WO1994023011A1 - Stabile, bifunktionelle, phosphat-, metasilikat- und polymerfreie niederalkalische reinigungsmitteltabletten für das maschinelle geschirrspülen und verfahren zu ihrer herstellung - Google Patents
Stabile, bifunktionelle, phosphat-, metasilikat- und polymerfreie niederalkalische reinigungsmitteltabletten für das maschinelle geschirrspülen und verfahren zu ihrer herstellung Download PDFInfo
- Publication number
- WO1994023011A1 WO1994023011A1 PCT/EP1994/000932 EP9400932W WO9423011A1 WO 1994023011 A1 WO1994023011 A1 WO 1994023011A1 EP 9400932 W EP9400932 W EP 9400932W WO 9423011 A1 WO9423011 A1 WO 9423011A1
- Authority
- WO
- WIPO (PCT)
- Prior art keywords
- weight
- sodium
- tablets
- sodium citrate
- stable
- Prior art date
Links
- 239000003599 detergent Substances 0.000 title claims abstract description 15
- 238000004851 dishwashing Methods 0.000 title claims abstract description 13
- 230000001588 bifunctional effect Effects 0.000 title claims abstract description 10
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 title claims abstract description 6
- 238000000034 method Methods 0.000 title claims description 14
- 239000000203 mixture Substances 0.000 claims abstract description 49
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 claims abstract description 27
- UIIMBOGNXHQVGW-UHFFFAOYSA-M Sodium bicarbonate Chemical compound [Na+].OC([O-])=O UIIMBOGNXHQVGW-UHFFFAOYSA-M 0.000 claims abstract description 26
- 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 abstract description 22
- 239000001509 sodium citrate Substances 0.000 claims abstract description 22
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 20
- 229910001868 water Inorganic materials 0.000 claims abstract description 20
- 239000005662 Paraffin oil Substances 0.000 claims abstract description 16
- 239000007844 bleaching agent Substances 0.000 claims abstract description 15
- 235000017557 sodium bicarbonate Nutrition 0.000 claims abstract description 13
- 229910000030 sodium bicarbonate Inorganic materials 0.000 claims abstract description 13
- 239000012190 activator Substances 0.000 claims abstract description 12
- 239000002736 nonionic surfactant Substances 0.000 claims abstract description 12
- 108090000790 Enzymes Proteins 0.000 claims abstract description 10
- 102000004190 Enzymes Human genes 0.000 claims abstract description 10
- 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 abstract description 10
- 150000001875 compounds Chemical class 0.000 claims abstract description 7
- 229960000999 sodium citrate dihydrate Drugs 0.000 claims abstract description 7
- 238000005187 foaming Methods 0.000 claims abstract description 5
- 238000002156 mixing Methods 0.000 claims abstract description 5
- 239000004094 surface-active agent Substances 0.000 claims abstract description 5
- 239000002304 perfume Substances 0.000 claims abstract description 4
- 239000003086 colorant Substances 0.000 claims abstract 3
- 238000004140 cleaning Methods 0.000 claims description 17
- 239000003205 fragrance Substances 0.000 claims description 13
- 125000005456 glyceride group Chemical group 0.000 claims description 8
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 6
- 239000001301 oxygen Substances 0.000 claims description 6
- 229910052760 oxygen Inorganic materials 0.000 claims description 6
- 108091005804 Peptidases Proteins 0.000 claims description 5
- 239000004365 Protease Substances 0.000 claims description 5
- 238000007906 compression Methods 0.000 claims description 5
- 230000006835 compression Effects 0.000 claims description 5
- 108010065511 Amylases Proteins 0.000 claims description 4
- 102000013142 Amylases Human genes 0.000 claims description 4
- 102100037486 Reverse transcriptase/ribonuclease H Human genes 0.000 claims description 4
- UIIMBOGNXHQVGW-DEQYMQKBSA-M Sodium bicarbonate-14C Chemical compound [Na+].O[14C]([O-])=O UIIMBOGNXHQVGW-DEQYMQKBSA-M 0.000 claims description 4
- 235000019418 amylase Nutrition 0.000 claims description 4
- VTIIJXUACCWYHX-UHFFFAOYSA-L disodium;carboxylatooxy carbonate Chemical compound [Na+].[Na+].[O-]C(=O)OOC([O-])=O VTIIJXUACCWYHX-UHFFFAOYSA-L 0.000 claims description 4
- 239000000975 dye Substances 0.000 claims description 4
- PMYUVOOOQDGQNW-UHFFFAOYSA-N hexasodium;trioxido(trioxidosilyloxy)silane Chemical compound [Na+].[Na+].[Na+].[Na+].[Na+].[Na+].[O-][Si]([O-])([O-])O[Si]([O-])([O-])[O-] PMYUVOOOQDGQNW-UHFFFAOYSA-N 0.000 claims description 4
