WO1997031096A1 - Process for producing dishwasher detergent tablets - Google Patents
Process for producing dishwasher detergent tablets Download PDFInfo
- Publication number
- WO1997031096A1 WO1997031096A1 PCT/EP1997/000700 EP9700700W WO9731096A1 WO 1997031096 A1 WO1997031096 A1 WO 1997031096A1 EP 9700700 W EP9700700 W EP 9700700W WO 9731096 A1 WO9731096 A1 WO 9731096A1
- Authority
- WO
- WIPO (PCT)
- Prior art keywords
- salts
- acids
- surfactants
- weight
- mixture
- Prior art date
Links
- 238000000034 method Methods 0.000 title claims abstract description 25
- 239000003599 detergent Substances 0.000 title claims abstract description 11
- 239000002253 acid Substances 0.000 claims abstract description 31
- 239000000203 mixture Substances 0.000 claims abstract description 24
- 150000003839 salts Chemical class 0.000 claims abstract description 21
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 19
- 150000007513 acids Chemical class 0.000 claims abstract description 18
- 239000004094 surface-active agent Substances 0.000 claims abstract description 17
- 239000005871 repellent Substances 0.000 claims abstract description 6
- 239000000654 additive Substances 0.000 claims abstract description 5
- 239000007791 liquid phase Substances 0.000 claims abstract description 3
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid group Chemical class C(CC(O)(C(=O)O)CC(=O)O)(=O)O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 claims description 40
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 19
- 239000007844 bleaching agent Substances 0.000 claims description 17
- 239000000470 constituent Substances 0.000 claims description 12
- BVKZGUZCCUSVTD-UHFFFAOYSA-M Bicarbonate Chemical compound OC([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-M 0.000 claims description 10
- 239000003513 alkali Substances 0.000 claims description 9
- 239000002736 nonionic surfactant Substances 0.000 claims description 9
- 238000004851 dishwashing Methods 0.000 claims description 8
- 239000007788 liquid Substances 0.000 claims description 8
- 102000004190 Enzymes Human genes 0.000 claims description 7
- 108090000790 Enzymes Proteins 0.000 claims description 7
- 239000006260 foam Substances 0.000 claims description 7
- 239000003112 inhibitor Substances 0.000 claims description 7
- 239000012190 activator Substances 0.000 claims description 6
- 239000000969 carrier Substances 0.000 claims description 6
- 238000002844 melting Methods 0.000 claims description 6
- 230000008018 melting Effects 0.000 claims description 6
- NLJMYIDDQXHKNR-UHFFFAOYSA-K sodium citrate Chemical compound O.O.[Na+].[Na+].[Na+].[O-]C(=O)CC(O)(CC([O-])=O)C([O-])=O NLJMYIDDQXHKNR-UHFFFAOYSA-K 0.000 claims description 6
- 239000001509 sodium citrate Substances 0.000 claims description 5
- FEWJPZIEWOKRBE-UHFFFAOYSA-N Tartaric Acid Chemical class [H+].[H+].[O-]C(=O)C(O)C(O)C([O-])=O FEWJPZIEWOKRBE-UHFFFAOYSA-N 0.000 claims description 4
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 4
- 239000001301 oxygen Substances 0.000 claims description 4
- 229910052760 oxygen Inorganic materials 0.000 claims description 4
- 230000002940 repellent Effects 0.000 claims description 4
- 239000011734 sodium Substances 0.000 claims description 4
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 claims description 3
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 claims description 3
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 claims description 3
- 150000001735 carboxylic acids Chemical class 0.000 claims description 3
- 238000005260 corrosion Methods 0.000 claims description 3
- 230000007797 corrosion Effects 0.000 claims description 3
- 229910052709 silver Inorganic materials 0.000 claims description 3
- 239000004332 silver Substances 0.000 claims description 3
- 229910052708 sodium Inorganic materials 0.000 claims description 3
- 235000000346 sugar Nutrition 0.000 claims description 3
- BVKZGUZCCUSVTD-UHFFFAOYSA-N carbonic acid Chemical class OC(O)=O BVKZGUZCCUSVTD-UHFFFAOYSA-N 0.000 claims description 2
- 229920001577 copolymer Polymers 0.000 claims description 2
- 239000000975 dye Substances 0.000 claims description 2
- 239000003205 fragrance Substances 0.000 claims description 2
- 159000000001 potassium salts Chemical class 0.000 claims description 2
- 239000003381 stabilizer Substances 0.000 claims description 2
- 235000002906 tartaric acid Nutrition 0.000 claims description 2
- HRXKRNGNAMMEHJ-UHFFFAOYSA-K trisodium citrate Chemical compound [Na+].[Na+].[Na+].[O-]C(=O)CC(O)(CC([O-])=O)C([O-])=O HRXKRNGNAMMEHJ-UHFFFAOYSA-K 0.000 claims description 2
- 229940038773 trisodium citrate Drugs 0.000 claims description 2
- 235000015165 citric acid Nutrition 0.000 claims 3
- 239000004615 ingredient Substances 0.000 claims 2
- 238000005538 encapsulation Methods 0.000 claims 1
- 150000004677 hydrates Chemical class 0.000 claims 1
- 229960004106 citric acid Drugs 0.000 description 11
- 239000000126 substance Substances 0.000 description 9
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 8
- UIIMBOGNXHQVGW-UHFFFAOYSA-M Sodium bicarbonate Chemical compound [Na+].OC([O-])=O UIIMBOGNXHQVGW-UHFFFAOYSA-M 0.000 description 8
- 238000004519 manufacturing process Methods 0.000 description 7
- 229940088598 enzyme Drugs 0.000 description 6
- -1 fatty alcohol ethers Chemical class 0.000 description 5
- 229910000288 alkali metal carbonate Inorganic materials 0.000 description 4
- 150000008041 alkali metal carbonates Chemical class 0.000 description 4
- 125000004432 carbon atom Chemical group C* 0.000 description 4
- 239000012459 cleaning agent Substances 0.000 description 4
- 229910000030 sodium bicarbonate Inorganic materials 0.000 description 4
- 235000017557 sodium bicarbonate Nutrition 0.000 description 4
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 3
- 229910052783 alkali metal Inorganic materials 0.000 description 3
- 150000002191 fatty alcohols Chemical class 0.000 description 3
- 238000002360 preparation method Methods 0.000 description 3
- 239000011814 protection agent Substances 0.000 description 3
- 159000000000 sodium salts Chemical class 0.000 description 3
- 239000007787 solid Substances 0.000 description 3
- AZQWKYJCGOJGHM-UHFFFAOYSA-N 1,4-benzoquinone Chemical compound O=C1C=CC(=O)C=C1 AZQWKYJCGOJGHM-UHFFFAOYSA-N 0.000 description 2
- YASYEJJMZJALEJ-UHFFFAOYSA-N Citric acid monohydrate Chemical compound O.OC(=O)CC(O)(C(O)=O)CC(O)=O YASYEJJMZJALEJ-UHFFFAOYSA-N 0.000 description 2
- QIGBRXMKCJKVMJ-UHFFFAOYSA-N Hydroquinone Chemical compound OC1=CC=C(O)C=C1 QIGBRXMKCJKVMJ-UHFFFAOYSA-N 0.000 description 2
- 108091005804 Peptidases Proteins 0.000 description 2
- 239000004365 Protease Substances 0.000 description 2
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 2
- BGRWYDHXPHLNKA-UHFFFAOYSA-N Tetraacetylethylenediamine Chemical compound CC(=O)N(C(C)=O)CCN(C(C)=O)C(C)=O BGRWYDHXPHLNKA-UHFFFAOYSA-N 0.000 description 2
- 150000001298 alcohols Chemical class 0.000 description 2
- 229910052910 alkali metal silicate Inorganic materials 0.000 description 2
- 150000001340 alkali metals Chemical class 0.000 description 2
- 125000000217 alkyl group Chemical group 0.000 description 2
- 239000003945 anionic surfactant Substances 0.000 description 2
- 238000006243 chemical reaction Methods 0.000 description 2
- 229960002303 citric acid monohydrate Drugs 0.000 description 2
- 238000004140 cleaning Methods 0.000 description 2
- 239000008187 granular material Substances 0.000 description 2
- ZFSLODLOARCGLH-UHFFFAOYSA-N isocyanuric acid Chemical compound OC1=NC(O)=NC(O)=N1 ZFSLODLOARCGLH-UHFFFAOYSA-N 0.000 description 2
- 229910052757 nitrogen Inorganic materials 0.000 description 2
- 239000007800 oxidant agent Substances 0.000 description 2
- 239000012188 paraffin wax Substances 0.000 description 2
- 229920001296 polysiloxane Polymers 0.000 description 2
- 239000000843 powder Substances 0.000 description 2
- 230000002441 reversible effect Effects 0.000 description 2
- 229910000029 sodium carbonate Inorganic materials 0.000 description 2
- 229910052723 transition metal Inorganic materials 0.000 description 2
- GHPCICSQWQDZLM-UHFFFAOYSA-N 1-(4-chlorophenyl)sulfonyl-1-methyl-3-propylurea Chemical compound CCCNC(=O)N(C)S(=O)(=O)C1=CC=C(Cl)C=C1 GHPCICSQWQDZLM-UHFFFAOYSA-N 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
- CIEZZGWIJBXOTE-UHFFFAOYSA-N 2-[bis(carboxymethyl)amino]propanoic acid Chemical compound OC(=O)C(C)N(CC(O)=O)CC(O)=O CIEZZGWIJBXOTE-UHFFFAOYSA-N 0.000 description 1
- XSVSPKKXQGNHMD-UHFFFAOYSA-N 5-bromo-3-methyl-1,2-thiazole Chemical compound CC=1C=C(Br)SN=1 XSVSPKKXQGNHMD-UHFFFAOYSA-N 0.000 description 1
- 102000013142 Amylases Human genes 0.000 description 1
- 108010065511 Amylases Proteins 0.000 description 1
