EP0692020B1 - Stable, bifunctional, phosphate-, metasilicate- and polymer-free low alkaline detergent tablets for dishwashing machines, and process for producing the same - Google Patents
Stable, bifunctional, phosphate-, metasilicate- and polymer-free low alkaline detergent tablets for dishwashing machines, and process for producing the same Download PDFInfo
- Publication number
- EP0692020B1 EP0692020B1 EP94912526A EP94912526A EP0692020B1 EP 0692020 B1 EP0692020 B1 EP 0692020B1 EP 94912526 A EP94912526 A EP 94912526A EP 94912526 A EP94912526 A EP 94912526A EP 0692020 B1 EP0692020 B1 EP 0692020B1
- Authority
- EP
- European Patent Office
- Prior art keywords
- weight
- sodium
- water
- tablets
- free
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Expired - Lifetime
Links
- 239000003599 detergent Substances 0.000 title claims abstract description 15
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 title claims abstract 3
- 238000000034 method Methods 0.000 title claims description 13
- 238000004851 dishwashing Methods 0.000 title claims description 11
- 230000001588 bifunctional effect Effects 0.000 title description 5
- 239000000203 mixture Substances 0.000 claims abstract description 48
- UIIMBOGNXHQVGW-UHFFFAOYSA-M Sodium bicarbonate Chemical compound [Na+].OC([O-])=O UIIMBOGNXHQVGW-UHFFFAOYSA-M 0.000 claims abstract description 30
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 claims abstract description 29
- 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 23
- 239000001509 sodium citrate Substances 0.000 claims abstract description 20
- 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
- 239000007844 bleaching agent Substances 0.000 claims abstract description 17
- 229910000030 sodium bicarbonate Inorganic materials 0.000 claims abstract description 15
- 235000017557 sodium bicarbonate Nutrition 0.000 claims abstract description 15
- 108010065511 Amylases Proteins 0.000 claims abstract description 7
- 102000013142 Amylases Human genes 0.000 claims abstract description 7
- 108091005804 Peptidases Proteins 0.000 claims abstract description 7
- 239000004365 Protease Substances 0.000 claims abstract description 7
- 235000019418 amylase Nutrition 0.000 claims abstract description 7
- XSVSPKKXQGNHMD-UHFFFAOYSA-N 5-bromo-3-methyl-1,2-thiazole Chemical compound CC=1C=C(Br)SN=1 XSVSPKKXQGNHMD-UHFFFAOYSA-N 0.000 claims abstract description 5
- 239000004382 Amylase Substances 0.000 claims abstract description 5
- 102100037486 Reverse transcriptase/ribonuclease H Human genes 0.000 claims abstract description 5
- VTIIJXUACCWYHX-UHFFFAOYSA-L disodium;carboxylatooxy carbonate Chemical compound [Na+].[Na+].[O-]C(=O)OOC([O-])=O VTIIJXUACCWYHX-UHFFFAOYSA-L 0.000 claims abstract description 5
- 229940045872 sodium percarbonate Drugs 0.000 claims abstract description 5
- FRPJTGXMTIIFIT-UHFFFAOYSA-N tetraacetylethylenediamine Chemical compound CC(=O)C(N)(C(C)=O)C(N)(C(C)=O)C(C)=O FRPJTGXMTIIFIT-UHFFFAOYSA-N 0.000 claims abstract description 5
- 239000003513 alkali Substances 0.000 claims abstract description 4
- 239000005662 Paraffin oil Substances 0.000 claims description 15
- 239000003205 fragrance Substances 0.000 claims description 15
- 238000004090 dissolution Methods 0.000 claims description 11
- 239000002736 nonionic surfactant Substances 0.000 claims description 11
- 239000012190 activator Substances 0.000 claims description 10
- 102000004190 Enzymes Human genes 0.000 claims description 9
- 108090000790 Enzymes Proteins 0.000 claims description 9
- 229910000029 sodium carbonate Inorganic materials 0.000 claims description 9
- 125000005456 glyceride group Chemical group 0.000 claims description 8
- 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 8
- -1 other builders Substances 0.000 claims description 7
- 239000000975 dye Substances 0.000 claims description 6
- 229960000999 sodium citrate dihydrate Drugs 0.000 claims description 6
- 238000002156 mixing Methods 0.000 claims description 5
- 238000005187 foaming Methods 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
- 239000004094 surface-active agent Substances 0.000 claims description 4
- 235000014113 dietary fatty acids Nutrition 0.000 claims description 3
- 239000000194 fatty acid Substances 0.000 claims description 3
- 229930195729 fatty acid Natural products 0.000 claims description 3
- 150000004665 fatty acids Chemical class 0.000 claims description 3
- 239000007788 liquid Substances 0.000 claims description 3
- 238000004519 manufacturing process Methods 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
- 150000003626 triacylglycerols Chemical class 0.000 claims description 3
- 230000002349 favourable effect Effects 0.000 claims description 2
- MPJRTONOKVZPBA-UHFFFAOYSA-N CC(O)=O.[N-3].[Na+].[Na+].[Na+] Chemical compound CC(O)=O.[N-3].[Na+].[Na+].[Na+] MPJRTONOKVZPBA-UHFFFAOYSA-N 0.000 claims 2
- 150000002927 oxygen compounds Chemical class 0.000 claims 2
- 229940038773 trisodium citrate Drugs 0.000 claims 1
- 238000004140 cleaning Methods 0.000 description 16
- 239000012459 cleaning agent Substances 0.000 description 7
- 229940088598 enzyme Drugs 0.000 description 6
- 238000003825 pressing Methods 0.000 description 6
- 239000008139 complexing agent Substances 0.000 description 5
- 235000017550 sodium carbonate Nutrition 0.000 description 5
- NTHWMYGWWRZVTN-UHFFFAOYSA-N sodium silicate Chemical compound [Na+].[Na+].[O-][Si]([O-])=O NTHWMYGWWRZVTN-UHFFFAOYSA-N 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
- 229910052783 alkali metal Inorganic materials 0.000 description 4
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 4
- 150000001875 compounds Chemical class 0.000 description 4
- 239000010794 food waste Substances 0.000 description 4
- 239000001301 oxygen Substances 0.000 description 4
- 229910052760 oxygen Inorganic materials 0.000 description 4
- 239000000126 substance 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
- 239000004115 Sodium Silicate Substances 0.000 description 3
- 239000000654 additive Substances 0.000 description 3
- 229910052910 alkali metal silicate Inorganic materials 0.000 description 3
- 238000007906 compression Methods 0.000 description 3
- 230000006835 compression Effects 0.000 description 3
- 239000000470 constituent Substances 0.000 description 3
- 239000006260 foam Substances 0.000 description 3
- 239000008187 granular material Substances 0.000 description 3
- 235000019589 hardness Nutrition 0.000 description 3
- 150000004682 monohydrates Chemical class 0.000 description 3
- 239000011734 sodium Substances 0.000 description 3
- 235000019795 sodium metasilicate Nutrition 0.000 description 3
- 229910052911 sodium silicate Inorganic materials 0.000 description 3
- 239000001226 triphosphate Substances 0.000 description 3
- 238000005406 washing Methods 0.000 description 3
- LYPVKWMHGFMDPD-UHFFFAOYSA-N 1,5-diacetyl-1,3,5-triazinane-2,4-dione Chemical compound CC(=O)N1CN(C(C)=O)C(=O)NC1=O LYPVKWMHGFMDPD-UHFFFAOYSA-N 0.000 description 2
- 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
- 229910019142 PO4 Inorganic materials 0.000 description 2
- 102000035195 Peptidases Human genes 0.000 description 2
- 239000002202 Polyethylene glycol Substances 0.000 description 2
- UIIMBOGNXHQVGW-DEQYMQKBSA-M Sodium bicarbonate-14C Chemical compound [Na+].O[14C]([O-])=O UIIMBOGNXHQVGW-DEQYMQKBSA-M 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
- 125000000217 alkyl group Chemical group 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
- 238000009472 formulation 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
- 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
- 229920001223 polyethylene glycol Polymers 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
- 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
- 239000008399 tap water Substances 0.000 description 2
- 235000020679 tap water Nutrition 0.000 description 2
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 description 1
- DBVJJBKOTRCVKF-UHFFFAOYSA-N Etidronic acid Chemical compound OP(=O)(O)C(O)(C)P(O)(O)=O DBVJJBKOTRCVKF-UHFFFAOYSA-N 0.000 description 1