- -1 other builders Substances 0.000 claims description 4
- 229940045872 sodium percarbonate Drugs 0.000 claims description 4
- XSVSPKKXQGNHMD-UHFFFAOYSA-N 5-bromo-3-methyl-1,2-thiazole Chemical compound CC=1C=C(Br)SN=1 XSVSPKKXQGNHMD-UHFFFAOYSA-N 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
- 229910019142 PO4 Inorganic materials 0.000 claims description 3
- 239000007788 liquid Substances 0.000 claims description 3
- 239000011734 sodium Substances 0.000 claims description 3
- 229910052708 sodium Inorganic materials 0.000 claims description 3
- YPPQYORGOMWNMX-UHFFFAOYSA-L sodium phosphonate pentahydrate Chemical compound [Na+].[Na+].[O-]P([O-])=O YPPQYORGOMWNMX-UHFFFAOYSA-L 0.000 claims description 3
- 229940038773 trisodium citrate Drugs 0.000 claims description 3
- QTBSBXVTEAMEQO-UHFFFAOYSA-M Acetate Chemical compound CC([O-])=O QTBSBXVTEAMEQO-UHFFFAOYSA-M 0.000 claims description 2
- 239000004382 Amylase Substances 0.000 claims description 2
- 239000000194 fatty acid Substances 0.000 claims description 2
- 230000002349 favourable effect Effects 0.000 claims description 2
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 claims description 2
- 239000010452 phosphate Substances 0.000 claims description 2
- 150000003626 triacylglycerols Chemical class 0.000 claims description 2
- PIICEJLVQHRZGT-UHFFFAOYSA-N Ethylenediamine Chemical compound NCCN PIICEJLVQHRZGT-UHFFFAOYSA-N 0.000 claims 1
- VMHLLURERBWHNL-UHFFFAOYSA-M Sodium acetate Chemical compound [Na+].CC([O-])=O VMHLLURERBWHNL-UHFFFAOYSA-M 0.000 claims 1
- XFEGQOMCPRIYGR-UHFFFAOYSA-N [N-3].[Na+].[Na+].[Na+] Chemical compound [N-3].[Na+].[Na+].[Na+] XFEGQOMCPRIYGR-UHFFFAOYSA-N 0.000 claims 1
- 238000004040 coloring Methods 0.000 claims 1
- 239000001632 sodium acetate Substances 0.000 claims 1
- 235000017281 sodium acetate Nutrition 0.000 claims 1
- 229910000029 sodium carbonate Inorganic materials 0.000 abstract description 7
- 238000009736 wetting Methods 0.000 abstract 1
- 239000012459 cleaning agent Substances 0.000 description 8
- 238000004090 dissolution Methods 0.000 description 7
- 238000003825 pressing Methods 0.000 description 7
- 235000017550 sodium carbonate Nutrition 0.000 description 6
- 239000003513 alkali Substances 0.000 description 5
- 239000008139 complexing agent Substances 0.000 description 5
- 229940088598 enzyme Drugs 0.000 description 5
- 239000000126 substance Substances 0.000 description 5
- 108010075550 termamyl Proteins 0.000 description 5
- 101000740449 Bacillus subtilis (strain 168) Biotin/lipoyl attachment protein Proteins 0.000 description 4
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 4
- 239000010794 food waste Substances 0.000 description 4
- NTHWMYGWWRZVTN-UHFFFAOYSA-N sodium silicate Chemical compound [Na+].[Na+].[O-][Si]([O-])=O NTHWMYGWWRZVTN-UHFFFAOYSA-N 0.000 description 4
- 239000001226 triphosphate Substances 0.000 description 4
- BJGMCBVGOYXEBZ-LBPRGKRZSA-N (2s)-5-amino-2-[4-[(5-methyl-1,2-oxazol-3-yl)sulfamoyl]anilino]-5-oxopentanoic acid Chemical compound O1C(C)=CC(NS(=O)(=O)C=2C=CC(N[C@@H](CCC(N)=O)C(O)=O)=CC=2)=N1 BJGMCBVGOYXEBZ-LBPRGKRZSA-N 0.000 description 3
- 239000000654 additive Substances 0.000 description 3
- 239000000470 constituent Substances 0.000 description 3
- 239000006260 foam Substances 0.000 description 3
- 238000009472 formulation Methods 0.000 description 3
- 239000008187 granular material Substances 0.000 description 3
- 235000019589 hardness Nutrition 0.000 description 3
- 238000004519 manufacturing process Methods 0.000 description 3
- 239000008399 tap water Substances 0.000 description 3
- 235000020679 tap water Nutrition 0.000 description 3
- IAYPIBMASNFSPL-UHFFFAOYSA-N Ethylene oxide Chemical compound C1CO1 IAYPIBMASNFSPL-UHFFFAOYSA-N 0.000 description 2
- CERQOIWHTDAKMF-UHFFFAOYSA-N Methacrylic acid Chemical compound CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 description 2
- 239000004115 Sodium Silicate Substances 0.000 description 2
- UAOKXEHOENRFMP-ZJIFWQFVSA-N [(2r,3r,4s,5r)-2,3,4,5-tetraacetyloxy-6-oxohexyl] acetate Chemical compound CC(=O)OC[C@@H](OC(C)=O)[C@@H](OC(C)=O)[C@H](OC(C)=O)[C@@H](OC(C)=O)C=O UAOKXEHOENRFMP-ZJIFWQFVSA-N 0.000 description 2
- 239000013543 active substance Substances 0.000 description 2
- 230000000996 additive effect Effects 0.000 description 2
