete Oberfläche sowie eine wasserlösliche oder wasserdispergierbare Folie umfasst, wobei die Beschichtung und die wasserlösliche oder wasserdispergierbare Folie wenigstens anteilsweise miteinander verschmolzen sind.Inventive detergent tablets are characterized in that the shaped body comprises a coated surface and a water-soluble or water-dispersible film, wherein the coating and the water-soluble or water-dispersible film are at least partially fused together.
Die zuvor beschriebenen erfindungsgemäßen Mittel bzw. die nach dem zuvor beschriebenen erfindungsgemäßen Verfahren hergestellten Mittel enthalten wasch- und reinigungsaktive Substanzen, vorzugsweise wasch- und reinigungsaktive Substanzen aus der Gruppe der Gerüststoffe, Tenside, Polymere, Bleichmittel, Bleichaktivatoren, Enzyme, Glaskorrosionsinhibitoren, Korrosionsinhibitoren, Desintegrationshilfsmittel, Duftstoffe und Parfümträger. Die Mittel sind daher in der Regel wasserlöslich oder wasserdispergierbar.The compositions according to the invention or the compositions prepared by the process according to the invention described above contain washing and cleaning substances, preferably washing and cleaning substances from the group of builders, surfactants, polymers, bleaches, bleach activators, enzymes, glass corrosion inhibitors, corrosion inhibitors, disintegration aids , Fragrances and perfume carriers. The agents are therefore usually water-soluble or water-dispersible.
Zusätzlich zu den bisher ausführlich beschriebenen Komponenten können die Wasch- und Reinigungsmittel weitere Inhaltsstoffe enthalten, welche die anwendungstechnischen und/oder ästhetischen Eigenschaften dieser Mittel weiter verbessern. Bevorzugte Mittel enthalten einen oder mehrere Stoffe aus der Gruppe der Elektrolyte, pH-Stellmittel, Fluoreszenzmittel, Hydrotope, Schauminhibitoren, Silikonöle, Antiredepositionsmittel, optische Aufheller, Vergrauungsinhibitoren, Einlaufverhinderer, Knitterschutzmittel, Farbübertragungsinhibitoren, antimikrobiellen Wirkstoffen, Germizide, Fungizide, Antioxidantien, Antistatika, Bügelhilfsmittel, Phobier- und Imprägniermittel, Quell- und Schiebefestmittel sowie UV-Absorber.In addition to the components described in detail so far, the detergents and cleaners can contain further ingredients which further improve the performance and / or aesthetic properties of these compositions. Preferred agents contain one or more of the group of electrolytes, pH adjusters, fluorescers, hydrotopes, foam inhibitors, silicone oils, anti redeposition agents, optical brighteners, grayness inhibitors, anti-shrinkage agents, anti-crease agents, color transfer inhibitors, antimicrobial agents, germicides, fungicides, antioxidants, antistatic agents, ironing aids , Phobic and impregnating agents, swelling and anti-slip agents and UV absorbers.
Claims (14)
- A method for manufacturing a shaped washing or cleaning agent body, comprising the steps of:a) providing a shaped body, which comprises a cavity in the form of a recess or a through-hole;b) applying a coating agent to the surface of the shaped body in such a way that the surface coverage of the coated shaped body surface with the coating agent is between 0.2 and 50 mg/cm2;c) sealing a water-soluble or water-dispersible film onto the coated surface of the shaped body by heat sealing;
characterized in that the coating agent is sprayed onto the shaped body. - A method according to claim 1, characterized in that the surface coverage of the shaped body is between 0.4 and 40 mg/cm2, preferably between 0.8 and 30 mg/cm2 and most preferably between 1 and 20 mg/cm2.
- A method according to either claim 1 or claim 2, characterized in that the coating agent is applied by means of a solution or a dispersion, preferably by means of an aqueous solution, preferably by means of an aqueous solution with a proportion by weight of the coating agent of less than 80 % by weight, preferably less than 65 % by weight, more preferably less than 50 % by weight and in particular less than 40 % by weight, based in each case on the total weight of the solution.
- A method according to one of claims 1 to 3, characterized in that a water-soluble organic polymer, preferably a polymer from the group of polyvinyl alcohol, polyvinyl pyrrolidone and cellulose ether is used as the coating agent.
- A method according to one of claims 1 to 4, characterized in that the coating agent is applied to the shaped body by spraying the body with a solution or dispersion of the coating agent a plurality of times.
- A method according to claim 5, characterized in that the coating in step b) takes place on the external surfaces of the shaped body but not inside the cavity.
- A method according to either claim 5 or claim 6, characterized in that the cavity is filled before or after the coating agent is applied in step b).