- 102000005575 Cellulases Human genes 0.000 description 1
- 108010084185 Cellulases Proteins 0.000 description 1
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 1
- KRKNYBCHXYNGOX-UHFFFAOYSA-K Citrate Chemical compound [O-]C(=O)CC(O)(CC([O-])=O)C([O-])=O KRKNYBCHXYNGOX-UHFFFAOYSA-K 0.000 description 1
- 235000013162 Cocos nucifera Nutrition 0.000 description 1
- 244000060011 Cocos nucifera Species 0.000 description 1
- LEVWYRKDKASIDU-QWWZWVQMSA-N D-cystine Chemical compound OC(=O)[C@H](N)CSSC[C@@H](N)C(O)=O LEVWYRKDKASIDU-QWWZWVQMSA-N 0.000 description 1
- QXNVGIXVLWOKEQ-UHFFFAOYSA-N Disodium Chemical class [Na][Na] QXNVGIXVLWOKEQ-UHFFFAOYSA-N 0.000 description 1
- KCXVZYZYPLLWCC-UHFFFAOYSA-N EDTA Chemical compound OC(=O)CN(CC(O)=O)CCN(CC(O)=O)CC(O)=O KCXVZYZYPLLWCC-UHFFFAOYSA-N 0.000 description 1
- IAYPIBMASNFSPL-UHFFFAOYSA-N Ethylene oxide Chemical compound C1CO1 IAYPIBMASNFSPL-UHFFFAOYSA-N 0.000 description 1
- 229920001503 Glucan Polymers 0.000 description 1
- HNDVDQJCIGZPNO-YFKPBYRVSA-N L-histidine Chemical compound OC(=O)[C@@H](N)CC1=CN=CN1 HNDVDQJCIGZPNO-YFKPBYRVSA-N 0.000 description 1
- 102000004882 Lipase Human genes 0.000 description 1
- 108090001060 Lipase Proteins 0.000 description 1
- 239000004367 Lipase Substances 0.000 description 1
- CERQOIWHTDAKMF-UHFFFAOYSA-N Methacrylic acid Chemical compound CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 description 1
- QPCDCPDFJACHGM-UHFFFAOYSA-N N,N-bis{2-[bis(carboxymethyl)amino]ethyl}glycine Chemical compound OC(=O)CN(CC(O)=O)CCN(CC(=O)O)CCN(CC(O)=O)CC(O)=O QPCDCPDFJACHGM-UHFFFAOYSA-N 0.000 description 1
- 102000035195 Peptidases Human genes 0.000 description 1
- 102100037486 Reverse transcriptase/ribonuclease H Human genes 0.000 description 1
- KEAYESYHFKHZAL-UHFFFAOYSA-N Sodium Chemical compound [Na] KEAYESYHFKHZAL-UHFFFAOYSA-N 0.000 description 1
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 1
- 239000000061 acid fraction Substances 0.000 description 1
- 239000013543 active substance Substances 0.000 description 1
- 150000007824 aliphatic compounds Chemical class 0.000 description 1
- 150000003973 alkyl amines Chemical class 0.000 description 1
- 125000004422 alkyl sulphonamide group Chemical group 0.000 description 1
- 150000001408 amides Chemical class 0.000 description 1
- 150000001413 amino acids Chemical class 0.000 description 1
- 150000003863 ammonium salts Chemical class 0.000 description 1
- 239000002280 amphoteric surfactant Substances 0.000 description 1
- 235000019418 amylase Nutrition 0.000 description 1
- 229940025131 amylases Drugs 0.000 description 1
- LBPABMFHQYNGEB-UHFFFAOYSA-N benzene;2h-triazole Chemical compound C=1C=NNN=1.C1=CC=CC=C1 LBPABMFHQYNGEB-UHFFFAOYSA-N 0.000 description 1
- 150000003857 carboxamides Chemical class 0.000 description 1
- 239000003093 cationic surfactant Substances 0.000 description 1
- 239000000460 chlorine Substances 0.000 description 1
- 229910052801 chlorine Inorganic materials 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 238000002425 crystallisation Methods 0.000 description 1
- 230000008025 crystallization Effects 0.000 description 1
- 229960003067 cystine Drugs 0.000 description 1
- 150000004985 diamines Chemical class 0.000 description 1
- 150000001991 dicarboxylic acids Chemical class 0.000 description 1
- 150000004683 dihydrates Chemical class 0.000 description 1
- RXCBCUJUGULOGC-UHFFFAOYSA-H dipotassium;tetrafluorotitanium;difluoride Chemical compound [F-].[F-].[F-].[F-].[F-].[F-].[K+].[K+].[Ti+4] RXCBCUJUGULOGC-UHFFFAOYSA-H 0.000 description 1
- 238000004090 dissolution Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- RTZKZFJDLAIYFH-UHFFFAOYSA-N ether Substances CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 1
- 150000002170 ethers Chemical class 0.000 description 1
- 150000004673 fluoride salts Chemical class 0.000 description 1
- 238000009472 formulation Methods 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- HNDVDQJCIGZPNO-UHFFFAOYSA-N histidine Natural products OC(=O)C(N)CC1=CN=CN1 HNDVDQJCIGZPNO-UHFFFAOYSA-N 0.000 description 1
- 230000002209 hydrophobic effect Effects 0.000 description 1
- 239000004569 hydrophobicizing agent Substances 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-M hydroxide Chemical compound [OH-] XLYOFNOQVPJJNP-UHFFFAOYSA-M 0.000 description 1
- 150000004679 hydroxides Chemical class 0.000 description 1
- 230000002401 inhibitory effect Effects 0.000 description 1
- 239000011872 intimate mixture Substances 0.000 description 1
- 235000019421 lipase Nutrition 0.000 description 1
- FPYJFEHAWHCUMM-UHFFFAOYSA-N maleic anhydride Chemical compound O=C1OC(=O)C=C1 FPYJFEHAWHCUMM-UHFFFAOYSA-N 0.000 description 1
- 150000002696 manganese Chemical class 0.000 description 1
- 229940099596 manganese sulfate Drugs 0.000 description 1
- 239000011702 manganese sulphate Substances 0.000 description 1
- 235000007079 manganese sulphate Nutrition 0.000 description 1
- SQQMAOCOWKFBNP-UHFFFAOYSA-L manganese(II) sulfate Chemical compound [Mn+2].[O-]S([O-])(=O)=O SQQMAOCOWKFBNP-UHFFFAOYSA-L 0.000 description 1
- 239000003595 mist Substances 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 150000002763 monocarboxylic acids Chemical class 0.000 description 1
- 150000004682 monohydrates Chemical class 0.000 description 1
- 230000007935 neutral effect Effects 0.000 description 1
- 238000006386 neutralization reaction Methods 0.000 description 1
- MGFYIUFZLHCRTH-UHFFFAOYSA-N nitrilotriacetic acid Chemical compound OC(=O)CN(CC(O)=O)CC(O)=O MGFYIUFZLHCRTH-UHFFFAOYSA-N 0.000 description 1
- QJGQUHMNIGDVPM-UHFFFAOYSA-N nitrogen group Chemical group [N] QJGQUHMNIGDVPM-UHFFFAOYSA-N 0.000 description 1
- 231100000252 nontoxic Toxicity 0.000 description 1
- 230000003000 nontoxic effect Effects 0.000 description 1
- 238000006384 oligomerization reaction Methods 0.000 description 1
- 150000007524 organic acids Chemical class 0.000 description 1
- 235000005985 organic acids Nutrition 0.000 description 1
- 150000004967 organic peroxy acids Chemical class 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 229960003330 pentetic acid Drugs 0.000 description 1
- 239000002304 perfume Substances 0.000 description 1
- 229920000151 polyglycol Polymers 0.000 description 1
- 239000010695 polyglycol Substances 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 150000004760 silicates Chemical class 0.000 description 1
- 239000000377 silicon dioxide Substances 0.000 description 1
- 239000000344 soap Substances 0.000 description 1
- 235000011182 sodium carbonates Nutrition 0.000 description 1
- 239000012418 sodium perborate tetrahydrate Substances 0.000 description 1
- IBDSNZLUHYKHQP-UHFFFAOYSA-N sodium;3-oxidodioxaborirane;tetrahydrate Chemical compound O.O.O.O.[Na+].[O-]B1OO1 IBDSNZLUHYKHQP-UHFFFAOYSA-N 0.000 description 1
- MWNQXXOSWHCCOZ-UHFFFAOYSA-L sodium;oxido carbonate Chemical compound [Na+].[O-]OC([O-])=O MWNQXXOSWHCCOZ-UHFFFAOYSA-L 0.000 description 1
- 239000011343 solid material Substances 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
- 239000003760 tallow Substances 0.000 description 1
- 239000002562 thickening agent Substances 0.000 description 1
- 150000003624 transition metals Chemical class 0.000 description 1
- 150000003626 triacylglycerols Chemical class 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
- 239000001993 wax Substances 0.000 description 1
- 150000003751 zinc Chemical class 0.000 description 1
- 229910052725 zinc Inorganic materials 0.000 description 1
- 239000011701 zinc Substances 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
- C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
- 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
- C11D17/0091—Dishwashing 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
- C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
- C11D3/16—Organic compounds
- C11D3/20—Organic compounds containing oxygen
- C11D3/2075—Carboxylic acids-salts thereof
- C11D3/2082—Polycarboxylic acids-salts thereof
-
- C—CHEMISTRY; METALLURGY
- C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
- C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
- C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
- C11D3/16—Organic compounds
- C11D3/20—Organic compounds containing oxygen
- C11D3/2075—Carboxylic acids-salts thereof
- C11D3/2086—Hydroxy carboxylic acids-salts thereof
Definitions
- the invention relates to a method for producing low-alkaline dishwasher tablets from a builder component based on polycarboxylic acids and their salts.
- European dishwashing detergents are known from European application EP 530635, which contain sodium citrate and citric acid as the builder system and non-ionic surfactants, enzymes and thickeners as additives but no alkalinity carriers such as soda or hydrogen carbonate.