- 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 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
- GOOHAUXETOMSMM-UHFFFAOYSA-N Propylene oxide Chemical group CC1CO1 GOOHAUXETOMSMM-UHFFFAOYSA-N 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
- VMHLLURERBWHNL-UHFFFAOYSA-M Sodium acetate Chemical compound [Na+].CC([O-])=O VMHLLURERBWHNL-UHFFFAOYSA-M 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
- 229910000288 alkali metal carbonate Inorganic materials 0.000 description 1
- 150000008041 alkali metal carbonates Chemical class 0.000 description 1
- 150000001447 alkali salts Chemical class 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
- 239000000969 carrier Substances 0.000 description 1
- 150000001805 chlorine compounds Chemical class 0.000 description 1
- 239000003086 colorant Substances 0.000 description 1
- 238000005056 compaction Methods 0.000 description 1
- 230000009918 complex formation Effects 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
- 150000002191 fatty alcohols Chemical class 0.000 description 1
- 235000021149 fatty food Nutrition 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
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 229910001463 metal phosphate Inorganic materials 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
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 description 1
- 239000010452 phosphate Substances 0.000 description 1
- 150000003013 phosphoric acid derivatives Chemical class 0.000 description 1
- 229920001748 polybutylene 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
- 102000004169 proteins and genes Human genes 0.000 description 1
- 108090000623 proteins and genes Proteins 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 150000004760 silicates Chemical class 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- 239000001632 sodium acetate Substances 0.000 description 1
- 235000017281 sodium acetate Nutrition 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
- POECFFCNUXZPJT-UHFFFAOYSA-M sodium;carbonic acid;hydrogen carbonate Chemical compound [Na+].OC(O)=O.OC([O-])=O POECFFCNUXZPJT-UHFFFAOYSA-M 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
- 235000011178 triphosphate Nutrition 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
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 a commercial dishwasher, hereinafter referred to as GGSM, the so-called pre-clearing zone corresponds in principle to the pre-wash cycle of an HGSM.
- the cleaning agent added to 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 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 in others Positioned in the machine, so that they could act both in the pre-rinse cycle and in the actual cleaning cycle, i.e. bifunctionally.
- Such tablet-shaped cleaning agents is described for example in DE-OS 35 41 145.
- These are uniform Compound detergent tablets with a broad dissolution profile for machine dishwashing, which contain the usual alkaline components, in particular from the group of alkali metal silicates and pentaalkali metal phosphates, active chlorine compounds and tableting aids, and in which the alkali metal silicates are made from a mixture of "sodium metasilicate nonahydrate 4 (Na. 2 H 2 Si.
- 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 metasilicate, each anhydrous, 2 to 1: 2, preferably 1: 1 to 1: 1.7.
- Tablets of this type have such a broad dissolving profile that they are dissolved by at least 10% by weight of tap water in the pre-rinsing phase of an HGSM, thereby developing a pH of at least 10.0 in the rinsing liquor and at least 60 with good hot water solubility % By weight, preferably at least 70% by weight, are available for the cleaning cycle.
- the dissolution profile is understood to mean the weight ratio of portions of the tablet to the entire tablet which are dissolved under the conditions of the pre-rinse cycle by conventional HGSM.
- phosphate-free detergent tablets for machine dishwashing e.g. Hui rinsing tabs from Roth GmbH, Bad Ems
- DE-OS 40 10 524 describes stable, bifunctional, phosphate-free detergent tablets for machine dishwashing containing silicate, low-foam nonionic surfactants, organic complexing agents, bleaching agents and water, the organic complexing agents according to DE-OS 39 37 469 in the form a granular, alkaline cleaning additive consisting of sodium salts containing 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 recipe 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 bicarbonate and the solid alkali salts of at least one homopolymeric or copolymeric (meth) acrylic acid together with the amount of water of about 5-40, preferably about 7-20% by weight, based on the anhydrous sodium carbonate used as the framework substance, required for the partial hydration of the anhydrous sodium carbonate, then added the remaining substances were 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 bicarbonate and the solid alkali salts of at least one homopolymeric or copolymeric (meth) acrylic acid together with the amount of water of about 5-40, preferably about 7-20% by weight, based on the anhydrous sodium carbonate used as the framework substance, required for the partial hydration of the anhydrous sodium carbonate, then added the remaining substances were added to the mixture
- the storage-stable tablets produced in this way have a high breaking strength (greater than 140 N with a diameter of about 30 to 40 mm and a density of about 1.4 to 1.7 g / cm 3 ), which likewise remains stable during storage and remains within it can significantly increase in a short time.
- the present invention now relates to stable, bifunctional, phosphate- and metasilicate-free, low-alkaline cleaning tablets for machine dishwashing containing sodium citrate and other builders, bleaching agents, bleach activators and enzymes and optionally nonionic surfactants, colorants and fragrances, characterized in that they optionally contain solution retardants and are polymer-free.
- Trisodium citrate dihydrate 5 50% 20-30% Nitrilotrine sodium acetate 0 - 25% 0 - 20% Sodium phosphonate 0 - 10% 0 - 5% Sodium carbonate, anhydrous 1 - 60% 1 - 20% Sodium disilicate 0 - 60% 2 - 30% Sodium bicarbonate 1 - 60% 30 - 50% Sodium perborate monohydrate and / or 0 - 15% 5 - 12% Sodium percarbonate 0 - 20% 5 - 15% Tetraacetylethylenediamine 0.5 - 4% 2 - 4% nonionic surfactant 0 - 4% 0.5 - 2% Protease 0.1 - 2% 0.5 - 1.5% Amylase 0.1 - 2% 0.5 - 1.5% Fragrance 0 - 1% 0.1 - 0.6% Paraffin oil 0 - 3% 0 - 1.5% Glyceride mixture 0 - 6% 1 -
- paraffin oil can also take place together with the addition of the sodium citrate, preferably in the form of a mixture which, in a preferred, separate mixed cut, preferably comprises 1-3% by weight, in particular approximately 2% by weight, of paraffin oil , based on the total detergent mixture and sodium citrate. Also advantageous is a hydrophobization of the sodium hydrogen carbonate 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 preferred method is that instead of adding a paraffin oil, the water used to moisten the sodium citrate is mixed with mixtures of mono-, di- and triglycerides of C 12 -C 18 , preferably C 16 -C 18 fatty acids.
- a further preferred embodiment of the process according to the invention is that first all liquid components of the composition are applied to the sodium citrate, then the anhydrous sodium carbonate is dusted on and then successively, in each case with low energy input, sodium bicarbonate, the bleach activator and finally the compound which releases active oxygen 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 mm and a density of about 1.4 to 1.7 g / cm 3 ), which increase significantly within a short time during storage can, and which also remain stable.
- alkali metal nitrilotriacetates, alkali metal phosphonates and alkali metal silicates 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. Anhydrous trisodium citrate or trisodium citrate dihydrate are suitable as sodium citrate. As alkali carbonate sodium carbonate of any quality is preferably used, such as. B. soda ash or compressed soda.