- 229910052783 alkali metal Inorganic materials 0.000 description 2
- 229910052910 alkali metal silicate Inorganic materials 0.000 description 2
- 229940025131 amylases Drugs 0.000 description 2
- 238000005452 bending Methods 0.000 description 2
- 239000003795 chemical substances by application Substances 0.000 description 2
- 229920001577 copolymer Polymers 0.000 description 2
- 238000010410 dusting Methods 0.000 description 2
- 239000013505 freshwater Substances 0.000 description 2
- 229920001519 homopolymer Polymers 0.000 description 2
- VYFOAVADNIHPTR-UHFFFAOYSA-N isatoic anhydride Chemical compound NC1=CC=CC=C1CO VYFOAVADNIHPTR-UHFFFAOYSA-N 0.000 description 2
- 229910052751 metal Inorganic materials 0.000 description 2
- 239000002184 metal Substances 0.000 description 2
- 150000004682 monohydrates Chemical class 0.000 description 2
- HWGNBUXHKFFFIH-UHFFFAOYSA-I pentasodium;[oxido(phosphonatooxy)phosphoryl] phosphate Chemical compound [Na+].[Na+].[Na+].[Na+].[Na+].[O-]P([O-])(=O)OP([O-])(=O)OP([O-])([O-])=O HWGNBUXHKFFFIH-UHFFFAOYSA-I 0.000 description 2
- 235000021317 phosphate Nutrition 0.000 description 2
- 239000004033 plastic Substances 0.000 description 2
- 229920003023 plastic Polymers 0.000 description 2
- 102000004169 proteins and genes Human genes 0.000 description 2
- 108090000623 proteins and genes Proteins 0.000 description 2
- 150000003839 salts Chemical class 0.000 description 2
- 239000000377 silicon dioxide Substances 0.000 description 2
- 229920002545 silicone oil Polymers 0.000 description 2
- 235000019795 sodium metasilicate Nutrition 0.000 description 2
- 229910052911 sodium silicate Inorganic materials 0.000 description 2
- PHIQPXBZDGYJOG-UHFFFAOYSA-N sodium silicate nonahydrate Chemical compound O.O.O.O.O.O.O.O.O.[Na+].[Na+].[O-][Si]([O-])=O PHIQPXBZDGYJOG-UHFFFAOYSA-N 0.000 description 2
- 235000019832 sodium triphosphate Nutrition 0.000 description 2
- 239000007787 solid Substances 0.000 description 2
- 238000005507 spraying Methods 0.000 description 2
- 238000003860 storage Methods 0.000 description 2
- 239000000725 suspension Substances 0.000 description 2
- FRPJTGXMTIIFIT-UHFFFAOYSA-N tetraacetylethylenediamine Chemical compound CC(=O)C(N)(C(C)=O)C(N)(C(C)=O)C(C)=O FRPJTGXMTIIFIT-UHFFFAOYSA-N 0.000 description 2
- 235000011178 triphosphate Nutrition 0.000 description 2
- FIDRAVVQGKNYQK-UHFFFAOYSA-N 1,2,3,4-tetrahydrotriazine Chemical compound C1NNNC=C1 FIDRAVVQGKNYQK-UHFFFAOYSA-N 0.000 description 1
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 description 1
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 description 1
- JLVVSXFLKOJNIY-UHFFFAOYSA-N Magnesium ion Chemical compound [Mg+2] JLVVSXFLKOJNIY-UHFFFAOYSA-N 0.000 description 1
- BPQQTUXANYXVAA-UHFFFAOYSA-N Orthosilicate Chemical compound [O-][Si]([O-])([O-])[O-] BPQQTUXANYXVAA-UHFFFAOYSA-N 0.000 description 1
- 102000035195 Peptidases Human genes 0.000 description 1
- ABLZXFCXXLZCGV-UHFFFAOYSA-N Phosphorous acid Chemical class OP(O)=O ABLZXFCXXLZCGV-UHFFFAOYSA-N 0.000 description 1
- 239000002202 Polyethylene glycol Substances 0.000 description 1
- GOOHAUXETOMSMM-UHFFFAOYSA-N Propylene oxide Chemical group CC1CO1 GOOHAUXETOMSMM-UHFFFAOYSA-N 0.000 description 1
- 241000220317 Rosa Species 0.000 description 1
- 229910004298 SiO 2 Inorganic materials 0.000 description 1
- PMZURENOXWZQFD-UHFFFAOYSA-L Sodium Sulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=O PMZURENOXWZQFD-UHFFFAOYSA-L 0.000 description 1
- 229920002472 Starch Polymers 0.000 description 1
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical group C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 1
- 150000001298 alcohols Chemical class 0.000 description 1
- 150000001447 alkali salts Chemical class 0.000 description 1
- 125000000217 alkyl group Chemical group 0.000 description 1
- 239000002518 antifoaming agent Substances 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 239000011575 calcium Substances 0.000 description 1
- 229910001424 calcium ion Inorganic materials 0.000 description 1
- BVKZGUZCCUSVTD-UHFFFAOYSA-N carbonic acid Chemical class OC(O)=O BVKZGUZCCUSVTD-UHFFFAOYSA-N 0.000 description 1
- 150000004649 carbonic acid derivatives Chemical class 0.000 description 1
- 239000000969 carrier Substances 0.000 description 1
- 150000001805 chlorine compounds Chemical class 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 230000009918 complex formation Effects 0.000 description 1