- low alkaline agents for machine cleaning of dishes which contain sodium citrate, alkali hydrogen carbonate, a bleaching agent as an essential component. tel, a bleach activator and common additives such as enzymes and the like.
- the agents mentioned there are described as granulated powders.
- the application also provides for the use of citric acid (for the partial replacement of sodium citrate). However, since water is present in the manufacturing process described, a chemical reaction takes place during the manufacturing process, so that ultimately citric acid is not present in the agents described there in addition to the bicarbonate.
- a water softener tablet is known from European patent application EP 628627 A1, which contains citrate and / or citric acid in addition to a polymer which acts as a softener and further auxiliaries. Sodium carbonate or sodium hydrogen carbonate is mentioned among the other auxiliaries. It is intended that the neutralization reaction which begins upon ingress of water will destroy the tablet and dissolve it rapidly.
- the tablet can also contain paraffin in amounts of up to 0.2% by weight, however the person skilled in the art will infer from this document that poor dissolution behavior must be prevented, i.e. the tablet is also soluble in cold water and would dissolve completely in the pre-wash cycle of a dishwasher and then no longer be available for the main wash cycle.
- a machine dishwashing detergent which contains citric acid as well as percarbonate.
- the citric acid is coated twice.
- the aim of the process according to this application is to adjust the dishwashing detergent which is used as granules in the main wash cycle so that the alkaline constituents dissolve faster than the acid constituents and thus the washing liquor undergoes a gradual shift in pH from strongly alkaline to neutral.
- tablets are required to be unbreakable and easy to manufacture. Since tablets of the type mentioned are not used in the detergent dispenser, but are freely placed in the interior of the dishwasher, they must be such that only a small part of the detergent dissolves in the pre-rinse cycle operated with cold water.
- the surfactants in cooperation with the hydrophobizing agent, protect the polycarboxylic acid or its sodium salt against the ingress of water at low temperatures, but that this protection no longer exists when warm water is admitted and that the tablet disintegrates the onset of reaction of the polycarboxylic acid with alkali carbonate or alkali hydrogen carbonate is accelerated.
- the invention therefore relates to a process for the production of a machine dishwashing detergent in tablet form, containing polycarboxylic acids and their salts as a builder component, alkalinity carriers, bleaching agents, surfactants and water repellents and, if desired, customary additives, characterized in that the polycarboxylic acid and its salts are in encloses a first treatment stage with a liquid phase of surfactants and hydrophobicizing agent, then adds the remaining constituents in a second treatment stage and finally compresses the mixture into tablets.
- the polycarboxylic acid or its sodium salt and, if desired, further components for example: a bleaching agent based on chlorine or on oxygen, initially with a liquid preparation, which in any case is a hydrophobizing agent, if desired also contains a surfactant.
- a liquid preparation which in any case is a hydrophobizing agent, if desired also contains a surfactant.
- the solid constituents are expediently placed in a mixer and the liquid constituents are added individually or in succession in any order.
- a liquid mixture of surfactant and hydrophobic agent can be used, but the individual components can also be melted and then added.
- the liquid component can expediently be used in molten form and solidify under normal conditions.
- the purpose of this process step is to encase the solid material with the liquid, which means that the components are enclosed, hydrophobicized and thus not easily accessible to water.
- Water-insoluble, oily or solid non-toxic organic substances are used as water repellents in the process according to the invention.
- Particularly suitable here are paraffins with melting points below the working temperature of dishwashers, but also triglycerides and / or M oleochemical derivatives such as fatty alcohols, fatty alcohol ethers and the like.
- the melting range of these substances is preferably between 40 and 60 ° C.
- the mixture of the surfactants with the hydrophobizing agents has a melting point above room temperature. Therefore, surfactants with melting points above 20 ° C can be used, in particular between 40 and 60 C C.
- the process according to the invention provides that the mixture treated in this way by the other constituents, e.g. due to the alkaline components such as alkali carriers and the small quantities such as e.g. Bleach activators, enzymes, corrosion protection agents, silver protection agents, foam inhibitors and the like, and to compress the mixture thus obtained into tablets in a manner known per se.
- the alkaline components such as alkali carriers
- the small quantities such as e.g. Bleach activators, enzymes, corrosion protection agents, silver protection agents, foam inhibitors and the like
- polycarboxylic acids are primarily polyfunctional hydroxycarboxylic acids, in particular citric acid.
- suitable polycarboxylic acids are sugar acids, mono- or dihydroxysuccinic acids, tartaric acids and related low molecular weight organic polycarboxylic acids.
- copolymers based on unsaturated mono- or dicarboxylic acids such as acrylic acid, methacrylic acid or maleic anhydride, as are generally known in the field of detergents and cleaning agents.
- the sodium or potassium salts are occasionally used as salts, and ammonium salts are also occasionally used. These salts can be anhydrous or as a hydrate.
- a particularly preferred mixture in the sense of the invention consists of citric acid or its hydrate with trisodium citrate, which can be present in particular as a dihydrate. These mixtures should contain an acid fraction of more than 5% by weight, in particular more than 30% by weight of anhydrous acid. Instead of the mixture mentioned, mono- or disodium salt of citric acid and mixtures of these salts with citric acid can also be used.
- the person skilled in the art must ensure that he chooses the amounts of polycarboxylic acids, their sodium salts and of the alkali metal carbonates or bicarbonates so that the resulting agent has a pH in the solution in percent by weight alkaline (from 8 to 9.5). If the salt of the polycarboxylic acid is completely dispensed with, corresponding amounts of alkali carbonate or alkali hydrogen carbonate must be present.
- the agents according to the invention can also contain nitrogen-containing polycarboxylic acids such as ethylenediaminetetraacetic acid, nitrilotriacetic acid, diethylenetriaminepentaacetic acid or triethylenetetraminehexaacetic acid or methylglycinediacetic acid and the like.
- nitrogen-containing polycarboxylic acids such as ethylenediaminetetraacetic acid, nitrilotriacetic acid, diethylenetriaminepentaacetic acid or triethylenetetraminehexaacetic acid or methylglycinediacetic acid and the like.
- the oxidation products of polyglucosans mentioned in DE-A 4228786 can also be used.
- the process according to the invention is usually carried out in a mixer, preferably in order to be able to carry out individual mixing steps in succession, as required, in a batch mixer. It is preferred not to add water.
- the mixer has the task of producing an intimate mixture of the individual components. Suitable mixers are, for example, Eirich (R> mixers of the R or RV series, manufactured by Maschinenfabrik Gustav Eirich, Hardheim, Germany, the Fukae (R) FS-G mixers, manufactured by Fukal Powertech Kogyo Co. Japan, the Lödige (R) FM , KM or CB mixer, manufactured by Lödige Maschinenbau GmbH, Paderborn, Germany or the Drais (R) series T or KT, manufactured by Drais Maschinene GmbH, Mannheim, Germany.
- Alkali metal carriers are alkali metal carbonates, alkali metal hydrogen carbonates, alkali metal sesquicarbonates, alkali silicates, alkali metal silicates and mixtures of the aforementioned substances.
- Sodium sequicarbonates While the carbonts or bicarbonates mentioned are compulsory constituents in the process according to the invention, silicates such as, for example, metasilicates are only used if the pH value needs to be raised. You can therefore only find them in quantities from 0 to 15, preferably from 2 to 10% by weight. Hydroxides can also be used, but only in the amount that the total pH of the preparation does not rise above 10 and preferably not above 9.5.
- the preparations according to the invention also contain surfactants.
- surfactants in principle, anionic surfactants, amphoteric surfactants or also cationic surfactants can be used, but nonionic surfactants are preferred, and among them nonionic surfactants which are liquid at room temperature.
- nonionic surfactants are adducts of preferably 2 to 20 moles of ethylene oxide with 1 mole of an aliphatic compound having essentially 10 to 20 carbon atoms from the group of alcohols, carboxylic acids, long-chain alkylamines, carboxamides or alkylsulfonamides.
- nonionic surfactants non-complete or incomplete water-soluble polyglycol ethers of long-chain alcohols with 2 to 7 ethylene glycol ether residues in the molecule are particularly important when they are used together with water-soluble nonionic or anionic surfactants.
- alkyl polyglycosides of the general formula RO- (G) x can be used as nonionic surfactants, in which R denotes a primary straight-chain or branched aliphatic radical having 8 to 22, in particular 8 to 14, 12 to 18 carbon atoms , G stands for a glycose unit with 5 to 6 carbon atoms and the degree of oligomerization x is between 1 and 10, preferably between 1.1 and 1.7.
- Alkyl glucamides can also be used. These are the amides of carboxylic acids with 8 to 22 carbon atoms and N-alkylamino sugars, especially N-methylglucamide.
- bleaching agents that can be used are, for example, peroxyearbonate (Na 2 CO 3 .1, 5 H 2 O 2 ) or peracidic salts of organic acids, such as perbenzoates or salts of diperdodecanedioic acid.
- peroxyearbonate Na 2 CO 3 .1, 5 H 2 O 2
- peracidic salts of organic acids such as perbenzoates or salts of diperdodecanedioic acid.
- the bleaches mentioned are preferably used directly in the process according to the invention with the polycarboxylic acid salts at the start of the process.
- Suitable bleach activators for these oxidizing agents are in particular the N-acrylic or O-acyl compounds forming with H 2 O 2 organic peracids, preferably N, N'-tetraacylated diamines such as N, N, N ', N'- Tetraacetylethylenediamine.
- the preliminary products are usually mixed with the bleaching agents and other constituents in amounts of about 7: 3 to 9: 1.
- the oxygen-based oxidizing agent content of the ready-made dishwashing agents is preferably about 5% by weight to 15% by weight, in particular in combination with 1% by weight to 10% by weight, in particular 2% by weight to 5 % By weight of a bleach activator.