- the preferred alkali metal phosphonate is the tetrasodium salt of 1-hydroxyethane-1,1-di-phosphonic acid (Turpinal (R) 4 NZ from Henkel).
- Turpinal (R) 4 NZ from Henkel.
- Dried water glass with the module SiO 2 : Na 2 O 1: 2-2.5 (e.g. 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 C 12 -C 18 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.
- C 12 -C 18 alkyl polyethylene glycol 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.
- 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 caroate. Since active oxygen only develops its full effect on its own at elevated temperatures, so-called bleach activators are expediently used to activate it at about 60 ° C., the temperatures of the cleaning process in the HGSM.
- Preferred bleach activators are TAED (tetraacetylenediamine), PAG (pentaacetylglucose), DADHT (1,5-diacetyl-2,4-dioxo-hexahydro-1,3,5-triazine) and ISA (isatoic anhydride).
- Enzymes such as proteases and amylases, for example proteases such as BLAP (R) from Henkel, Opitmase (R) -M-440, Optimase (R) - -M-330, can also be used to better remove protein or starch-containing food residues , Opticlean (R) -M-375, Opticlean (R) -M-250 from Solvay Enzymes, 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.
- proteases such as BLAP (R) from Henkel, Opitmase (R) -M-440, Optimase (R) - -M-330,
- 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.
- tabletting aids such as mold release agents, for example paraffin oil, or mixtures of mono-, di- and triglycerides of C 12 -C 18 , preferably C 16 -C 18 fatty acids, for example commercially available glyceride mixtures sold as baking agents, such as 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 bicarbonate portion.
- the mixture prepared as described would be compressed on conventional tablet presses with a compression pressure of about 2 to 11 MPa, preferably about 4 to 6 MPa.
- the pressing could be carried out in a 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, supplied tablets with smooth surfaces, so that in most cases there was no need to coat 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, regardless of their format, can be determined by the degree of compaction, i. H. the baling pressure can be controlled.
- 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, preferably from approximately 0.4 to 1.2 g / cm 3 , preferably approximately 0.6 to 1.0 g / cm 3 to approximately 1.2 to 2.0 g / cm 3 increased about 1.4 to 1.6 g / cm 3 .
- the shape of the tablet can also influence the breaking strength and the dissolution rate via the outer surface exposed to the H 2 O attack. For reasons of stability, cylindrical compacts with a diameter / height ratio of approximately 0.6 to 4.0: 1 were produced.
- the tablet was loaded with a wedge to measure the breaking strength.
- the breaking strength corresponds to the weight of the wedge-shaped load that causes the tablet to break.
- 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.
- 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 on 0.9 part by weight of Dehydol LS4 and 0.6 part by weight of fragrance. 5 parts by weight of perborate monohydrate 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 breakability with too rapid dissolution 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, then 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 Dehydol LS4, the perborate monohydrate was finally mixed in separately.
- the mixture was prepared as described in Example 1, but in addition 1% paraffin oil was additionally sprayed onto the mixture.
- a mixture of water, Dehydol LS4 and fragrance was applied to the sodium citrate dihydrate placed in the Lödige ploughshare mixer, then dusted with soda and then the remaining components were added.
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Abstract
Description
Maschinelles Geschirrspülen besteht im allgemeinen aus einem Vorspülgang, einem Reinigungsgang, einem oder mehreren Zwischenspülgängen, einem Klarspülgang und einem Trocknungsgang. Dies gilt für das maschinelle Spülen sowohl im Haushalt als auch im Gewerbe.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.
Bisher ist es überwiegend üblich, in Haushaltsgeschirrspülmaschinen, im folgenden als HGSM bezeichnet, das Reinigungsmittel in einem Dosierkästchen zu bevorraten, das sich meist in der Tür der Maschine befindet und sich zu Beginn des Reinigungsganges automatisch öffnet. Der zuvor ablaufende Vorspülgang wird dabei ohne Wirksubstanz, also ausschließlich mit dem zulaufenden Leitungswasser betrieben.So far, it has been common practice in household dishwashers, hereinafter referred to as HGSM, to store the detergent in a dosing box, which is usually located in the door of the machine and opens automatically at the start of the cleaning cycle. The pre-rinse cycle that is running beforehand is operated without any active substance, i.e. exclusively with the tap water that is flowing in.
Bei einer gewerblichen Geschirrspülmaschine, im folgenden als GGSM bezeichnet, entspricht die sogenannte Vorabräumzone im Prinzip dem Vorspülgang einer HGSM. Beim maschinellen Spülen in Großküchen wird das der Reinigungszone zudosierte Reinigungsmittel durch Überlauf schon in der Vorabräumzone zur unterstützenden Reinigung der anhaftenden Speisereste eingesetzt. Es gibt zwar auch GGSM, bei denen die Vorabräumzone nur mit Frischwasser betrieben wird, eine Vorabräumzone mit Reinigungsmittelzusatz ist aber effektiver als eine Vorabräumung allein mit Frischwasser.In a commercial dishwasher, hereinafter referred to as GGSM, the so-called pre-clearing zone corresponds in principle to the pre-wash cycle of an HGSM. When machine washing in commercial kitchens, the cleaning agent added to the cleaning zone is used by overflow in the pre-clearing zone to support the cleaning of the adhering food residues. There are also 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.
Man hat das Wirkungsprinzip der Vorabräumzonenreinigung von GGSM auch schon auf HGSM übertragen und eine Zudosierung von Reinigungsmitteln bereits zum Vorspülgang ermöglicht, indem man die Dosierung von Reinigungsmitteln in Tablettenform vornahm und eine oder mehrere geeignete Tabletten beispielsweise in einem freien Teil des Besteckkorbes, aber auch an anderer Stelle in der Maschine positionierte, wodurch sie sowohl im Vorspülgang als auch im eigentlichen Reinigungsgang, also bifunktionell, wirken konnten.The principle of pre-clearing zone cleaning from GGSM has 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 in others Positioned in the machine, so that they could act both in the pre-rinse cycle and in the actual cleaning cycle, i.e. bifunctionally.
Der Einsatz solcher tablettenförmiger Reinigungsmittel ist beispielsweise in der DE-OS 35 41 145 beschrieben. Dabei handelt es sich um einheitlich zusammengesetzte Reinigungsmitteltabletten mit breitem Löseprofil für das maschinelle Geschirrspülen, die übliche alkalisch reagierende Komponenten, insbesondere aus der Gruppe der Alkalimetasilikate und Pentaalkalitriphosphate, Aktivchlorverbindungen und Tablettierhilfsmittel enthalten, und bei denen die Alkalimetasilikate aus einem Gemisch aus "Natriummetasilikatnonahydrat" (Na2H2SiO4.8H2O) und wasserfreiem Natriummetasilikat und das Pentaalkalitriphosphat aus wasserfreiem Pentanatriumtriphosphat besteht, wobei das Gewichtsverhältnis von wasserfreiem Natriummetasilikat : Natriummetasilikatnonahydrat zwischen 1 : 0,3 und 1 : 1,5 liegt und das Gewichtsverhältnis von Pentanatriumtriphosphat zu Natriummetasilikat, jeweils wasserfrei, 2 : 1 bis 1 : 2, vorzugsweise 1 : 1 bis 1 : 1,7 beträgt.The use of such tablet-shaped cleaning agents is described for example in DE-OS 35 41 145. These are uniform Compound detergent tablets with a broad dissolution profile for machine dishwashing, which contain the usual alkaline components, in particular from the group of alkali metal silicates and pentaalkali metal phosphates, active chlorine compounds and tableting aids, and in which the alkali metal silicates are made from a mixture of "sodium metasilicate nonahydrate 4 (Na. 2 H 2 Si. 8H 2 O) 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 metasilicate, each anhydrous, 2 to 1: 2, preferably 1: 1 to 1: 1.7.