- 235000014113 dietary fatty acids Nutrition 0.000 description 1
- MTHSVFCYNBDYFN-UHFFFAOYSA-N diethylene glycol Chemical compound OCCOCCO MTHSVFCYNBDYFN-UHFFFAOYSA-N 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 150000002170 ethers Chemical class 0.000 description 1
- 229930195729 fatty acid Natural products 0.000 description 1
- 150000004665 fatty acids Chemical class 0.000 description 1
- 150000002191 fatty alcohols Chemical class 0.000 description 1
- 235000021149 fatty food Nutrition 0.000 description 1
- 238000011049 filling Methods 0.000 description 1
- 238000011010 flushing procedure Methods 0.000 description 1
- 230000036571 hydration Effects 0.000 description 1
- 238000006703 hydration reaction Methods 0.000 description 1
- 238000005461 lubrication Methods 0.000 description 1
- 229910001425 magnesium ion Inorganic materials 0.000 description 1
- 108010003855 mesentericopeptidase Proteins 0.000 description 1
- 108010020132 microbial serine proteinases Proteins 0.000 description 1
- 239000006082 mold release agent Substances 0.000 description 1
- 229920000620 organic polymer Polymers 0.000 description 1
- 150000003013 phosphoric acid derivatives Chemical class 0.000 description 1
- 229920001748 polybutylene Polymers 0.000 description 1
- 229920001223 polyethylene glycol Polymers 0.000 description 1
- 229920001451 polypropylene glycol Polymers 0.000 description 1
- 235000019353 potassium silicate Nutrition 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 230000003763 resistance to breakage Effects 0.000 description 1
- 150000004760 silicates Chemical class 0.000 description 1
- 229960001922 sodium perborate Drugs 0.000 description 1
- 159000000000 sodium salts Chemical class 0.000 description 1
- 229910052938 sodium sulfate Inorganic materials 0.000 description 1
- 235000011152 sodium sulphate Nutrition 0.000 description 1
- MWNQXXOSWHCCOZ-UHFFFAOYSA-L sodium;oxido carbonate Chemical compound [Na+].[O-]OC([O-])=O MWNQXXOSWHCCOZ-UHFFFAOYSA-L 0.000 description 1
- 235000019698 starch Nutrition 0.000 description 1
- 239000008107 starch Substances 0.000 description 1
- 150000004685 tetrahydrates Chemical class 0.000 description 1
- 125000002264 triphosphate group Chemical class [H]OP(=O)(O[H])OP(=O)(O[H])OP(=O)(O[H])O* 0.000 description 1
- UNXRWKVEANCORM-UHFFFAOYSA-N triphosphoric acid Chemical compound OP(O)(=O)OP(O)(=O)OP(O)(O)=O UNXRWKVEANCORM-UHFFFAOYSA-N 0.000 description 1
- 238000005406 washing 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
- C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
- C11D3/39—Organic or inorganic per-compounds
- C11D3/3902—Organic or inorganic per-compounds combined with specific additives
- C11D3/3905—Bleach activators or bleach catalysts
- C11D3/3907—Organic compounds
- C11D3/3917—Nitrogen-containing compounds
-
- 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
- C11D1/00—Detergent compositions based essentially on surface-active compounds; Use of these compounds as a detergent
- C11D1/66—Non-ionic compounds
- C11D1/667—Neutral esters, e.g. sorbitan esters
-
- 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
- C11D3/02—Inorganic compounds ; Elemental compounds
- C11D3/04—Water-soluble compounds
- C11D3/10—Carbonates ; Bicarbonates
-
- 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
-
- 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
- C11D3/38—Products with no well-defined composition, e.g. natural products
- C11D3/386—Preparations containing enzymes, e.g. protease or amylase
- C11D3/38609—Protease or amylase in solid compositions only
Definitions
- Machine dishwashing generally consists of a pre-rinse cycle, a cleaning cycle, one or more intermediate rinse cycles, a rinse cycle and a drying cycle. This applies to machine washing both in the home and in business.
- HGSM HGSM
- GGSM In the case of a commercial dishwasher, hereinafter referred to as GGSM, the so-called pre-clearing zone corresponds in principle to the pre-rinse cycle of an HGSM.
- the cleaning agent metered into the cleaning zone is used by overflow in the pre-clearing zone to support the cleaning of the adhering food residues.
- GGSM in which the pre-clearing zone is only operated with fresh water, but a pre-clearing zone with detergent additive is more effective than pre-clearing with fresh water alone.