- a preferred embodiment of the tablets is prepared by enclosing 20 to 60 parts by weight of polycarboxylic acids or their salts with 2 to 5 parts of surfactants and water repellents in the presence of up to 20 parts by weight of oxygen bleach and then 5 to 50 parts of alkali metal carbonate and / or hydrogen carbonate as well as other usual components.
- other active substances which are usually only present in small amounts, can be added to the pre-products according to the invention.
- the total amount of all these substances is preferably 5 to 10% by weight, based on the final cleaning agent.
- These small components include, for example, foam inhibitors, fragrances, dyes, stabilizers and enzymes of the type of proteases, amylases, lipases and / or cellulases and water which is not bound as water of crystallization or is associated with the constituents in a similarly solid form.
- the enzymes can be adsorbed onto carrier substances in a conventional manner and / or embedded in coating substances and are preferably used in amounts of not more than 5% by weight, in particular 2 to 4% by weight.
- Suitable non-surfactant-containing and preferably used foam inhibitors are organopolysiloxanes and their mixtures with microfine, optionally signed silica.
- the foam-inhibiting use of long-chain soaps is also possible.
- Mixtures of different foam inhibitors can also be suitable, for example those composed of silicones and paraffins or waxes. These foam inhibitors are preferably bound to a granular, water-soluble or dispersible carrier substance.
- silver protection agents in particular inorganic transition metal salts, for example manganese salts such as manganese sulfate, if desired in combination with fluorides, potassium hexafluorotitanate and the like, inorganic transition metal complexes, nitrogen-containing heterocycles such as benzene triazole or isocyanuric acid, natural amino acids such as cystine, histidine reversible organic redox systems such as quinone / hydroquinone and / or reversible inorganic redox systems such as Fe 2+ / Fe 3+ .
- substances to prevent glass corrosion can be used, for example zinc salts or zinc (hydroxide).
- the preliminary products produced by the process according to the invention are usually processed into tablets.
- the preliminary products with the other constituents mentioned as a mixture by means of conventional tablet presses, for example eccentric presses or rotary presses, with pressures in the range of 200. 10 5 Pa to 1 500. 10 5 Pa pressed.
- break-resistant tablets are obtained which, under application conditions, dissolve sufficiently quickly and have a beige strength of normally over 150 N.
- a tablet produced in this way has a weight of 15 g to 40 g, in particular 20 g to 30 g, with a diameter of 35 mm up to 40 mm.
- non-ionic surfactant (coconut fatty alcohol 4 EO) 0.75 kg
- Enzymes prote, amlyase mixture 1: 1) 1.8 kg,
- the approx. 950 g / l heavy mixture was compressed on a Korsch eccentric press type EKIV to cylindrical, 25 g heavy tablets with a diameter of 34 mm and a height of 17.6 mm with a compressive force of 48 KN. Immediately after production, the tablets could be broken under a wedge-shaped load of 135 N. After 1 day of storage, the load leading to breakage increased to 600 N.
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Abstract
In a process for producing dishwasher detergent in tablet form containing polycarboxylic acids and their salts as builders, alkalinity vehicles, bleaches, tensides and water-repellent finishing agents and, where desired, conventional additives, the solubility at high temperature and the breakage resistance of the tablets is to be improved. This is achieved in that the polycarboxylic acid and its salts are surrounded in a first stage treatment by a liquid phase of tensides and water-repellent finishing agents, whereafter in a second treatment stage the remaining components are added and finally the mixture is pressed into tablet form.
Description
Verfahren zur Herstellung von Geschirrspülmitteltabletten Process for the production of dishwasher tablets
Die Erfindung betrifft ein Verfahren zur Herstellung von niedrig alkalischen Ge¬ schirrspülmitteltabletten aus einer Builderkomponente auf Basis von Polycar¬ bonsäuren und ihren Salzen.The invention relates to a method for producing low-alkaline dishwasher tablets from a builder component based on polycarboxylic acids and their salts.
Bei der Geschirrreinigung in Haushaltsgeschirrspülmaschinen haben in den letzten Jahren Produkte auf Basis von Polycarbonsäuren bzw. ihren Salzen an Bedeutung gewonnen, da sie bei vergleichsweise niedrigerem Anwendungs- pH gute Reinigungsergebnisse liefern. Derartige Mittel werden üblicherweise als granulierte Pulver oder als Tabletten im Markt angeboten.In recent years, products based on polycarboxylic acids or their salts have become more important for dishwashing in household dishwashers, since they deliver good cleaning results with a comparatively lower application pH. Such agents are usually offered on the market as granulated powders or as tablets.
Aus der europäischen Anmeldung EP 530635 sind neutrale Geschirrspülmittel bekannt, die als Buildersystem Natriumeitrat und Citronensäure enthalten und als Zusätze nichtionische Tenside, Enzyme und Verdickungsmittel aber keine Alkalitätsträger, wie beispielsweise Soda oder Hydrogencarbonat.European dishwashing detergents are known from European application EP 530635, which contain sodium citrate and citric acid as the builder system and non-ionic surfactants, enzymes and thickeners as additives but no alkalinity carriers such as soda or hydrogen carbonate.
Aus der deutschen Offenlegungsschrift DE 4232170 der Anmelderin sind nie¬ deralkalische Mittel für das maschinelle Reinigen von Geschirr bekannt, die als wesentliche Komponente Natriumeitrat, Alkalihydrogencarbonat, ein Bleichmit-
tel, ein Bleichaktivator und übliche Zusatzstoffe wie Enzyme und dergleichen enthalten. Die dort genannten Mittel werden als granulierte Pulver beschrieben. Die Anmeldung sieht auch die Verwendung von Citronensäure (zum teiiweisen Ersatz von Natriumeitrat) vor. Da jedoch bei dem beschriebenen Herstellverfahren Wasser mitzugegen ist, findet bei der Herstellung eine chemische Reaktion statt, so daß in den dort beschriebenen Mitteln letztendlich nicht Citronensäure neben dem Hydrogencarbonat vorliegt.From the German patent application DE 4232170 of the applicant, low alkaline agents for machine cleaning of dishes are known which contain sodium citrate, alkali hydrogen carbonate, a bleaching agent as an essential component. tel, a bleach activator and common additives such as enzymes and the like. The agents mentioned there are described as granulated powders. The application also provides for the use of citric acid (for the partial replacement of sodium citrate). However, since water is present in the manufacturing process described, a chemical reaction takes place during the manufacturing process, so that ultimately citric acid is not present in the agents described there in addition to the bicarbonate.
Aus der europäischen Patentanmeldung EP 628627 A1 ist eine Wasserenthärtertablette bekannt, die Zitrat und/oder Citronensäure neben einem als Enthärter wirksamen Polymer sowie weitere Hilfsstoffe enthält. Unter den weiteren Hilfsstoffen ist Natriumcarbonat bzw. Natriumhydrogencarbonat genannt. Es ist beabsichtigt, daß durch die bei Wasserzutritt einsetzende Neutralisationsreaktion die Tablette zerstört wird und sich rasch auflöst. Die Tablette kann auch Paraffin in Mengen bis zu 0,2 Gew.-% enthalten, jedoch entnimmt der Fachmann diesem Dokument, daß schlechtes Auflöseverhalten zu verhindern sei, d.h. die Tablette ist auch in kaltem Wasser löslich und würde im Vorspülgang einer Geschirrspülmaschine sich völlig auflösen und dann für den Hauptspülgang nicht mehr zur Verfügung stehen.A water softener tablet is known from European patent application EP 628627 A1, which contains citrate and / or citric acid in addition to a polymer which acts as a softener and further auxiliaries. Sodium carbonate or sodium hydrogen carbonate is mentioned among the other auxiliaries. It is intended that the neutralization reaction which begins upon ingress of water will destroy the tablet and dissolve it rapidly. The tablet can also contain paraffin in amounts of up to 0.2% by weight, however the person skilled in the art will infer from this document that poor dissolution behavior must be prevented, i.e. the tablet is also soluble in cold water and would dissolve completely in the pre-wash cycle of a dishwasher and then no longer be available for the main wash cycle.
Aus der internationalen Anmeldung WO 95/12657 ist ein maschinelle Geschirrspülmittel bekannt, das neben Percarbonat auch Citronensäure enthält. Die Citronensäure wird doppelt umhüllt (gecoated). Ziel des Verfahrens gemäß dieser Anmeldung ist es, das Geschirrspülmittel, das als Granulat im Hauptspülgang zur Anwendung kommt, so einzustellen, daß die alkalischen Bestandteile sich schneller lösen als die sauren Bestandteile und
somit die Spülflotte einer allmählichen Verschiebung des pH-Werts von stark alkalischen nach neutralen durchläuft.From the international application WO 95/12657 a machine dishwashing detergent is known which contains citric acid as well as percarbonate. The citric acid is coated twice. The aim of the process according to this application is to adjust the dishwashing detergent which is used as granules in the main wash cycle so that the alkaline constituents dissolve faster than the acid constituents and thus the washing liquor undergoes a gradual shift in pH from strongly alkaline to neutral.
Aufgrund der besseren Handhabbarkeit ist es auf dem hier betroffenen Arbeitsgebiet für den Verbraucher von immer größerem Interesse, die Mittel in Form von Tabletten oder Preßlingen angeboten zu bekommen. An die Tabletten wird dabei die Anforderung gestellt, bruchfest und leicht herstellbar zu sein. Da Tabletten der genannten Art nicht über das Reinigungsmittelfach zur Anwendung gelangen, sondern frei in den Innenraum der Geschirrspülmaschine gegeben werden, müssen sie so beschaffen sein, daß bei dem mit kaltem Wasser betriebenen Vorspülgang nur geringe Teile des Reinigers in Lösung gehen.Because of the better manageability, it is of increasing interest for the consumer in the area concerned here to be offered the agents in the form of tablets or tablets. The tablets are required to be unbreakable and easy to manufacture. Since tablets of the type mentioned are not used in the detergent dispenser, but are freely placed in the interior of the dishwasher, they must be such that only a small part of the detergent dissolves in the pre-rinse cycle operated with cold water.