- A coated shaped washing or cleaning agent body, characterized in that the shaped body comprises a cavity in the form of a recess or a through-hole and the surface coverage of the coated shaped-body surface with the coating agent is between 0.2 and 50 mg/cm2 and a water-soluble or water-dispersible film is sealed onto the coated surface of the shaped body, characterized in that the shaped body comprises a coated surface and a water-soluble or water-dispersible film, the coating and the water-soluble or water-dispersible film being melted together at least in part and the coating agent having been sprayed onto the shaped body.
- A coated shaped washing or cleaning agent body according to claim 8, characterized in that the surface coverage of the coated shaped-body surface with the coating agent is between 0.4 and 40 mg/cm2, preferably between 0.8 and 30 mg/cm2 and in particular between 1 and 20 mg/cm2.
- A coated shaped washing or cleaning agent body according to either claim 8 or claim 9, characterized in that the coating agent is a water-soluble organic polymer, preferably a polymer from the group of polyvinyl alcohol, polyvinyl pyrrolidone and cellulose ether.
- A coated shaped washing or cleaning agent body according to one of claims 8 to 10, characterized in that the coated shaped body has a fracture toughness of more than 60 N, preferably more than 80 N, more preferably more than 100 N and in particular more than 110 N.
- A coated shaped washing or cleaning agent body according to one of claims 8 to 11, characterized in that the shaped body is coated on the external surfaces but not inside the cavity.
- A coated shaped washing or cleaning agent body according to one of claims 8 to 12, characterized in that the cavity has a filling.
- A washing or cleaning method using a coated shaped washing or cleaning agent body according to one of claims 8 to 13.
Priority Applications (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
PL05769966T PL1781768T5 (en) | 2004-08-20 | 2005-07-28 | Coated shaped detergent or cleaning agent body |
Applications Claiming Priority (2)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
DE102004040330A DE102004040330A1 (en) | 2004-08-20 | 2004-08-20 | Coated washing or cleaning agent shaped body |
PCT/EP2005/008180 WO2006021284A1 (en) | 2004-08-20 | 2005-07-28 | Coated shaped detergent or cleaning agent body |
Publications (3)
Publication Number | Publication Date |
---|---|
EP1781768A1 EP1781768A1 (en) | 2007-05-09 |
EP1781768B1 EP1781768B1 (en) | 2010-02-10 |
EP1781768B2 true EP1781768B2 (en) | 2014-10-08 |
Family
ID=34979903
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
EP05769966.2A Active EP1781768B2 (en) | 2004-08-20 | 2005-07-28 | Coated shaped detergent or cleaning agent body |
Country Status (6)
Country | Link |
---|---|
US (2) | US20080255020A1 (en) |
EP (1) | EP1781768B2 (en) |
AT (1) | ATE457344T1 (en) |
DE (2) | DE102004040330A1 (en) |
PL (1) | PL1781768T5 (en) |
WO (1) | WO2006021284A1 (en) |
Families Citing this family (7)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
DE102005022786B4 (en) * | 2005-05-12 | 2016-09-15 | Henkel Ag & Co. Kgaa | Detergent or detergent dosing unit |
DE102008060470A1 (en) * | 2008-12-05 | 2010-06-10 | Henkel Ag & Co. Kgaa | cleaning supplies |
DE102008060471A1 (en) * | 2008-12-05 | 2010-06-10 | Henkel Ag & Co. Kgaa | Machine dishwashing detergent |
PL2388309T3 (en) * | 2010-05-17 | 2017-07-31 | Dalli-Werke Gmbh & Co. Kg | Detergent tablets having more than four side surfaces |
US9879206B2 (en) | 2013-03-14 | 2018-01-30 | Ecolab Usa Inc. | Enzyme-containing detergent and presoak composition and methods of using |
JP6810060B2 (en) * | 2015-06-09 | 2021-01-06 | ダウ グローバル テクノロジーズ エルエルシー | Support material for 3D printing |
DE102018106720A1 (en) * | 2018-03-21 | 2019-09-26 | Miele & Cie. Kg | Detergent body for use in a washing machine or dishwasher designed as cleaning device and cleaning device |
Citations (5)
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WO1995018215A1 (en) † | 1993-12-30 | 1995-07-06 | Ecolab Inc. | Stable hygroscopic detergent article |