- pre-clearing zone cleaning from GGSM has also already been transferred to HGSM and dosing of cleaning agents has already been made possible for the pre-rinse cycle by dosing cleaning agents in tablet form and one or more suitable tablets, for example in a free part of the cutlery basket. but also positioned elsewhere in the machine, as a result of which they could act both in the pre-rinse cycle and in the actual cleaning cycle, that is to say bifunctionally.
- Such tablet-shaped cleaning agents is described, for example, in DE-OS 3541 145.
- These are uniform Compound cleaning agent tablets with a broad dissolving profile for machine dishwashing, which contain the usual alkaline components, in particular from the group of alkali metal silicates and pentaalkali metal triphosphates, active chlorine compounds and tabletting aids, and in which the alkali metal silicates are made from a mixture of "sodium metasilicate nonahydrate" (Na2 ) and anhydrous sodium metasilicate and the pentaalkali metal triphosphate consists of anhydrous pentasodium triphosphate, the weight ratio of anhydrous sodium metasilicate: sodium metasilicate nonahydrate being between 1: 0.3 and 1: 1.5 and the weight ratio of pentasodium triphosphate to sodium metasikate, each being water-free , 2: 1 to 1: 2, preferably 1: 1 to 1: 1.7.
- Tablets of this type have such a broad dissolution profile that they are already dissolved in the tap water to at least 10% by weight in the pre-rinsing step of an HGSM, thereby developing a pH value of at least 10.0 in the rinsing liquor and with good hot water solubility at least 60% by weight, preferably at least 70% by weight, are still available for the cleaning process.
- the dissolution profile is understood to mean the weight ratio of the proportions of the tablet to the entire tablet which are dissolved from the usual HGSM under the conditions of the pre-rinse cycle.
- phosphate-free detergent tablets for machine dishwashing have also been on the market for some time and contain essentially silicates, nonionic surfactants, organic complexing agents and percarbonate. If these tablets are placed inside the machine (e.g. in the basket), they will dissolve as far as possible, even completely, during the pre-rinse cycle, so that the actual cleaning cycle table no more detergent is available. In addition, the stability of these tablets is unsatisfactory.
- DE-OS 4010524 describes stable, bifunctional, phosphate-free detergent tablets for machine dishwashing containing silicate, low-foam nonionic surfactants, organic complexing agents, bleaches and water, the organic complexing agents according to DE-OS 39 37 469 in the form of a granular, alkaline cleaning additive consisting of sodium salts of at least one homopolymeric or copolymeric (meth) acrylic acid, sodium carbonate, sodium sulfate and water.
- the granular alkaline cleaning additives were mechanically mixed with the other mostly powdery formulation components and pressed in a manner known per se.
- the sodium carbonate serving as part of the builders was used in anhydrous form and initially in a mixing cycle, preferably alone or with the other builders such as sodium citrate and optionally sodium hydrogen carbonate and the solid alkali salts of at least one homopolymer or copolymer ( Meth-) acrylic acid together with the amount of water required for the partial hydration of the anhydrous sodium carbonate of about 5-40, preferably about 7-20% by weight, based on the anhydrous sodium carbonate used as the framework substance, added - The remaining substances were then added to the mixture and the mixture thus obtained was compressed on a conventional tablet press.
- the other builders such as sodium citrate and optionally sodium hydrogen carbonate and the solid alkali salts of at least one homopolymer or copolymer ( Meth-) acrylic acid
- the storage-stable tablets produced in this way have a high breaking strength (greater than 140 N with a diameter of approximately 30 to 40 mm and a density of approximately 1.4 to 1.7 g / cm 3), which also remains stable during storage and thereby changes within a short time Time can still increase significantly.
- the present invention now relates to stable, bifunctional, phosphate-, etasilicate- and now also polymer-free, low-alkaline cleaning tablets for automatic dishwashing, which are characterized in that they contain sodium citrate, further builders, enzymes and optionally bleach activators, nonionic surfactants, color - and contain fragrances. They correspond to the following basic formulation:
- Trisodium citrate dihydrate 5 - 50% 20 - 30%
- Tetraacetylethylenediamine 0.5 - 4% 2 - 4% non-ionic surfactant 0 - 4% 0.5 - 2%
- a process has been found in which such stable, bifunctional, phosphate-, metasilicate- and now also polymer-free, lower-alkaline detergent tablets for automatic dishwashing with a content of sodium citrate, other scaffold substances, low-foam surfactants, bleaches and optionally Enzymes, bleach activators, fragrances and dyes come when you first moisten sodium citrate dihydrate and / or sodium citrate with a small amount of water of about 3 - 10, preferably about 4 - 6 wt .-%, based on the total composition, then dusted with anhydrous sodium carbonate and then sodium hydrogen carbonate and the bleach activator are added, enzymes, non-ionic surfactants, fragrances / dyes and optionally paraffin oil are added, finally the active oxygen-releasing compound is mixed in with a low energy input and the total mixture obtained in this way on a conventional tablet press at a relative atmospheric humidity 15 to 60, preferably about 20 to 30% with a compression pressure of about 2 to 11, preferably about 4 to 6, MPa to tablets.