Andererseits wird aber erwartet, daß im Hauptspülgang das Reinigungsmittel vollständig und möglichst schnell freigesetzt werden kann, damit es insbeson¬ dere bei verkürzten Taktzeiten der Maschinen seine Wirkung entfaltet. Vor dem Hintergrund dieses Standes der Technik war es Aufgabe der Erfindung, niederalkalische Geschirrspülmitteltabletten zur Verfügung zu stellen, die bei hinreichender Bruchstabilität in kaltem Wasser nur gering löslich sind, jedoch in warmen Wasser schnell und vollständig in Lösung gehen.On the other hand, however, it is expected that the cleaning agent can be released completely and as quickly as possible in the main rinse cycle, so that it has its effect, in particular, with shortened cycle times of the machines. Against the background of this prior art, it was an object of the invention to provide lower-alkaline dishwashing detergent tablets which are only slightly soluble in cold water with sufficient breaking stability, but which dissolve quickly and completely in warm water.
Ohne die Erfindung auf eine Theorie einzuschränken wird vermutet, daß die Tenside in Zusammenwirkung mit dem Hydrophobiermittel die Polycarbonsäure bzw. ihr Natriumsalz gegen Wasserzutritt bei tiefen Temperaturen schützt, daß jedoch bei Zutritt von warmen Wasser dieser Schutz nicht mehr besteht und daß der Zerfall der Tablette durch die einsetzende Reaktion der Polycarbonsäure mit Alkalicarbonat oder Alkalihydrogencarbonat stärkt beschleunigt wird.
Gegenstand der Erfindung ist daher ein Verfahren zur Herstellung eines ma¬ schinellen Geschirrspülmittels in Tablettenform, enthaltend Polycarbonsäuren und ihre Salze als Builderkomponente, Alkalitätsträger, Bleichmittel, Tenside und Hydrophobierungsmittel sowie gewünschtenfalls übliche Zusatzstoffe, da¬ durch gekennzeichnet, daß man die Polycarbonsäure und ihre Salze in einer ersten Behandlungsstufe mit einer Flüssigphase aus Tensiden und Hydropho¬ bierungsmittel umschließt, sodann in einer zweiten Behandlungsstufe die restlichen Bestandteile hinzufügt und schließlich die Mischung zu Tabletten verpreßt.Without restricting the invention to any theory, it is assumed that the surfactants, in cooperation with the hydrophobizing agent, protect the polycarboxylic acid or its sodium salt against the ingress of water at low temperatures, but that this protection no longer exists when warm water is admitted and that the tablet disintegrates the onset of reaction of the polycarboxylic acid with alkali carbonate or alkali hydrogen carbonate is accelerated. The invention therefore relates to a process for the production of a machine dishwashing detergent in tablet form, containing polycarboxylic acids and their salts as a builder component, alkalinity carriers, bleaching agents, surfactants and water repellents and, if desired, customary additives, characterized in that the polycarboxylic acid and its salts are in encloses a first treatment stage with a liquid phase of surfactants and hydrophobicizing agent, then adds the remaining constituents in a second treatment stage and finally compresses the mixture into tablets.
Im Rahmen des erfindungsgemäßen Verfahrens ist es vorgesehen, die Poly¬ carbonsäure bzw. ihr Natriumsalz und gewünschtenfalls noch weitere Kompo¬ nenten z.B: ein Bleichmittel auf Chlor- oder auf Sauerstoffbasis zunächst mit einer flüssigen Zubereitung, die in jedem Falle ein Hydrophobiermittel, ge¬ wünschtenfalls auch ein Tensid enthält, zu behandeln. Zweckmäßigerweise werden die festen Bestandteile dazu in einen Mischer gegeben und die flüssi¬ gen Bestandteile einzeln oder nacheinander in beliebiger Reihenfolge zugege¬ ben. So kann beispielsweise eine flüssige Mischung aus Tensid und Hy- drohphobiermittel eingesetzt werden, es können jedoch auch die Einzelbe¬ standteile aufgeschmolzen und dann eingetragen werden. Zweck¬ mäßigerweise kann dabei die flüssige Komponente in aufgeschmolzener Form eingesetzt werden und unter Normalbedingungen erstarren. Sinn dieses Verfahrensschrittes ist die Umhüllung des festen Guts mit dem flüssigen, die dazu führt, daß die Bestandteile umschlossen, hydrophobiert und damit wenig schnell für Wasser zugänglich sind.
Als Hydrophobierungsmittel werden in dem erfindungsgemäßen Verfahren was-serunlösliche, öllige oder feste nicht toxische organische Substanzen eingesetzt. Geeignet sind hier insbesondere Paraffine mit Schmelzpunkten unterhalb der Arbeitstemperatur von Geschirrspülmaschinen, aber auch Triglyceride und/oder Mme oleochemischen Derivate wie Fettalkohole, Fettalkoholether und dergleichen. Bevorzugt liegt der Schmelzbereich dieser Substanzen zwischen 40 und 60 °C. Insbesondere ist es bevorzugt, wenn die Mischung der Tenside mit den Hydrophobierungsmitteln einen Schmelzpunkt oberhalb Raumtemperatur aufweist. Daher können auch Tenside mit Schmelzpunkten über 20 °C, insbesondere zwischen 40 und 60 CC eingesetzt werden.Within the scope of the process according to the invention, it is provided that the polycarboxylic acid or its sodium salt and, if desired, further components, for example: a bleaching agent based on chlorine or on oxygen, initially with a liquid preparation, which in any case is a hydrophobizing agent, if desired also contains a surfactant. For this purpose, the solid constituents are expediently placed in a mixer and the liquid constituents are added individually or in succession in any order. For example, a liquid mixture of surfactant and hydrophobic agent can be used, but the individual components can also be melted and then added. The liquid component can expediently be used in molten form and solidify under normal conditions. The purpose of this process step is to encase the solid material with the liquid, which means that the components are enclosed, hydrophobicized and thus not easily accessible to water. Water-insoluble, oily or solid non-toxic organic substances are used as water repellents in the process according to the invention. Particularly suitable here are paraffins with melting points below the working temperature of dishwashers, but also triglycerides and / or M oleochemical derivatives such as fatty alcohols, fatty alcohol ethers and the like. The melting range of these substances is preferably between 40 and 60 ° C. In particular, it is preferred if the mixture of the surfactants with the hydrophobizing agents has a melting point above room temperature. Therefore, surfactants with melting points above 20 ° C can be used, in particular between 40 and 60 C C.
Das erfindungsgemäße Verfahren sieht vor, die so behandelte Mischung durch die anderen Bestandteile, z.B. durch die alkalischen Bestandteile wie Alkaliträger und durch die mengenmäßig kleinen Bestandteile wie z.B. Bleichaktivatoren,, Enzyme, Korrosionsschutzmittel, Silberschutzmittel, Schauminhibitoren und dergleichen zu ergänzen und die so erhaltene Mischung in an sich bekannter Weise zu Tabletten zu verpressen.The process according to the invention provides that the mixture treated in this way by the other constituents, e.g. due to the alkaline components such as alkali carriers and the small quantities such as e.g. Bleach activators, enzymes, corrosion protection agents, silver protection agents, foam inhibitors and the like, and to compress the mixture thus obtained into tablets in a manner known per se.
Aus Polycarbonsäuren werden im Sinne der Erfindung in erster Linie mehrfunktionelle Hydroxycarbonsäuren, insbesondere Citronensäure eingesetzt. Weiter geeignete Polycarbonsäuren sind Zuckersäuren, Mono- bzw. Dihydroxybemsteinsäuren, Weinsäuren und verwandte niedermolekulare organische Polycarbonsäuren. Weiterhin geeignet sind auch Copolymere auf Basis ungesättigter Mono- oder Dicarbonsäuren wie Acrylsaure, Methacrylsäure oder Maleinsäureanhydrrt wie sie allgemein auf dem Gebiet der Wasch- und Reinigungsmittel bekannt sind. Als Salze finden in erster Linie die Natrium- oder Kaliumsalze vereinzelt auch Ammoniumsalze Anwendung.
Diese Salze können wasserfrei oder als Hydrat vorliegen. Eine im Sinne der Erfindung besonders bevorzugte Mischung beseht aus Zitronensäure bzw. deren Hydrat mit Trinatriumcitrat, das insbesondere als Dihydrat vorliegen kann. Diese Mischungen sollen einen Säureanteil von mehr als 5 Gew.-%, insbesondere mehr als 30 Gew.-% wasserfreie Säure enthalten. Anstelle der genannten Mischung können auch Mono- oder Di-Natriumsalz der Zitronensäure sowie Gemische dieser Salze mit Zitronensäure eingesetzt werden.For the purposes of the invention, polycarboxylic acids are primarily polyfunctional hydroxycarboxylic acids, in particular citric acid. Other suitable polycarboxylic acids are sugar acids, mono- or dihydroxysuccinic acids, tartaric acids and related low molecular weight organic polycarboxylic acids. Also suitable are copolymers based on unsaturated mono- or dicarboxylic acids such as acrylic acid, methacrylic acid or maleic anhydride, as are generally known in the field of detergents and cleaning agents. The sodium or potassium salts are occasionally used as salts, and ammonium salts are also occasionally used. These salts can be anhydrous or as a hydrate. A particularly preferred mixture in the sense of the invention consists of citric acid or its hydrate with trisodium citrate, which can be present in particular as a dihydrate. These mixtures should contain an acid fraction of more than 5% by weight, in particular more than 30% by weight of anhydrous acid. Instead of the mixture mentioned, mono- or disodium salt of citric acid and mixtures of these salts with citric acid can also be used.