CA2313875A1 (en) † | 1999-07-14 | 2001-01-14 | Henkel Kommanditgesellschaft Auf Aktien | A filled detergent tablet |
US20020006890A1 (en) † | 2000-03-04 | 2002-01-17 | Matthias Sunder | Multiphase laundry detergent and cleaning product shaped bodies having noncompressed parts |
US6548473B1 (en) † | 1997-11-26 | 2003-04-15 | The Procter & Gamble Company | Multi-layer detergent tablet having both compressed and non-compressed portions |
WO2004046297A1 (en) † | 2002-11-21 | 2004-06-03 | Henkel Kommanditgesellschaft Auf Aktien | Method for producing washing and cleaning agents in the form of filled moulded bodies |
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US3324038A (en) * | 1964-04-17 | 1967-06-06 | Procter & Gamble | Detergent composition |
CA1182371A (en) * | 1980-12-18 | 1985-02-12 | Jeyes Group Limited | Lavatory cleansing blocks |
GB9422924D0 (en) | 1994-11-14 | 1995-01-04 | Unilever Plc | Detergent compositions |
US6232284B1 (en) * | 1996-12-06 | 2001-05-15 | The Procter & Gamble Company | Coated detergent tablet with disintegration means |
ATE380235T1 (en) | 1996-12-06 | 2007-12-15 | Procter & Gamble | COATED CLEANING AGENT IN TABLET FORM |
ATE387486T1 (en) * | 1999-03-12 | 2008-03-15 | Procter & Gamble | PERFUMED DETERGENT TABLET |
DE19920118B4 (en) * | 1999-05-03 | 2016-08-11 | Henkel Ag & Co. Kgaa | Detergent tablets with coating and process for its preparation |
DE19940547A1 (en) * | 1999-08-26 | 2001-03-01 | Henkel Kgaa | Detergent tablets with partial coating |
DE19959875A1 (en) * | 1999-12-10 | 2001-07-05 | Henkel Kgaa | Pressing process for multi-phase moldings |
DE10026334A1 (en) | 2000-05-26 | 2001-12-06 | Henkel Kgaa | Detergent tablets with graft copolymer coating |
DE10064635A1 (en) * | 2000-12-22 | 2002-07-04 | Henkel Kgaa | Detergent tablets with delayed solubility comprise compressed particulate detergents ingredients including builder(s) and surfactant(s) |
DE10064985A1 (en) | 2000-12-23 | 2002-07-11 | Henkel Kgaa | Detergent tablets with coating |
DE10233564A1 (en) * | 2002-07-24 | 2003-10-16 | Henkel Kgaa | Packaged portions of detergent or cleaning agent for use in domestic washing machines or dishwashers fit tightly within a water-soluble cover |
-
2004
- 2004-08-20 DE DE102004040330A patent/DE102004040330A1/en not_active Ceased
-
2005
- 2005-07-28 EP EP05769966.2A patent/EP1781768B2/en active Active
- 2005-07-28 DE DE502005008999T patent/DE502005008999D1/en active Active
- 2005-07-28 WO PCT/EP2005/008180 patent/WO2006021284A1/en active Application Filing
- 2005-07-28 PL PL05769966T patent/PL1781768T5/en unknown
- 2005-07-28 AT AT05769966T patent/ATE457344T1/en active
- 2005-07-28 US US11/816,703 patent/US20080255020A1/en not_active Abandoned
-
2007
- 2007-02-21 US US11/709,043 patent/US20090029055A1/en not_active Abandoned
Patent Citations (5)
Publication number | Priority date | Publication date | Assignee | Title |
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WO1995018215A1 (en) † | 1993-12-30 | 1995-07-06 | Ecolab Inc. | Stable hygroscopic detergent article |
US6548473B1 (en) † | 1997-11-26 | 2003-04-15 | The Procter & Gamble Company | Multi-layer detergent tablet having both compressed and non-compressed portions |
CA2313875A1 (en) † | 1999-07-14 | 2001-01-14 | Henkel Kommanditgesellschaft Auf Aktien | A filled detergent tablet |
US20020006890A1 (en) † | 2000-03-04 | 2002-01-17 | Matthias Sunder | Multiphase laundry detergent and cleaning product shaped bodies having noncompressed parts |
WO2004046297A1 (en) † | 2002-11-21 | 2004-06-03 | Henkel Kommanditgesellschaft Auf Aktien | Method for producing washing and cleaning agents in the form of filled moulded bodies |
Also Published As
Publication number | Publication date |
---|---|
PL1781768T3 (en) | 2010-07-30 |
US20080255020A1 (en) | 2008-10-16 |
EP1781768B1 (en) | 2010-02-10 |
DE502005008999D1 (en) | 2010-03-25 |
DE102004040330A1 (en) | 2006-03-02 |
PL1781768T5 (en) | 2015-05-29 |
EP1781768A1 (en) | 2007-05-09 |
US20090029055A1 (en) | 2009-01-29 |
WO2006021284A1 (en) | 2006-03-02 |
ATE457344T1 (en) | 2010-02-15 |
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