- paraffin oil can also take place together with the addition of the sodium citrate, preferably in the form of a mixture which, in an advanced, separate mixed cut, preferably comprises 1 to 3% by weight, in particular approximately 2% by weight.
- Paraffin oil based on the total detergent mixture and sodium citrate. Also advantageous is a hydrophobization of the sodium bicarbonate carried out in a preferred mixing step with paraffin oil.
- a desired further delay in the dissolution in the pre-rinse cycle of an HGSM can take place if the water added at the beginning is already mixed with the nonionic surfactant, to which the fragrance can also be added, or with a glyceride mixture and sprayed onto the sodium citrate and then adding the residual substances.
- a further preferred embodiment of the process according to the invention consists in first applying all liquid components of the composition to the sodium citrate, then dusting the anhydrous sodium carbonate and then in succession, each with a low energy input, sodium bicarbonate, the bleach activator and finally the active oxygen releasing compound are added and the total mixture thus obtained is pressed as indicated above.
- Low energy input means gentle mixing without using the high-speed cutter heads with only short dwell times in the mixer.
- the storage-stable tablets produced according to the invention have a high breaking strength (greater than 140 N with a diameter of about 30 to 40 m and a density of about 1.4 to 1.7 g / atß), which can increase significantly within a short time during storage , and which also remain stable.
- alkali metal nitrilotriacetates, alkali phosphonates and alkali disilicates can also be used as builders. They bind hardening agents such as calcium and magnesium ions from the water or from the food residues through complex formation or dispersion and thus prevent the formation of limescale deposits in the dishwasher and on the dishes. They can be used as anhydrous and / or as hydrate salts. Water-free trisodium citrate or trisodium citrate dihydrate are suitable as sodium citrate. Sodium carbonate of any quality is preferably used as the alkali carbonate, such as. B. soda ash or compressed soda. Any origin can be used as sodium hydrogen carbonate.
- Preferred alkali metal phosphonate is the tetrasodium salt of l-hydroxyethane-1,1-di-phosphonic acid (Turpinal ( R ) 4 NZ from Henkel).
- Dried water glass with the module SiO 2 : Na2 ⁇ 1: 2-2.5, (for example Portil ( R ) A or AW from Henkel, Britesil ( R ) H 24 or C) is suitable as sodium disilicate 24 from Akzo).
- Extremely low-foaming nonionic compounds are preferably used as low-foaming surfactants, which serve to better remove fatty food residues and as pressing aids. These preferably include C12-C18 alkyl polyethylene glycol polypropylene glycol ethers, each with up to 8 moles of ethylene oxide and propylene oxide units in the molecule. Their share in the total weight of the finished tablets is generally about 0.2 to 5, preferably about 0.5 to 3,% by weight. But you can also use other non-foaming surfactants known as low foams, such as. B.
- Ci2-Ci8-Alkylpolyethy- lenglykol-polybutylene glycol ether each with up to 8 moles of ethylene oxide and butylene oxide units in the molecule and then optionally about 0.2 to 2, preferably about 0.2 to 1 wt .-%, based on the total Tablet, on defoaming agents such.
- B. Add silicone oils, mixtures of silicone oil and hydrophobicized silica, paraffin oil / Guerbet alcohols and hydrophobicized silica.
- Active oxygen carriers are now preferably bleaches which are customary constituents of cleaning agents for HGSM. These include primarily sodium perborate mono- and tetrahydrate as well as sodium percarbonate and sodium uearoat. Since active oxygen only develops its full effect on its own at elevated temperatures, so-called bleach activators are also expediently used to activate it at about 60 ° C., the temperatures of the cleaning process in the HGSM.
- TAED tetraacetylenediamine
- PAG penentaacetylglucose
- DADHT 1,5-di-acetyl-2,4-dioxo-hexahydro-l, 3,5-triazine
- ISA isatoic anhydride
- Enzymes such as proteases and amylases can also be used to better remove protein or starch-containing food residues, for example proteins such as BLAP ( R ) from Henkel, Opitmase ( R ) -M-440, Optimase ( R ) - -M -330, Opticlean ( R ) -M-375, Opticlean ( R ) -M-250 from Solvay Enzy ⁇ mes, Maxacal ( R ) CX 450,000, Maxapem ( R ) from Ibis, Savinase ( R ) T from Novo or Esperase ( R ) T from Ibis and amylases such as Termamyl ( R ) 60 T, 90 T from Novo, Amylase-LT ( R ) from Solvay Enzymes or Maxamyl ( R ) P 5000 from Ibis.
- proteins such as BLAP ( R ) from Henkel, Opitmase ( R ) -M-440, Optimase (
- Customary oxidation-stable dyes and fragrances can also be added to the tablet mixtures.
- the tablets can also be pressed in colored layers with otherwise the same composition.