Bei der Festlegung der Rezeptur der erfindungsgemäßen Mittel, hat der Fach¬ mann darauf zu achten, daß er die Mengen an Polycarbonsäuren, deren Natri¬ umsalzen und an den Alkalicarbonaten bzw. Hydrogencarbonaten so wählt, daß das resultierende Mittel in eingewichtsprozentiger Lösung einen pH im schwach alkalischen (von 8 bis 9,5) aufweist. Wenn also auf das Salz der Polycarbonsäure gänzlich verzichtet wird, müssen entsprechende Mengen an Alkalicarbonat bzw. Alkalihydrogencarbonat zugegen sein. Im allgemeinen hat es sich als günstig erwiesen, von den 20 bis 60 % vorzugsweise 30 bis 50 Gew.-% der Salze der Polycarbonsäuren die in dem Gesamtreiniguπgsmittel vorhanden sein sollen 5 bis 50 Gew.-% gegen Citronensäure auszutauschen und die Menge an Alkalicarbonat bzw. Alkalihydrogencarbonat dazu äquimolekular zu erhöhen. Diese Menge soll im Bereich von 5 bis 50 Gew.-%, vorzugsweise 20 bis 40 Gew -% liegen.When determining the formulation of the agents according to the invention, the person skilled in the art must ensure that he chooses the amounts of polycarboxylic acids, their sodium salts and of the alkali metal carbonates or bicarbonates so that the resulting agent has a pH in the solution in percent by weight alkaline (from 8 to 9.5). If the salt of the polycarboxylic acid is completely dispensed with, corresponding amounts of alkali carbonate or alkali hydrogen carbonate must be present. In general, it has proven to be advantageous to exchange 5 to 50% by weight for citric acid of the 20 to 60%, preferably 30 to 50% by weight, of the salts of the polycarboxylic acids which are to be present in the total cleaning agent and to replace the amount of alkali metal carbonate or To increase the alkali hydrogen carbonate equimolecularly. This amount should be in the range from 5 to 50% by weight, preferably 20 to 40% by weight.
In einer besonders bevorzugten Ausführungsform der Erfindung setzt man da¬ her 25 bis 45 Gew.-% Trinatriumcitratdihydrat mit 2 bis 10 Gew.-% Citronensäuremonohydrat ein und gibt 15 bis 30 Gew.-% Natriumhydrogencarbonat sowie 5 bis 10 Gew.-% Natriumcarbonat hinzu.
Außer den genannten Polycarbonsäuren können die erfindungsgemäßen Mittel auch noch stickstoffhaltige Polycarbonsäuren wie Ethylendiamintetra- essigsääure, Nitrilotriessigsäure, Diethylentriaminpentaessigsäure oder Triethylentetraminhexaessigsäure bzw. Methylglycindiessigsäure und dergleichen enthalten. Eingesetzt werden können auch die in der DE-A 4228786 genannten Oxidationsprodukte von Polyglucosanen.In a particularly preferred embodiment of the invention, 25 to 45% by weight of trisodium citrate dihydrate with 2 to 10% by weight of citric acid monohydrate is therefore used, and 15 to 30% by weight of sodium hydrogen carbonate and 5 to 10% by weight of sodium carbonate are added . In addition to the polycarboxylic acids mentioned, the agents according to the invention can also contain nitrogen-containing polycarboxylic acids such as ethylenediaminetetraacetic acid, nitrilotriacetic acid, diethylenetriaminepentaacetic acid or triethylenetetraminehexaacetic acid or methylglycinediacetic acid and the like. The oxidation products of polyglucosans mentioned in DE-A 4228786 can also be used.
Das erfindungsgemäße Verfahren wird üblicherweise in einem Mischer, vor¬ zugsweise um einzelne Mischschritte, wie erforderlich nacheinander durchfüh¬ ren zu können, in einem diskontinuierlich arbeitenden Mischer durchgeführt. Dabei wird bevorzugt auf die Zugabe von Wasser verzichtet. Der Mischer hat die Aufgabe ein inniges Gemenge der einzelnen Bestandteile herzustellen. Geeignete Mischer sind z.B. Eirich (R> Mischer der Serien R oder RV, hergestellt durch Maschinenfabrik Gustav Eirich, Hardheim, Deutschland, die Fukae (R) FS-G Mischer, hergestellt durch Fukal Powertech Kogyo Co. Japan, die Lödige (R) FM, KM oder CB-Mischer, hergestellt durch Lödige Maschinenbau GmbH, Paderborn, Deutschland oder die Drais (R) Serien T oder K-T, hergestellt durch die Drais Werke GmbH, Mannheim, Deutschland.The process according to the invention is usually carried out in a mixer, preferably in order to be able to carry out individual mixing steps in succession, as required, in a batch mixer. It is preferred not to add water. The mixer has the task of producing an intimate mixture of the individual components. Suitable mixers are, for example, Eirich (R> mixers of the R or RV series, manufactured by Maschinenfabrik Gustav Eirich, Hardheim, Germany, the Fukae (R) FS-G mixers, manufactured by Fukal Powertech Kogyo Co. Japan, the Lödige (R) FM , KM or CB mixer, manufactured by Lödige Maschinenbau GmbH, Paderborn, Germany or the Drais (R) series T or KT, manufactured by Drais Werke GmbH, Mannheim, Germany.
In dem erfindungsgemäßen Verfahren werden als weitere Bestandteile Alka¬ liträger zugegeben. Als Alkaliträger gelten Alkalimetallcarbonate, Alkalimetall- hydrogencarbonate, Alkalimetallsesquicarbonate, Alkalisilikate, Alkalimetasili¬ kate und Mischungen der vorgenannten Stoffe. Bevorzugt ist der Einsatz von Natriumcarbonaten bzw. Natriumhydrogencarbonat oderIn the process according to the invention alkali carriers are added as further constituents. Alkali metal carriers are alkali metal carbonates, alkali metal hydrogen carbonates, alkali metal sesquicarbonates, alkali silicates, alkali metal silicates and mixtures of the aforementioned substances. The use of sodium carbonates or sodium hydrogen carbonate or is preferred
Natriumsequicarbonaten. Während die genannten Carbonte bzw. Hydrogencarbonate zwingende Bestandteile im erfindungsgemäßen Verfahren sind, werden Silikate wie beispielsweise Metasilikate nur dann eingesetzt, wenn es gilt den ph-Wert zu heben. Sie finden daher höchstens in Mengen
von 0 bis 15 vorzugsweise von 2 bis 10 Gew.-% Einsatz. Auch Hydroxide können eingesetzt werden, jedoch nur in der Menge, daß der Gesamt-pH der Zubereitung nicht über 10 und vorzugsweise nicht über 9,5 steigt.Sodium sequicarbonates. While the carbonts or bicarbonates mentioned are compulsory constituents in the process according to the invention, silicates such as, for example, metasilicates are only used if the pH value needs to be raised. You can therefore only find them in quantities from 0 to 15, preferably from 2 to 10% by weight. Hydroxides can also be used, but only in the amount that the total pH of the preparation does not rise above 10 and preferably not above 9.5.
Die erfindungsgemäßen Zubereitungen enthalten weiterhin Tenside. Prinzipiell können anionische Tenside, Amphotenside oder auch kationische Tenside eingesetzt werden, bevorzugt sind jedoch nichtionische Tenside und unter diesen wiederum bei Raumtemperatur flüssige nichtionische Tenside.The preparations according to the invention also contain surfactants. In principle, anionic surfactants, amphoteric surfactants or also cationic surfactants can be used, but nonionic surfactants are preferred, and among them nonionic surfactants which are liquid at room temperature.
Als nichtionische Tenside sind vor allem Anlagerungsprodukte von vorzugs¬ weise 2 bis 20 Mol Ethylenoxid an 1 mol einer aliphatischen Verbindung mit im wesentlichen 10 bis 20 Kohlenstoffatomen aus der Gruppe der Alkohole, Car¬ bonsäuren, langkettige Alkylamine, Carbonsäureamide bzw. Alkylsulfonamide von Interesse. Wichtig sind neben den wasserlöslichen Niotensiden aber auch nicht bzw. nicht vollständige wasserlösliche Polyglykolether langkettiger Alko¬ hole mit 2 bis 7 Ethylenglykoletherresten im Molekül insbesondere dann wenn sie zusammen mit wasserlöslichen nichtionischen oder anionschen Tensiden eingesetzt werden. Außerdem können als nichtionische Tenside Alkylpolygly- koside der allgemeinen Formel R-O-(G)x eingesetzt werden in der R einen pri¬ mären geradkettigen oder verzweigten aliphatischen Rest mit 8 bis 22, insbe¬ sondere 8 bis 14, 12 bis 18 C-Atomen bedeutet, G für eine Glykose-Einheit mit 5 bis 6 C-Atomen steht und der Oligomerisierungsgrad x zwischen 1 und 10, vorzugsweise zwischen 1,1 und 1 ,7 liegt. Gleichfalls eingesetzt werden können Alkylglukamide. Es sind dies die Amide aus Carbonsäuren mit 8 bis 22 C-Atomen und N-Alkylaminozuckern insbesondere N-Methylglucamid.Of particular interest as nonionic surfactants are adducts of preferably 2 to 20 moles of ethylene oxide with 1 mole of an aliphatic compound having essentially 10 to 20 carbon atoms from the group of alcohols, carboxylic acids, long-chain alkylamines, carboxamides or alkylsulfonamides. In addition to the water-soluble nonionic surfactants, non-complete or incomplete water-soluble polyglycol ethers of long-chain alcohols with 2 to 7 ethylene glycol ether residues in the molecule are particularly important when they are used together with water-soluble nonionic or anionic surfactants. In addition, alkyl polyglycosides of the general formula RO- (G) x can be used as nonionic surfactants, in which R denotes a primary straight-chain or branched aliphatic radical having 8 to 22, in particular 8 to 14, 12 to 18 carbon atoms , G stands for a glycose unit with 5 to 6 carbon atoms and the degree of oligomerization x is between 1 and 10, preferably between 1.1 and 1.7. Alkyl glucamides can also be used. These are the amides of carboxylic acids with 8 to 22 carbon atoms and N-alkylamino sugars, especially N-methylglucamide.