Derartige Tabletten besitzen ein solches breites Löseprofil, daß sie bereits im Vorspülgang einer HGSM vom zulaufenden Leitungswasser zu mindestens 10 Gew.-% aufgelöst werden, dabei in der Spülflotte einen pH-Wert von mindestens 10,0 entwickeln und bei guter Warmwasserlöslichkeit zu noch mindestens 60 Gew.-%, vorzugsweise mindestens 70 Gew.-%, für den Reinigungsgang zu Verfügung stehen.Tablets of this type have such a broad dissolving profile that they are dissolved by at least 10% by weight of tap water in the pre-rinsing phase of an HGSM, thereby developing a pH of at least 10.0 in the rinsing liquor and at least 60 with good hot water solubility % By weight, preferably at least 70% by weight, are available for the cleaning cycle.
Unter Löseprofil wird das Gewichtsverhältnis von unter den Bedingungen des Vorspülganges von üblichen HGSM gelösten Anteilen der Tablette zur gesamten Tablette verstanden.The dissolution profile is understood to mean the weight ratio of portions of the tablet to the entire tablet which are dissolved under the conditions of the pre-rinse cycle by conventional HGSM.
Diese bekannten Tabletten enthielten jedoch noch Phosphate, die wie man weiß unerwünscht sind.However, these known tablets still contained phosphates, which are known to be undesirable.
Es sind aber seit einiger Zeit auch schon phosphatfreie Reinigungsmitteltabletten für das maschinelle Geschirrspülen im Handel (z. b. Hui Spül-Tabs der Firma Roth GmbH, Bad Ems), die im wesentlichen Silikate, nichtionische Tenside, organische Komplexbildner und Percarbonat enthalten. Bei einer Placierung dieser Tabletten innerhalb der Maschine (z. B. im Besteckkorb) lösen sie sich jedoch schon während des Vorspülganges weitestgehend bis vollständig auf, so daß im eigentlichen Reinigungsgang praktisch kein Reinigungsmittel mehr zur Verfügung steht. Darüber hinaus ist die Stabilität dieser Tabletten nicht befriedigend.However, phosphate-free detergent tablets for machine dishwashing (e.g. Hui rinsing tabs from Roth GmbH, Bad Ems) have been on the market for some time, which essentially contain silicates, nonionic surfactants, organic complexing agents and percarbonate. If these tablets are placed inside the machine (e.g. in the cutlery basket), however, they dissolve as far as possible, even completely, during the pre-rinse cycle, so that they are practical in the actual cleaning cycle no cleaning agent is available. In addition, the stability of these tablets is unsatisfactory.
In der DE-OS 40 10 524 werden stabile, bifunktionelle, phosphatfreie Reinigungsmitteltabletten für das maschinelle Geschirrspülen mit einem Gehalt an Silikat, schaumarmen nichtionischen Tensiden, organischen Komplexbildnern, Bleichmitteln und Wasser beschrieben, die organische Komplexbildner gemäß der DE-OS 39 37 469 in Form eines granularen, alkalischen Reinigungsadditivs, bestehend aus Natriumsalzen mindestens einer homopolymeren bzw. copolymeren (Meth-)Acrylsäure, Natriumcarbonat, Natriumsulfat und Wasser enthalten. Bei der Herstellung der Tabletten wurden die granularen alkalischen Reinigungsadditive mit den übrigen meist pulverförmigen Rezepturbestandteilen mechanisch gemischt und in an sich bekannter Weise verpreßt.DE-OS 40 10 524 describes stable, bifunctional, phosphate-free detergent tablets for machine dishwashing containing silicate, low-foam nonionic surfactants, organic complexing agents, bleaching agents and water, the organic complexing agents according to DE-OS 39 37 469 in the form a granular, alkaline cleaning additive consisting of sodium salts containing at least one homopolymeric or copolymeric (meth) acrylic acid, sodium carbonate, sodium sulfate and water. In the manufacture of the tablets, the granular alkaline cleaning additives were mechanically mixed with the other mostly powdery recipe components and pressed in a manner known per se.
Einem weiteren Markttrend folgend wurden unter anderem gemäß der DE-OS 41 21 307 stabile, bifunktionelle, phosphat- und metasilikatfreie niederalkalische Reinigungsmitteltablette mit breitem Löseprofil für das maschinelle Geschirrspülen zur Verfügung gestellt, die ebenfalls bereits im Vorspülgang einer HGSM vom zulaufenden Leitungswasser zu mindestens 10 Gew.-% bis etwa 50 Gew.-% aufgelöst werden, dabei in der Spülflotte einen pH-Wert von höchstens etwa 10,5 entwickeln und bei guter Warmwasserlöslichkeit zu noch mindestens 50 Gew.-% bis etwa 90 Gew.-% für den Reinigungsgang zur Verfügung stehen. Sie enthalten als Komplexbildner organische Polymere.Following a further market trend, stable, bifunctional, phosphate- and metasilicate-free, low-alkaline detergent tablets with a broad dissolving profile for machine dishwashing were made available, among other things, according to DE-OS 41 21 307 .-% to about 50 wt .-% are dissolved, thereby developing a pH value of at most about 10.5 in the washing liquor and with good hot water solubility to at least 50 wt .-% to about 90 wt .-% for the cleaning cycle be available. They contain organic polymers as complexing agents.
Zur Herstellung dieser bekannten Reinigungsmitteltabletten wurde das als Teil der Gerüstsubstanzen dienende Natriumcarbonat in wasserfreier Form eingesetzt und zunächst in einem Mischgang, vorzugsweise allein oder mit den anderen Gerüstsubstanzen wie Natriumcitrat und gegebenenfalls Natriumhydrogencarbonat und den festen Alkalisalzen mindestens einer homopolymeren bzw. copolymeren (Meth-)Acrylsäure zusammen mit der für die Teilhydratisation des wasserfreien Natriumcarbonats erforderlichen Menge Wasser von etwa 5-40, vorzugsweise etwa 7-20 Gew.-%, bezogen auf das als Gerüstsubstanz eingesetzte wasserfreie Natriumcarbonat, versetzt, anschliessend wurden die restlichen Stoffe der Mischung zufügt und das so erhaltene Gemisch auf einer üblichen Tablettenpresse verpreßt. Die so hergestellten lagerstabilen Tabletten besitzen eine hohe Bruchfestigkeit (größer 140 N bei einem Durchmesser von etwa 30 bis 40 mm und einer Dichte von etwa 1,4 bis 1,7 g/cm3), die bei Lagerung ebenfalls stabil bleibt und sich dabei innerhalb kurzer Zeit noch deutlich erhöhen kann.To produce these known detergent tablets, 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 bicarbonate and the solid alkali salts of at least one homopolymeric or copolymeric (meth) acrylic acid together with the amount of water of about 5-40, preferably about 7-20% by weight, based on the anhydrous sodium carbonate used as the framework substance, required for the partial hydration of the anhydrous sodium carbonate, then added the remaining substances were added to the mixture and the mixture thus obtained was compressed on a conventional tablet press. The storage-stable tablets produced in this way have a high breaking strength (greater than 140 N with a diameter of about 30 to 40 mm and a density of about 1.4 to 1.7 g / cm 3 ), which likewise remains stable during storage and remains within it can significantly increase in a short time.
Bei dem Versuch, ohne organische Komplexbildner auszukommen und dafür etwa die Anteile an Natriumcitrat und Natriumhydrogencarbonat zu erhöhen, konnten zunächst keine bruchstabilen Tabletten erhalten werden. Außerdem waren die Tabletten zu "gut" löslich, d.h. sie lösten sich bereits fast vollständig im Vorspülgang, so daß für den eigentlichen Reinigungsprozeß praktisch kein Reinigungsmittel mehr zur Verfügung stand.In an attempt to get by without organic complexing agents and to increase the proportions of sodium citrate and sodium bicarbonate, it was initially not possible to obtain break-stable tablets. In addition, the tablets were too "well" soluble, i.e. they already dissolved almost completely in the pre-rinse cycle, so that there was practically no detergent available for the actual cleaning process.