- tableting aids such as mold release agents, for example paraffin oil, or mixtures of mono-, di- and triglycerides of C12-C18, preferably Ci ⁇ -Ci ⁇ fatty acids, for example commercially available glyceride mixtures sold as baking agents, e.g. Boeson VP (Boehringer, Ingelheim) is not necessary for compressing the tablets according to the invention and can usually be omitted if the tablet mixtures contain nonionic surfactants which essentially take on this task.
- the addition of paraffin oil and / or glyceride mixtures can nevertheless be expedient, as indicated, because it leads to a delay in dissolution of the tablets, so that a higher proportion of the tablet is available in the cleaning cycle.
- the desired pH is preferably set via the sodium hydrogen carbonate portion.
- the mixture produced as described would be pressed on conventional tablet presses with a pressure of about 2 to 11 MPa, preferably about 4 to 6 MPa.
- the pressing could be carried out in known manner without die lubrication using commercially available eccentric presses, hydraulic presses or rotary presses. No caking of the tablet mixture was observed on the pressing tools. Tools coated with hard plastic as well as uncoated delivered tablets with smooth surfaces, so that in most cases it was also possible to dispense with coating the punches with soft plastic.
- the pressing conditions were optimized with regard to the setting of the desired dissolution profile with sufficient tablet hardness.
- the flexural strength can serve as a measure of the tablet hardness (method: compare Ritschel. Die Tablette, Ed. Cantor, 1966, p. 313). According to this, tablets with a bending strength greater than 100 N, preferably greater than 150 N, are sufficiently stable under simulated transport conditions.
- the bending or breaking strength of the tablets can be controlled by the degree of compression, ie the compression pressure, regardless of their
- the specific weight of the compacts was between about 1.2 and 2 g / cm 3, preferably between about 1.4 and 1.8 g / cm 3.
- the compression during the pressing process caused changes in the density, which ranged from about 0.4 to 1.2 g / cm 3, preferably about 0.6 to 1.0 g / i 3 to about 1.2 to 2.0 g /, preferably about 1 .4 to 1.6 g / cm3 rose.
- the shape of the tablet can also influence the breaking strength and the dissolving speed via the outer surface exposed to the H2O attack. For reasons of stability, cylindrical compacts with a diameter / height ratio of approximately 0.6 to 4.0: 1 were produced.
- the breaking strength corresponds to the weight of the wedge-shaped load, which leads to the tablet breaking.
- the amounts of the substance mixture to be compressed for the individual tablets can be varied as desired within technically reasonable limits. Depending on their size, 1 to 2 or even more tablets per machine filling are preferably used in order to provide the entire cleaning process with the necessary active substance content of cleaning agent. Tablets of about 20 to 40 g in weight and a diameter of about 35 to 40 mm are preferred, of which one must be used in each case. If sodium carbonate was not hydrated or used as a full hydrate, the quality of the tablets obtained from the mixture was unusable for the trade since, among other things, they had insufficient breaking strength. The tablets also caked on the mixtures on the upper ram of the presses.
- a batch of 50 kg was prepared in a 130 l Lödige ploughshare mixer by first spraying 4 parts by weight of water onto 7.5 parts by weight of sodium carbonate and 48 parts by weight of sodium hydrogen carbonate and then with 30 parts by weight of sodium citrate dihydrate, 2 parts by weight of TAED granules and 1 part by weight of BLAP ( R ). 170 and 1 part by weight of Termamyl ( R ) 60 parts were mixed while spraying 0.9 parts by weight of Dehydol LS4 and 0.6 parts by weight of fragrance. 5 parts by weight of perborate onohydrate were then gently mixed into the mixture thus obtained. As can be seen from the table containing the pressing conditions and tablet properties, the mixture gave tablets with only limited resistance to breakage that dissolve too quickly in the pre-rinse cycle.
- Example A With the same composition as described in Example A, the sodium citrate dihydrate was first sprayed with water in 130 l Lödige mixer according to the invention, followed by dusting with soda. Then TAED granules, sodium hydrogen carbonate, Blap 170, Termamyl 60 T and a mixture of perborate monohydrate, fragrance and dehydol LS4 were added. The much more favorable properties of the tablets obtained in this way can be seen from the tables below, as in the examples below.
- the mixture was prepared as in Example 1, but after the addition of the dehydol LS4, the perborate monohydrate was finally mixed in separately.
- Example 4 The mixture was prepared as described in Example 1, but 1% paraffin oil was additionally sprayed onto the mixture at the end.