Unter den als Bleichmittel dienenden, in Wasser H2O2 liefernden Verbindungen haben das Natriumperborat-Tetrahydrat und das
Natriumperborat-Monohydrat besondere Bedeutung. Weitere brauchbare Bleichmittel sind beispielsweise Peroxyearbonat (Na2CO3 . 1 ,5 H2O2) oder persaure Salze organischer Säuren, wie Perbenzoate oder Salze der Diperdodecandisäure. Die genannten Bleichmittel werden in dem erfindungsgemaßen Verfahren bevorzugt direkt mit dem Polycarbonsäuresalzen zu Verfahrensbeginn eingesetzt. Geeignete Bleichaktivatoren für diese Oxidationsmittel sind insbesondere die mit H2O2 or¬ ganische Persäuren bildenden N-Acryl bzw. O-Acyl-Verbindungen, vorzugs¬ weise N,N'-tetraacylierte Diamine wie N,N,N',N'-Tetraacetylethylendiamin.Among the compounds which serve as bleaching agents and produce H 2 O 2 in water, sodium perborate tetrahydrate and Sodium perborate monohydrate of particular importance. Other bleaching agents that can be used are, for example, peroxyearbonate (Na 2 CO 3 .1, 5 H 2 O 2 ) or peracidic salts of organic acids, such as perbenzoates or salts of diperdodecanedioic acid. The bleaches mentioned are preferably used directly in the process according to the invention with the polycarboxylic acid salts at the start of the process. Suitable bleach activators for these oxidizing agents are in particular the N-acrylic or O-acyl compounds forming with H 2 O 2 organic peracids, preferably N, N'-tetraacylated diamines such as N, N, N ', N'- Tetraacetylethylenediamine.
Üblicherweise werden die Vorprodukte mit den Bleichmitteln und sonstigen Bestandteilen in Mengen von etwa 7 : 3 bis 9 : 1 gemischt. Der Gehalt der dann fertig konfektionierten Geschirrspülmittel an Oxidationsmittel auf Sauerstoffbasis beträgt vorzugsweise etwa 5 Gew.-% bis 15 Gew.-%, insbesondere in Kombination mit 1 Gew.-% bis 10 Gew.-%, insbesondere 2 Gew.-% bis 5 Gew.-%, eines Bleichaktivators.The preliminary products are usually mixed with the bleaching agents and other constituents in amounts of about 7: 3 to 9: 1. The oxygen-based oxidizing agent content of the ready-made dishwashing agents is preferably about 5% by weight to 15% by weight, in particular in combination with 1% by weight to 10% by weight, in particular 2% by weight to 5 % By weight of a bleach activator.
Eine bevorzugte Ausführungsform der Tabletten wird hergestellt, indem man 20 bis 60 Gewichtsteile Polycarbonsäuren bzw. ihre Salze mit 2 bis 5 Teilen Tensiden und Hydrophobierungsmittel in Gegenwart von bis zu 20 Gew.- Teilen Sauerstoffbleichmittel umschließt und anschließend 5 bis 50 Teile Alkalicarbonat und/oder Hydrogencarbonat sowie sonstige übliche Bestandteile zugibt.A preferred embodiment of the tablets is prepared by enclosing 20 to 60 parts by weight of polycarboxylic acids or their salts with 2 to 5 parts of surfactants and water repellents in the presence of up to 20 parts by weight of oxygen bleach and then 5 to 50 parts of alkali metal carbonate and / or hydrogen carbonate as well as other usual components.
Zu den erfindungsgemäßen Vorprordukten können außer den erwähnten Bleichmitteln und Bleichaktivatoren noch weitere, üblicherweise jeweils nur in kleinen Mengen vorliegende, Wirkstoffe gegeben werden. Die Menge all dieser Stoffe beträgt in Summe vorzugsweise 5 bis 10 Gew.-%, bezogen auf
das endgültig hergestellte Reinigungsmittel. Zu diesen Kleinkomponenten gehören beispielsweise Schauminhibitoren, Duftstoffe, Farbstoffe, Stabilisatoren und Enzyme von der Art der Proteasen, Amylasen, Lipasen und/oder Cellulasen sowie nicht als Kristallwasser gebundenes oder in ähnlich fester Form mit den Bestandteilen assoziertes Wasser. Die Enzyme können in üblicher Weise an Trägerstoffen adsorbiert und/oder in Hüllsubstanzen eingebettet sein und werden vorzugsweise in Mengen von insgesamt nicht über 5 Gew.-%, insbesondere 2 bis 4 Gew.-% eingesetzt. Geeignete nicht- tensidhaltige und bevorzugt eingesetzte Schauminhibitoren sind Organopolysiloxane und deren Gemische mit mikrofeiner, gegebenenfalls signierter Kieselsäure. Möglich ist auch der schauminhibierende Einsatz langkettiger Seifen. Geeignet können auch Gemische verschiedener Schauminhibitoren sein, zum Beispiel solche aus Silikonen und Paraffinen oder Wachsen. Bevorzugt sind diese Schauminhibitoren an eine granuläre, in Wasser lösliche bzw. dispergierbare Trägersubstanz gebunden.In addition to the bleaching agents and bleach activators mentioned, other active substances, which are usually only present in small amounts, can be added to the pre-products according to the invention. The total amount of all these substances is preferably 5 to 10% by weight, based on the final cleaning agent. These small components include, for example, foam inhibitors, fragrances, dyes, stabilizers and enzymes of the type of proteases, amylases, lipases and / or cellulases and water which is not bound as water of crystallization or is associated with the constituents in a similarly solid form. The enzymes can be adsorbed onto carrier substances in a conventional manner and / or embedded in coating substances and are preferably used in amounts of not more than 5% by weight, in particular 2 to 4% by weight. Suitable non-surfactant-containing and preferably used foam inhibitors are organopolysiloxanes and their mixtures with microfine, optionally signed silica. The foam-inhibiting use of long-chain soaps is also possible. Mixtures of different foam inhibitors can also be suitable, for example those composed of silicones and paraffins or waxes. These foam inhibitors are preferably bound to a granular, water-soluble or dispersible carrier substance.
Weitere hier einsetzbare Substanzen sind Silberschutzmittel, dies sind insbe¬ sondere anorganische Übergangsmetallsalze, z.B. Mangansalze wie Mangan¬ sulfat, gewünschtenfalls in Kombination mit Fluoriden Kaliumhexafluorotitanat und dergleichen, anorganische Übergangsmetallkomplexe, stickstoffhaltige Heterocyclen wie Benzoltriazol oder Isocyanursäure, natürliche Aminosäuren wie Cystin, Histidin, Methionin, reversible organische Redoxsysteme wie Chinon/Hydrochinon und/oder reversible anorganische Redoxsysteme wie Fe2+ /Fe3+ . Weiterhin können Stoffe zur Verhinderung der Glaskorrosion eingesetzt werden, beispielsweise Zinksalze oder Zink (hydr-oxid).Other substances which can be used here are silver protection agents, in particular inorganic transition metal salts, for example manganese salts such as manganese sulfate, if desired in combination with fluorides, potassium hexafluorotitanate and the like, inorganic transition metal complexes, nitrogen-containing heterocycles such as benzene triazole or isocyanuric acid, natural amino acids such as cystine, histidine reversible organic redox systems such as quinone / hydroquinone and / or reversible inorganic redox systems such as Fe 2+ / Fe 3+ . In addition, substances to prevent glass corrosion can be used, for example zinc salts or zinc (hydroxide).
Die nach dem erfindungsgemäßen Verfahren hergestellten Vorprodukte werden üblicherweise zu Tabletten verarbeitet. Dazu werden die Vorprodukte
mit den genannten weiteren Bestandteilen als Gemisch mittels herkömmlichen Tablettenpressen, beispielsweise Exzenterpressen oder Rundläuferpressen, mit Preßdrucken im Bereich von 200 . 105 Pa bis 1 500 . 105 Pa verpreßt. Man erhält so problemlos bruchfeste und dennoch unter Anwendungsbedingungen ausreichend schnell lösliche Tabletten mit Beigefestigkeiten von normalerweise über 150 N. Vorzugsweise weist eine derart hergestellte Tablette ein Gewicht von 15 g bis 40 g, insbesondere von 20 g bis 30 g, bei einem Durchmesser von 35 mm bis 40 mm auf.
The preliminary products produced by the process according to the invention are usually processed into tablets. To do this, the preliminary products with the other constituents mentioned as a mixture by means of conventional tablet presses, for example eccentric presses or rotary presses, with pressures in the range of 200. 10 5 Pa to 1 500. 10 5 Pa pressed. In this way, break-resistant tablets are obtained which, under application conditions, dissolve sufficiently quickly and have a beige strength of normally over 150 N. Preferably, a tablet produced in this way has a weight of 15 g to 40 g, in particular 20 g to 30 g, with a diameter of 35 mm up to 40 mm.