Gegenstand der vorliegenden Erfindung sind nun stabile, bifunktionelle, phosphat- und metasilikatfreie, niederalkalische Reinigungstabletten für das maschinelle Geschirrspülen mit einem Gehalt an Natriumcitrat und weiteren Gerüstsubstanzen, Bleichmitteln, Bleichaktivatoren und Enzymen sowie gegebenenfalls nichtionischen Tensiden, Farb- und Duftstoffen, dadurch gekennzeichnet, daß sie gegebenenfalls Lösungsverzögerungsmitteln enthalten und polymerfrei sind.The present invention now relates to stable, bifunctional, phosphate- and metasilicate-free, low-alkaline cleaning tablets for machine dishwashing containing sodium citrate and other builders, bleaching agents, bleach activators and enzymes and optionally nonionic surfactants, colorants and fragrances, characterized in that they optionally contain solution retardants and are polymer-free.
Sie entsprechen folgender Rahmenrezeptur:
Es wurde ein Verfahren gefunden, bei dem man zu solchen stabilen, bifunktionellen, phosphat-, metasilikat- und nunmehr auch polymerfreien, niederalkalischen Reinigungsmitteltabletten für das maschinelle Geschirrspülen mit einem Gehalt an Natriumcitrat, weiteren Gerüstsubstanzen, schaumarmen Tensiden, Bleichmitteln und Enzymen, Bleichaktivatoren, Duft- und Farbstoffen kommt, wenn man zunächst Natriumcitratdihydrat und/oder Natriumcitrat mit einer geringen Menge Wasser von 3 - 10, vorzugsweise 4 - 6 Gew.-%, bezogen auf die Gesamtzusammensetzung, befeuchtet, anschließend wasserfreies Natriumcarbonat aufstäubt und dann Natriumhydrogencarbonat und den Bleichaktivator zumischt, Enzyme, nichtionische Tenside, Duft-/Farbstoffe und gegebenenfalls Paraffinöl zugibt, zum Schluß mit geringem Energieeintrag die Aktivsauerstoff abspaltende Verbindung zumischt und das so erhaltene Gesamtgemisch auf einer üblichen Tablettenpresse bei einer relativen Luftfeuchtigkeit von 15 bis 60, vorzugsweise 20 bis 30 % mit einem Preßdruck von 2 bis 11, vorzugsweise 4 bis 6 MPa zu Tabletten verpreßt.A process has been found in which such stable, bifunctional, phosphate, metasilicate and now also polymer-free, low-alkaline detergent tablets for automatic dishwashing containing sodium citrate, other builders, low-foam surfactants, bleaching agents and enzymes, bleach activators, and fragrances - and dyes come if you first moisten sodium citrate dihydrate and / or sodium citrate with a small amount of water of 3 - 10, preferably 4 - 6 wt .-%, based on the total composition, then dusted with anhydrous sodium carbonate and then add sodium hydrogen carbonate and the bleach activator , Enzymes, nonionic surfactants, fragrances / dyes and optionally paraffin oil are added, at the end the active oxygen-releasing compound is mixed in with a low energy input and the overall mixture thus obtained on a conventional tablet press at a relative atmospheric humidity of 15 to 60, preferably e 20 to 30% pressed into tablets with a pressure of 2 to 11, preferably 4 to 6 MPa.
Die - fakultative - Zugabe des Paraffinöls kann auch bereits gemeinsam mit der Zugabe des Natriumcitrats erfolgen, vorzugsweise in Form eines Gemisches, das in einem vorgezogenen, separaten Mischschnitt aus vorzugsweise 1 - 3 Gew.-%, insbesondere ca. 2 Gew.-% Paraffinöl, bezogen auf die gesamte Reinigungsmittelmischung und Natriumcitrat hergestellt wird. Vorteilhaft ist auch eine in einem vorgezogenen Mischschritt mit Paraffinöl durchgeführte Hydrophobierung des Natriumhydrogencarbonates.The - optional - addition of the paraffin oil can also take place together with the addition of the sodium citrate, preferably in the form of a mixture which, in a preferred, separate mixed cut, preferably comprises 1-3% by weight, in particular approximately 2% by weight, of paraffin oil , based on the total detergent mixture and sodium citrate. Also advantageous is a hydrophobization of the sodium hydrogen carbonate carried out in a preferred mixing step with paraffin oil.
Eine erwünschte weitere Verzögerung der Auflösung im Vorspülgang einer HGSM kann erfolgen, wenn man das eingangs zugegebene Wasser bereits mit dem nichtionischen Tensid, dem auch der Duftstoff zugefügt werden kann, oder mit einem Glyceridgemisch vermischt und auf das Natriumcitrat düst und dann die Restsubstanzen zufügt.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.
Ein bevorzugtes Verfahren besteht darin, daß man an Stelle eines Paraffinölzusatzes das der Befeuchtung des Natriumcitrat dienende Wasser mit Gemischen aus Mono-, Di- und Triglyceriden von C12-C18-, vorzugsweise C16-C18-Fettsäuren versetzt.A preferred method is that instead of adding a paraffin oil, the water used to moisten the sodium citrate is mixed with mixtures of mono-, di- and triglycerides of C 12 -C 18 , preferably C 16 -C 18 fatty acids.
Eine weitere bevorzugte Ausführungsform des erfindungsgemäßen Verfahrens besteht darin, daß zuerst alle flüssigen Komponenten der Zusammensetzung auf das Natriumcitrat aufgetragen werden, dann das wasserfreie Natriumcarbonat aufgestäubt wird und anschließend nacheinander, jeweils mit geringem Energieeintrag, Natriumhydrogencarbonat, der Bleichaktivator und abschließend die Aktivsauerstoff abspaltende Verbindung zugegeben werden und das so erhaltene Gesamtgemisch wie vorstehend angegeben verpreßt wird. Unter "geringen Energieeintrag" versteht man eine schonende Vermischung ohne Einsatz der hochtourig laufenden Messerköpfe bei nur kurzen Verweilzeiten im Mischer.A further preferred embodiment of the process according to the invention is that first all liquid components of the composition are applied to the sodium citrate, then the anhydrous sodium carbonate is dusted on and then successively, in each case with low energy input, sodium bicarbonate, the bleach activator and finally the compound which releases active oxygen 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.
Die erfindungsgemäß hergestellten lagerstabilen Tabletten besitzen eine hohe Bruchfestigkeit (größer 140 N bei einem Durchmesser von etwa 30 bis 40 mm und einer Dichte von etwa 1,4 bis 1,7 g/cm3), die sich bei Lagerung innerhalb kurzer Zeit noch deutlich erhöhen kann, und die ebenfalls stabil bleiben.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 mm and a density of about 1.4 to 1.7 g / cm 3 ), which increase significantly within a short time during storage can, and which also remain stable.