- Example 4
- TAED tetraacetylethylenediamine
- Boeson VP commercially available glyceride mixture Examples table
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Abstract
Description
Claims
Priority Applications (5)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
EP94912526A EP0692020B1 (de) | 1993-04-01 | 1994-03-23 | Stabile, bifunktionelle, phosphat-, metasilikat- und polymerfreie niederalkalische reinigungsmitteltabletten für das maschinelle geschirrspülen und verfahren zu ihrer herstellung |
DK94912526T DK0692020T3 (da) | 1993-04-01 | 1994-03-23 | Stabile, bifunktionelle, phosphat-, metasilicat- og polymerfrie, lavalkaliske detergenttabletter tilmaskinopvask og fremgan |
PL94310951A PL177250B1 (pl) | 1993-04-01 | 1994-03-23 | Trwałe, dwufunkcyjne, niskoalkaliczne tabletki środka czyszczącego do mechanicznego mycia naczyń oraz sposób ich wytwarzania |
US08/530,114 US5691293A (en) | 1993-04-01 | 1994-03-23 | Stable, dual-function, phosphate-, metasilicate- and polymer-free low-alkali detergent tablets for dishwashing machines and a process for their production |
DE59404581T DE59404581D1 (de) | 1993-04-01 | 1994-03-23 | Stabile, bifunktionelle, phosphat-, metasilikat- und polymerfreie niederalkalische reinigungsmitteltabletten für das maschinelle geschirrspülen und verfahren zu ihrer herstellung |
Applications Claiming Priority (2)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
DEP4315048.9 | 1993-04-01 | ||
DE4315048A DE4315048A1 (de) | 1993-04-01 | 1993-04-01 | Verfahren zur Herstellung stabiler, bifunktioneller, phosphat-, metasilikat- und polymerfreier niederalkalischer Reinigungsmitteltabletten für das maschinelle Geschirrspülen |
Publications (1)
Publication Number | Publication Date |
---|---|
WO1994023011A1 true WO1994023011A1 (de) | 1994-10-13 |
Family
ID=6487366
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
PCT/EP1994/000932 WO1994023011A1 (de) | 1993-04-01 | 1994-03-23 | Stabile, bifunktionelle, phosphat-, metasilikat- und polymerfreie niederalkalische reinigungsmitteltabletten für das maschinelle geschirrspülen und verfahren zu ihrer herstellung |
Country Status (10)
Country | Link |
---|---|
US (1) | US5691293A (de) |
EP (1) | EP0692020B1 (de) |
AT (1) | ATE160169T1 (de) |
CZ (1) | CZ286894B6 (de) |
DE (2) | DE4315048A1 (de) |
DK (1) | DK0692020T3 (de) |
ES (1) | ES2110742T3 (de) |
HU (1) | HUT72020A (de) |
PL (1) | PL177250B1 (de) |
WO (1) | WO1994023011A1 (de) |
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WO1995025161A1 (de) * | 1994-03-15 | 1995-09-21 | Henkel Kommanditgesellschaft Auf Aktien | Bruch- und lagerstabile, polyfunktionelle reinigungstabletten, verfahren zu ihrer herstellung und ihre verwendung |
WO2000066699A1 (de) * | 1999-04-29 | 2000-11-09 | Henkel Kommanditgesellschaft Auf Aktien | Brausetabletten mit tablettierhilfsmittel und verfahren zu ihrer herstellung |
EP2754708B1 (de) * | 2013-01-10 | 2018-01-17 | Budich International GmbH | Reinigertablette mit integriertem Vorreiniger |
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US20080274931A1 (en) * | 2007-05-02 | 2008-11-06 | Veripak, Inc. | Bio-friendly automatic dish washing tablets processes and all natural products thereby |
US7759300B2 (en) * | 2007-07-02 | 2010-07-20 | Ecolab Inc. | Solidification matrix including a salt of a straight chain saturated mono-, di-, or tri- carboxylic acid |
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DE102011007695A1 (de) | 2011-04-19 | 2012-10-25 | Henkel Ag & Co. Kgaa | Phosphatfreies Geschirrspülmittel |
DE102016212248A1 (de) | 2016-07-05 | 2018-01-11 | Henkel Ag & Co. Kgaa | Geschirrspülmittel enthaltend Zuckersäure und Aminocarbonsäure |
DE102017212561A1 (de) | 2017-07-21 | 2019-01-24 | Henkel Ag & Co. Kgaa | Geschirrspülmittel enthaltend Citratdihydrat und -anhydrat |
WO2019232387A1 (en) | 2018-06-01 | 2019-12-05 | Altered Labs, Llc | Reducing compositions and processes for producing the same |
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- 1994-03-23 ES ES94912526T patent/ES2110742T3/es not_active Expired - Lifetime
- 1994-03-23 DE DE59404581T patent/DE59404581D1/de not_active Expired - Lifetime
- 1994-03-23 PL PL94310951A patent/PL177250B1/pl unknown
- 1994-03-23 AT AT94912526T patent/ATE160169T1/de active
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Also Published As
Publication number | Publication date |
---|---|
US5691293A (en) | 1997-11-25 |
DK0692020T3 (da) | 1998-07-27 |
EP0692020A1 (de) | 1996-01-17 |
PL177250B1 (pl) | 1999-10-29 |
ES2110742T3 (es) | 1998-02-16 |
PL310951A1 (en) | 1996-01-08 |
DE59404581D1 (de) | 1997-12-18 |
CZ253195A3 (en) | 1996-05-15 |
DE4315048A1 (de) | 1994-10-06 |
CZ286894B6 (en) | 2000-07-12 |
HU9502850D0 (en) | 1995-11-28 |
ATE160169T1 (de) | 1997-11-15 |
HUT72020A (en) | 1996-03-28 |
EP0692020B1 (de) | 1997-11-12 |
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