Beispielexample
In einem Lödige FKM 130 D Mischer wurden 17,25 kg Trinatriumcitratdihydrat, 2,5 kg Perboratmonohydrat und 4,1 kg Zitronensäuremonohydrat vorgelegt und ohne Mantelheizung vermischt. Über eine sich im Dom des Mischers befindlichen Kreisnebeldüse der Firma Schlick wurde ein 50 °C warmes Flüssigkeitsgemisch aus 1 ,5 kg Paraffin P 144 (Fp= 42 °C) und 0,75 kg Dehypon ® LT 104 (Taigfettalkohol 10 EO; 4 PO) in den laufenden Mischer eingedüst. Im Anschluß wurde dieses Gemisch mit den Restkomponenten in folgender Reihenfolge vermischt:17.25 kg of trisodium citrate dihydrate, 2.5 kg of perborate monohydrate and 4.1 kg of citric acid monohydrate were placed in a Lödige FKM 130 D mixer and mixed without jacket heating. A 50 ° C warm liquid mixture of 1.5 kg paraffin P 144 (mp = 42 ° C) and 0.75 kg Dehypon® LT 104 (tallow fatty alcohol 10 EO; 4 PO) was passed through a circular mist nozzle from Schlick located in the dome of the mixer ) injected into the running mixer. This mixture was then mixed with the remaining components in the following order:
1. Soda 6,9 kg,1. soda 6.9 kg,
2. Natriumhydrogencarbonat 13,35 kg,2. sodium bicarbonate 13.35 kg,
3. Parfüm 0,1 kg,3. perfume 0.1 kg,
4. Niotensid (Kokosfettalkohol 4 EO) 0,75 kg,4. non-ionic surfactant (coconut fatty alcohol 4 EO) 0.75 kg,
5. Enzyme (Protease-, Amlyase-Mischung 1 : 1) 1,8 kg,5. Enzymes (protease, amlyase mixture 1: 1) 1.8 kg,
6. TAED-Granulat 1 ,0 kg.6. TAED granules 1.0 kg.
Das ca. 950 g/l schwere Gemisch wurde auf einer Korsch Exzenterpresse Typ EKIV zu zylindrischen, 25 g schweren Tabletten mit einem Durchmesser von 34 mm und einer Höhe von 17,6 mm mit einer Preßkraft von 48 KN verpreßt. Direkt nach Herstellung ließen sich die Tabletten bei einer keilförmigen Belastung von 135 N Zerbrechen. Nach 1 Tag Lagerung erhöhte sich die zum Bruch führende Belastung auf 600 N.
The approx. 950 g / l heavy mixture was compressed on a Korsch eccentric press type EKIV to cylindrical, 25 g heavy tablets with a diameter of 34 mm and a height of 17.6 mm with a compressive force of 48 KN. Immediately after production, the tablets could be broken under a wedge-shaped load of 135 N. After 1 day of storage, the load leading to breakage increased to 600 N.
Claims
1. Verfahren zur Herstellung eines maschinellen Geschirrspülmittels in Tablettenform, enthaltend Polycarbonsäuren und ihre Salze als Builderkomponente, Alkalitätsträger, Bleichmittel, Tenside und Hydrophobierungsmittel sowie gewünschtenfalls übliche Zusatzstoffe, dadurch gekennzeichnet, daß man die Polycarbonsäure und ihre Salze in einer ersten Behandlungsstufe mit einer Flüssigphase aus Tensiden und Hydrophobierungsmittel umschließt, sodann in einer zweiten Behandlungsstufe die restlichen Bestandteile hinzufügt und schließlich diese Mischung zu Tabletten verpreßt.1. A process for producing a machine dishwashing detergent in tablet form, containing polycarboxylic acids and their salts as a builder component, alkalinity carriers, bleaching agents, surfactants and water repellents and, if desired, conventional additives, characterized in that the polycarboxylic acid and its salts are treated in a first treatment step with a liquid phase composed of surfactants and hydrophobizing agent, then in a second treatment step, adding the remaining constituents and finally compressing this mixture into tablets.
2. Verfahren nach Anspruch 1 , dadurch gekennzeichnet, daß man ohne Zu¬ satz von Wasser arbeitet.2. The method according to claim 1, characterized in that one works without addition of water.
3. Verfahren nach einem der Ansprüche 1 oder 2, dadurch gekennzeichnet, daß man das Umschließen der Polycarbonsäuren und/oder ihre Salze durchführt, in dem man die Tenside und die Hydrophobierungsmittel gleichzeitig oder nacheinander in beliebiger Reihenfolge flüssig auf die vorgelegte Mischung aufbringt.3. The method according to any one of claims 1 or 2, characterized in that the encapsulation of the polycarboxylic acids and / or their salts is carried out by applying the surfactants and the hydrophobizing agents simultaneously or in succession in any order in liquid order to the mixture.
4. Verfahren nach einem der Ansprüche 1 bis 3, dadurch gekennzeichnet, daß man vor dem Aufbringen der Tenside und/oder Hydrophobierungsmit¬ tel weitere Bestandteile, insbesondere Bleichmittel mit den Polycarbonsäu¬ ren und ihren Salzen mischt.4. The method according to any one of claims 1 to 3, characterized in that before the application of the surfactants and / or Hydrophobierungsmit¬ tel further ingredients, in particular bleaching agents with the Polycarbonsäu¬ ren and their salts.
5. Verfahren nach einem der Ansprüche 1 bis 4, dadurch gekennzeichnet, daß man als Polycarbonsäuren mehrfunktionelle Hydroxycarbonsäuren, insbesondere Citronensäuren, Zuckersäuren, Mono- bzw. Dihydroxybern- steinsäuren, Weinsäuren oder Copolymere auf Basis ungesättigter Carbonsäuren einsetzt und daß man als Salze die Natrium oder Kaliumsalze in wasserfreiem Zustand oder ais Hydrate einsetzt.5. The method according to any one of claims 1 to 4, characterized in that polyfunctional hydroxycarboxylic acids as polycarboxylic acids, in particular citric acids, sugar acids, mono- or dihydroxysuccinic acids, tartaric acids or copolymers based on unsaturated carboxylic acids and that the salts used are the sodium or potassium salts in the anhydrous state or as hydrates.
6. Verfahren nach einem der Ansprüche 1 bis 5 dadurch gekennzeichnet, daß man Mischungen aus Zitronensäure und Trinatriumcitratdihydrat einsetzt, die bezogen auf Mischung mehr als 5 Gew.-% und bis zu 100 Gew.-% der Säure (wasserfrei oder als Hydrat) enthalten.6. The method according to any one of claims 1 to 5, characterized in that mixtures of citric acid and trisodium citrate dihydrate are used which, based on the mixture, contain more than 5% by weight and up to 100% by weight of the acid (anhydrous or as a hydrate) .
7. Verfahren nach einem der Ansprüche 1 bis 6, dadurch gekennzeichnet, daß man Mischungen aus 5 bis 30 Gew.-% Zitronensäure und 70 bis 95 % Trinatriumcitrat einsetzt.7. The method according to any one of claims 1 to 6, characterized in that mixtures of 5 to 30 wt .-% citric acid and 70 to 95% trisodium citrate are used.
8. Verfahren nach einem der Ansprüche 1 bis 7, dadurch gekennzeichnet, daß man 20 bis 60 Teile Polycarbonsäuren bzw. ihre Salze mit 2 bis 5 Tei¬ len Tensiden und Hydrophobierungsmittel in Gegenwart von bis zu 20 Gew.-Teilen Sauerstoffbleichmittel umschließt und anschließend 5 bis 50 Teile Alkalicarbonat und/oder Hydrogencarbonat sowie sonstige übliche Bestandteile zugibt.8. The method according to any one of claims 1 to 7, characterized in that 20 to 60 parts of polycarboxylic acids or their salts with 2 to 5 Tei¬ len surfactants and hydrophobizing agents in the presence of up to 20 parts by weight of oxygen bleach and then 5 up to 50 parts of alkali carbonate and / or hydrogen carbonate and other customary ingredients.
9. Verfahren nach einem der Ansprüche 1 bis 8, dadurch gekennzeichnet, daß man als weitere Bestandteile Bleichaktivatoren, Enzyme, Duftstoffe, Farbstoffe, Schauminhibitoren, Stabilisatoren, Silberschutzmittel, Korrosionsschutzmittel und dergleichen zusetzt.9. The method according to any one of claims 1 to 8, characterized in that bleach activators, enzymes, fragrances, dyes, foam inhibitors, stabilizers, silver protectants, corrosion inhibitors and the like are added as further components.
10. Verfahren nach einem der Ansprüche 1 bis 9, dadurch gekennzeichnet, daß als Hydrophobiermittel Parafine mit einem Schmelzpunkt zwischen 40 und 60 °C ohne nichtionische Tenside mit demselben Schmelzbereich eingesetzt werden. 10. The method according to any one of claims 1 to 9, characterized in that Parafine with a melting point between 40th as a hydrophobizing agent and 60 ° C without nonionic surfactants with the same melting range.
Applications Claiming Priority (2)
Application Number | Priority Date | Filing Date | Title |
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DE19606765.0 | 1996-02-23 | ||
DE1996106765 DE19606765A1 (en) | 1996-02-23 | 1996-02-23 | Process for the production of dishwasher tablets |
Publications (1)
Publication Number | Publication Date |
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WO1997031096A1 true WO1997031096A1 (en) | 1997-08-28 |
Family
ID=7786209
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
PCT/EP1997/000700 WO1997031096A1 (en) | 1996-02-23 | 1997-02-14 | Process for producing dishwasher detergent tablets |
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WO (1) | WO1997031096A1 (en) |
Cited By (2)
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EP0903405A3 (en) * | 1997-09-23 | 1999-08-11 | Unilever Plc | Machine dish washing composition |
EP0915957A4 (en) * | 1996-07-31 | 2001-12-12 | Procter & Gamble | A process and composition for detergents |
Families Citing this family (6)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
GB2320254A (en) * | 1996-12-12 | 1998-06-17 | Procter & Gamble | Process for making tabletted detergent compositions |
US6177398B1 (en) | 1996-12-12 | 2001-01-23 | The Procter & Gamble Company | Process for making tabletted detergent compositions |
US6177393B1 (en) * | 1996-12-12 | 2001-01-23 | The Procter & Gamble Company | Process for making tabletted detergent compositions |
GB2320255A (en) * | 1996-12-12 | 1998-06-17 | Procter & Gamble | Process for making tabletted detergent compositions |
DE19752601C1 (en) * | 1997-11-28 | 1998-12-10 | Henkel Kgaa | Production of dishwasher detergent tablet with good breaking strength |
EP0933421B1 (en) * | 1997-12-18 | 2006-11-22 | Mifa Ag Frenkendorf | Compact phosphate-free cleaning tablets |
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Cited By (2)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
EP0915957A4 (en) * | 1996-07-31 | 2001-12-12 | Procter & Gamble | A process and composition for detergents |
EP0903405A3 (en) * | 1997-09-23 | 1999-08-11 | Unilever Plc | Machine dish washing composition |
Also Published As
Publication number | Publication date |
---|---|
DE19606765A1 (en) | 1997-08-28 |
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