Als Gerüstsubstanzen können neben Natriumcitrat und Alkalihydrogencarbonaten und/oder Alkalicarbonaten noch Alkalinitrilotriacetate, Alkaliphosphonate und Alkalidisilikate dienen. Sie binden durch Komplexbildung bzw. Dispergierung Härtebildner wie Calcium- und Magnesiumionen aus dem Wasser bzw. aus den Speiseresten und verhindern damit die Bildung von Kalkbelägen in der Spülmaschine und auf dem Geschirr. Sie können als wasserfreie und/-oder als Hydratsalze eingesetzt werden. Als Natriumcitrat kommen wasserfreies Trinatriumcitrat bzw. Trinatriumcitrat-dihydrat in Betracht. Als Alkalicarbonat wird vorzugsweise Natriumcarbonat beliebiger Qualität eingesetzt, wie z. B. calcinierte Soda oder verdichtete Soda. Als Natriumhydrogencarbonat kann solches beliebiger Herkunft verwendet werden. Bevorzugtes Alkaliphosphonat ist das Tetranatriumsalz der 1-Hydroxyethan-1,1-di-phosphonsäure (Turpinal (R) 4 NZ der Firma Henkel). Als Natriumdisilikat eignet sich getrocknetes Wasserglas mit dem Modul SiO2 : Na2O = 1 : 2-2,5, (z. B. Portil (R) A bzw. AW der Firma Henkel, Britesil (R) H 24 bzw. C 24 der Firma Akzo).In addition to sodium citrate and alkali metal bicarbonates and / or alkali metal carbonates, alkali metal nitrilotriacetates, alkali metal phosphonates and alkali metal silicates 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. Anhydrous trisodium citrate or trisodium citrate dihydrate are suitable as sodium citrate. As alkali carbonate sodium carbonate of any quality is preferably used, such as. B. soda ash or compressed soda. Any of these sources can be used as sodium hydrogen carbonate. The preferred alkali metal phosphonate is the tetrasodium salt of 1-hydroxyethane-1,1-di-phosphonic acid (Turpinal (R) 4 NZ from Henkel). Dried water glass with the module SiO 2 : Na 2 O = 1: 2-2.5 (e.g. Portil (R) A or AW from Henkel, Britesil (R) H 24 or C ) is suitable as sodium disilicate 24 from Akzo).
Als schaumarme Tenside, die der besseren Ablösung fetthaltiger Speisereste und als Preßhilfsmittel dienen, werden vorzugsweise extrem schaumarme nichtionische Verbindungen eingesetzt. Hierzu zählen vorzugsweise C12-C18-Alkylpolyethylenglykol-polypropylenglykolether mit jeweils bis zu 8 Mol Ethylenoxid- und Propylenoxideinheiten im Molekül. Ihr Anteil am Gesamtgewicht der fertigen Tabletten beträgt im allgemeinen etwa 0,2 bis 5, vorzugsweise etwa 0,5 bis 3 Gew.-%. Man kann aber auch andere als schaumarm bekannte nichtionische Tenside verwenden, wie z. B. C12-C18-Alkylpolyethylenglykol-polybutylenglykolether mit jeweils bis zu 8 Mol Ethylenoxid- und Butylenoxideinheiten im Molekül und dann gegebenenfalls noch etwa 0,2 bis 2, vorzugsweise etwa 0,2 bis 1 Gew.-%, bezogen auf die gesamte Tablette, an Entschäumungsmitteln wie z. B. Silikonöle, Gemische aus Silikonöl und hydrophobierter Kieselsäure, Paraffinöl/Guerbetalkoholen und hydrophobierter Kieselsäure zusetzen.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 C 12 -C 18 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. C 12 -C 18 alkyl polyethylene glycol 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. silicone oils, mixtures of silicone oil and hydrophobicized silica, paraffin oil / Guerbet alcohols and hydrophobicized silica.
Als Bleichmittel sind nunmehr vorzugsweise Aktivsauerstoffträger übliche Bestandteile von Reinigungsmitteln für HGSM. Dazu gehören in erster Linie Natriumperboratmono- und -tetrahydrat sowie Natriumpercarbonat und Natriumcaroat. Da Aktivsauerstoff erst bei erhöhten Temperaturen von allein seine volle Wirkung entfaltet, werden zu seiner Aktivierung bei ca. 60°C, den Temperaturen des Reinigungsprozesses in der HGSM, zweckmäßig noch sogenannte Bleichaktivatoren eingesetzt. Als Bleichaktivatoren dienen bevorzugt TAED (Tetraacetylendiamin), PAG (Pentaacetylglucose), DADHT (1,5-Diacetyl-2,4-dioxo-hexahydro-1,3,5-triazin) und ISA (Isatosäureanhydrid).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 caroate. Since active oxygen only develops its full effect on its own at elevated temperatures, so-called bleach activators are expediently used to activate it at about 60 ° C., the temperatures of the cleaning process in the HGSM. Preferred bleach activators are TAED (tetraacetylenediamine), PAG (pentaacetylglucose), DADHT (1,5-diacetyl-2,4-dioxo-hexahydro-1,3,5-triazine) and ISA (isatoic anhydride).
Zur besseren Ablösung Eiweiß- bzw. Stärke-haltiger Speisereste können noch Enzyme wie Proteasen und Amylasen eingesetzt werden, beispielsweise Proteasen wie BLAP (R) der Firma Henkel, Opitmase (R) -M-440, Optimase (R) - -M-330, Opticlean(R) -M-375, Opticlean (R) -M-250 der Firma Solvay Enzymes, Maxacal (R) CX 450.000, Maxapem (R) der Firma Ibis, Savinase (R) T der Firma Novo oder Esperase (R) T der Firma Ibis und Amylasen wie Termamyl (R) 60 T, 90 T der Firma Novo, Amylase-LT (R) der Firma Solvay Enzymes oder Maxamyl (R) P 5000 der Firma Ibis.Enzymes such as proteases and amylases, for example proteases such as BLAP (R) from Henkel, Opitmase (R) -M-440, Optimase (R) - -M-330, can also be used to better remove protein or starch-containing food residues , Opticlean (R) -M-375, Opticlean (R) -M-250 from Solvay Enzymes, 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.
Den Tablettenmischungen können auch übliche oxidationsstabile Farb- und Duftstoffe zugefügt werden. Aus ästhetischen Gründen kann man die Tabletten bei sonst gleicher Zusammensetzung auch in farbigen Schichten verpressen.Customary oxidation-stable dyes and fragrances can also be added to the tablet mixtures. For aesthetic reasons, the tablets can also be pressed in colored layers with otherwise the same composition.
Der Einsatz von Tablettierungshilfsmitteln, wie Formtrennmitteln, beispielsweise Paraffinöl, oder Gemischen aus Mono-, Di- und Triglyceriden von C12-C18-, vorzugsweise C16-C18-Fettsäuren etwa handelsüblichen als Backmittel vertriebenen Glyceridgemischen wie z.B. Boeson VP (Boehringer, Ingelheim) ist zum Verpressen der erfindungsgemäßen Tabletten nicht erforderlich und kann meist weggelassen werden, wenn die Tablettenmischungen nichtionische Tenside enthalten, die diese Aufgabe im wesentlichen übernehmen. Ein Zusatz von Paraffinöl und/oder Glyceridgemischen kann dennoch wie angegeben zweckmäßig sein, weil er zu einer Lösungsverzögerung der Tabletten führt, so daß ein höherer Anteil der Tablette im Reinigungsgang zur Verfügung steht. Die Einstellung des gewünschten pH-Wertes erfolgt vorzugsweise über den Natriumhydrogencarbonatanteil.The use of tabletting aids, such as mold release agents, for example paraffin oil, or mixtures of mono-, di- and triglycerides of C 12 -C 18 , preferably C 16 -C 18 fatty acids, for example commercially available glyceride mixtures sold as baking agents, such as 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 bicarbonate portion.
Das wie beschrieben hergestellte Gemisch würde auf herkömmlichen Tablettenpressen mit einem Preßdruck von etwa 2 bis 11 MPa, vorzugsweise etwa 4 bis 6 MPa verpreßt. Das Verpressen konnte ohne Matrizenschmierung in bekannter Weise mit Hilfe von handelsüblichen Excenterpressen, hydraulischen Pressen oder Rundläuferpressen erfolgen. Es wurden keine Anbackungen des Tablettengemisches an den Preßwerkzeugen beobachtet. Mit hartem Kunststoff beschichtete Werkzeuge lieferten, ebenso wie unbeschichtete, Tabletten mit glatten Oberflächen, so daß auch in den meisten Fällen auf eine Beschichtung der Stempel mit weichem Kunststoff verzichtet werden konnte.The mixture prepared as described would be compressed on conventional tablet presses with a compression pressure of about 2 to 11 MPa, preferably about 4 to 6 MPa. The pressing could be carried out in a 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, supplied tablets with smooth surfaces, so that in most cases there was no need to coat the punches with soft plastic.
Die Preßbedingungen wurden im Hinblick auf die Einstellung des gewünschten Löseprofils bei gleichzeitig ausreichender Tablettenhärte optimiert. Als Maß für die Tablettenhärte kann die Biegefestigkeit dienen (Methode: vergleiche Ritschel. Die Tablette, Ed. Cantor, 1966, S. 313). Ausreichend stabil sind danach unter simulierten Transportbedingungen Tabletten mit einer Biegefestigkeit größer als 100 N, vorzugsweise größer als 150 N. Die Biege- bzw. Bruchfestigkeit der Tabletten kann unabhängig von ihrem Format durch den Grad der Verdichtung, d. h. den Preßdruck gesteuert werden.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, regardless of their format, can be determined by the degree of compaction, i. H. the baling pressure can be controlled.
Entsprechende Tablettenhärten wurden bei den vorstehend angegebenen Preßdrücken erreicht. Löslichkeitsdifferenzen können bei unterschiedlichen Zusammensetzungen durch Varianten des Preßdrucks in Grenzen ausgeglichen werden.Corresponding tablet hardnesses were achieved at the compression pressures given above. Differences in solubility can be compensated to a limited extent for different compositions by means of variations in the pressure.
Das spezifische Gewicht der Preßlinge lag dabei zwischen etwa 1,2 und 2 g/cm3, vorzugsweise zwischen etwa 1,4 bis 1,8 g/cm3. Die Verdichtung beim Preßvorgang bewirkte Änderungen der Dichte, die von etwa 0,4 bis 1,2 g/cm3, vorzugsweise etwa 0,6 bis 1,0 g/cm3 auf etwa 1,2 bis 2,0 g/cm3, vorzugsweise etwa 1,4 bis 1,6 g/cm3 stieg.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, preferably from approximately 0.4 to 1.2 g / cm 3 , preferably approximately 0.6 to 1.0 g / cm 3 to approximately 1.2 to 2.0 g / cm 3 increased about 1.4 to 1.6 g / cm 3 .
Auch die Form der Tablette kann die Bruchfestigkeit und die Lösegeschwindigkeit über die dem H2O-Angriff ausgesetzte äußere Oberfläche beeinflussen. Aus Stabilitätsgründen wurden zylindrische Preßlinge mit einem Durchmesser/Höhe-Verhältnis von etwa 0,6 bis 4,0 : 1 hergestellt.The shape of the tablet can also influence the breaking strength and the dissolution rate via the outer surface exposed to the H 2 O attack. For reasons of stability, cylindrical compacts with a diameter / height ratio of approximately 0.6 to 4.0: 1 were produced.
Zur Messung der Bruchfestigkeit wurde die Tablette durch einen Keil belastet. Die Bruchfestigkeit entspricht dem Gewicht der keilförmigen Belastung, das zum Bruch der Tablette führt.The tablet was loaded with a wedge to measure the breaking strength. The breaking strength corresponds to the weight of the wedge-shaped load that causes the tablet to break.
Die Mengen des zu verpressenden Substanzgemisches für die Einzeltabletten können in technisch sinnvollen Grenzen beliebig variiert werden. Je nach ihrer Größe kommen vorzugsweise 1 bis 2 oder aber auch mehr Tabletten pro Maschinenfüllung zur Anwendung, um den gesamten Reinigungsprozeß mit dem notwendigen Aktivsubstanzgehalt an Reinigungsmittel zu versehen. Bevorzugt werden Tabletten von etwa 20 bis 40 g Gewicht und einem Durchmesser von etwa 35 bis 40 mm, von denen jeweils eine eingesetzt werden muß.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.
Wurde Na-carbonat nicht hydratisiert oder als Vollhydrat eingesetzt, war die Qualität der aus der Mischung gewonnenen Tabletten für den Handel unbrauchbar, da sie u. a. eine zu geringe Bruchfestigkeit aufwiesen. Auch kam es beim Tablettieren zum Anbacken der Mischungen am Oberstempel der Pressen.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 because, among other things, they had insufficient breaking strength. The tablets also caked on the mixtures on the upper ram of the presses.
In einem 130 l Lödige-Pflugscharmischer wurde eine 50 kg Gemischcharge hergestellt, indem zunächst auf 7,5 Gewichtsteilen Natriumcarbonat und 48 Gewichtsteilen Natriumhydrogencarbonat 4 Gewichtsteile Wasser aufgedüst wurden und anschließend mit 30 Gewichtsteilen Natriumcitratdihydrat, 2 Gewichtsteilen TAED-Granulat, 1 Gewichtsteil BLAP(R) 170 und 1 Gewichtsteil Termamyl(R) 60 Teile unter Aufdüsung von 0,9 Gewichtsteilen Dehydol LS4 und 0,6 Gewichtsteilen Duftstoff gemischt wurde. Dem so erhaltenen Gemisch wurden nun schonend 5 Gewichtsteile Perboratmonohydrat zugemischt. Wie der die Preßbedingungen und Tabletteneigenschaften enthaltenden Tabelle zu ersehen ist, ließen sich mit dem Gemisch nur bedingt bruchstabile Tabletten mit einer zu schnellen Auflösung im Vorspülgang erhalten.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 on 0.9 part by weight of Dehydol LS4 and 0.6 part by weight of fragrance. 5 parts by weight of perborate monohydrate 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 breakability with too rapid dissolution in the pre-rinse cycle.
Bei gleicher Zusammensetzung wie im Beispiel A beschrieben, wurde im 130 l Lödigemischer zunächst erfindungsgemäß das Natriumcitratdihydrat mit Wasser bedüst, anschließend wurde mit Soda bestäubt. Dann erfolgte die Zumischung von TAED-Granulat, Natriumhydrogencarbonat, Blap 170, Termamyl 60 T und eines Gemisches aus Perboratmonohydrat, Duftstoff und Dehydol LS4. Die wesentlich günstigeren Eigenschaften der so erhaltenen Tabletten sind wie auch bei den folgenden Beispielen nach nachfolgenden Tabellen zu entnehmen.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, then 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.
Die Gemischherstellung erfolgte wie im Beispiel 1, jedoch wurde nach Zugabe der Dehydol LS4 zum Schluß das Perboratmonohydrat gesondert zugemischt.The mixture was prepared as in Example 1, but after the addition of Dehydol LS4, the perborate monohydrate was finally mixed in separately.
Die Gemischherstellung erfolgte wie im Beispiel 1 beschrieben, es wurden jedoch zusätzlich zum Schluß noch 1 % Paraffinöl auf das Gemisch aufgedüst.The mixture was prepared as described in Example 1, but in addition 1% paraffin oil was additionally sprayed onto the mixture.
Auf das im Lödige-Pflugscharmischer vorgelegte Natriumcitratdihydrat wurde ein Gemisch aus Wasser, Dehydol LS4 und Duftstoff aufgetragen, dann wurde mit Soda bestäubt und im Anschluß daran die Restkomponenten zugemischt.A mixture of water, Dehydol LS4 and fragrance was applied to the sodium citrate dihydrate placed in the Lödige ploughshare mixer, then dusted with soda and then the remaining components were added.
Auf das im Lödige-Pflugscharmischer vorgelegte Natriumcitratdihydrat wurde eine Suspension aus jeweils 4 Teilen Wasser und Glyceridgemisch (Boeson VP) aufgetragen, anschließend wurde mit Soda bestäubt und entsprechend Beispiel 3 aufgemischt.A suspension of 4 parts water and glyceride mixture (Boeson VP) was applied to each of the sodium citrate dihydrate placed in the Lödige ploughshare mixer, followed by dusting with soda and mixing in accordance with Example 3.
Gemischherstellung entsprechend Beispiel 2, jedoch wurde Boeson VP zum Schluß zugemischt.
Wie sich zeigte, wurden in bezug auf die Bruchfestigkeit und das gewünschte Löseprofil die besten Ergebnisse erhalten, wenn man zuerst flüssige Gemische oder Suspensionen von Rezepturbestandteilen auf das Natriumcitrat aufbrachte und dann die restlichen Feststoffbestandteile zumischte.It was found that the best results in terms of breaking strength and the desired dissolution profile were obtained if liquid mixtures or suspensions of formulation constituents were first applied to the sodium citrate and then the remaining solid constituents were mixed in.
Claims (8)
- Stable, dual-function, phosphate- and metasilicate-free, low alkali detergent tablets for dishwashing machines containing sodium citrate and other builders, bleaching agents, bleach activators and enzymes and optionally nonionic surfactants, dyes and fragrances, characterized in that they optionally contain dissolution retarders and are polymer-free.
- Detergent tablets as claimed in claim 1, characterized in that they contain 5 to 50% by weight of trisodium citrate, up to 25% by weight of nitrilotrisodium acetate, up to 10% by weight of sodium phosphonate, 1 to 60% by weight of sodium carbonate, water-free, up to 60% by weight of sodium disilicate, 1 to 60% by weight of sodium hydrogen carbonate, up to 15% by weight of sodium perborate monohydrate and/or up to 20% by weight of sodium percarbonate, one of these bleaching agents having to be present, 0.5 to 4% by weight of tetraacetyl ethylenediamine, up to 4% by weight of nonionic surfactant, 0. 1 to 2% by weight of protease, 0. 1 to 2% by weight of amylase, up to 1 % by weight of fragrance, up to 3% by weight of paraffin oil, up to 6% by weight of glyceride mixture and 3 to 10% by weight of water.
- Tablets as claimed in claim 1, characterized in that they contain 20 to 30% by weight of trisodium citrate dihydrate, up to 20% by weight of nitrilotrisodium acetate, up to 5% by weight of sodium phosphonate, 1 to 20% by weight of sodium carbonate, water-free, 2 to 30% by weight of sodium disilicate, 30 to 50% by weight of sodium hydrogen carbonate, 5 to 12% by weight of sodium perborate monohydrate and/or 5 to 15% by weight of sodium percarbonate, 2 to 4% by weight of tetraacetyl ethylenediamine, 0.5 to 2% by weight of nonionic surfactant, 0.5 to 1.5% by weight of protease, 0.5 to 1.5% by weight of amylase, 0.1 to 0.6% by weight of fragrance, up to 1.5% by weight of paraffin oil, 1 to 4% by weight of glyceride mixture and 4 to 6% by weight of water.
- A process for the production of stable, dual-function, phosphate-, metasilicate- and polymer-free, low-alkali detergent tablets for dishwashing machines as claimed in claims 1 and 2 containing sodium citrate, other builders, bleaching agents, bleach activators and enzymes and optionally low-foaming surfactants, dissolution retarders, fragrances and dyes, characterized in that sodium citrate dihydrate and/or sodium citrate is/are first moistened with a small quantity of water of 3 to 10% by weight and preferably around 4 to 6% by weight, based on the composition as a whole, after which water-free sodium carbonate is dusted on and sodium hydrogen carbonate and the bleach activator are then added, enzymes, optionally nonionic surfactants, fragrances/dyes and dissolution retarders are introduced and, finally, the active oxygen compound is incorporated with minimal introduction of energy and the overall mixture thus obtained is tabletted in a conventional tablet press at a relative air humidity level of 15 to 60% and preferably 20 to 30% under a pressure of 2 to 11 and preferably 4 to 6 MPa.
- A process as claimed in claim 4, characterized in that, instead of adding paraffin oil, mixtures of mono-, di- and triglycerides of C12-18 and preferably C16-18 fatty acids are added to the water used to moisten the sodium citrate.
- A process as claimed in claim 4, characterized in that the sodium hydrogen carbonate is hydrophobicized with paraffin oil in a preliminary mixing step.
- A process as claimed in claim 4, characterized in that all the liquid components of the composition are first applied to the sodium citrate, the water-free sodium carbonate is then dusted on, sodium hydrogen carbonate and the bleach activator are successively added and, finally, the active oxygen compound is incorporated with minimal introduction of energy and the overall mixture thus obtained is tabletted.
- The use of the tablets claimed in claims 1 to 3, characterized in that the tablets are added to the dishwashing machine in a favorable place in terms of flow and are exposed to the prerinse cycle.
Applications Claiming Priority (3)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| DE4315048 | 1993-04-01 | ||
| DE4315048A DE4315048A1 (en) | 1993-04-01 | 1993-04-01 | Process for the production of stable, bifunctional, phosphate, metasilicate and polymer-free, low-alkaline detergent tablets for automatic dishwashing |
| PCT/EP1994/000932 WO1994023011A1 (en) | 1993-04-01 | 1994-03-23 | Stable, bifunctional, phosphate-, metasilicate- and polymer-free low alkaline detergent tablets for dishwashing machines, and process for producing the same |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| EP0692020A1 EP0692020A1 (en) | 1996-01-17 |
| EP0692020B1 true EP0692020B1 (en) | 1997-11-12 |
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| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| EP94912526A Expired - Lifetime EP0692020B1 (en) | 1993-04-01 | 1994-03-23 | Stable, bifunctional, phosphate-, metasilicate- and polymer-free low alkaline detergent tablets for dishwashing machines, and process for producing the same |
Country Status (10)
| Country | Link |
|---|---|
| US (1) | US5691293A (en) |
| EP (1) | EP0692020B1 (en) |
| AT (1) | ATE160169T1 (en) |
| CZ (1) | CZ286894B6 (en) |
| DE (2) | DE4315048A1 (en) |
| DK (1) | DK0692020T3 (en) |
| ES (1) | ES2110742T3 (en) |
| HU (1) | HUT72020A (en) |
| PL (1) | PL177250B1 (en) |
| WO (1) | WO1994023011A1 (en) |
Cited By (16)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE102007006630A1 (en) | 2007-02-06 | 2008-08-07 | Henkel Ag & Co. Kgaa | cleaning supplies |
| DE102007006627A1 (en) | 2007-02-06 | 2008-08-07 | Henkel Ag & Co. Kgaa | cleaning supplies |
| DE102007006629A1 (en) | 2007-02-06 | 2008-08-07 | Henkel Ag & Co. Kgaa | cleaning supplies |
| DE102007006628A1 (en) | 2007-02-06 | 2008-08-07 | Henkel Ag & Co. Kgaa | cleaning supplies |
| DE102007044418A1 (en) | 2007-09-17 | 2009-03-19 | Henkel Ag & Co. Kgaa | cleaning supplies |
| DE102007044417A1 (en) | 2007-09-17 | 2009-03-19 | Henkel Ag & Co. Kgaa | cleaning supplies |
| DE102007059677A1 (en) | 2007-12-10 | 2009-06-25 | Henkel Ag & Co. Kgaa | cleaning supplies |
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| US5898025A (en) * | 1992-09-25 | 1999-04-27 | Henkel Kommanditgesellschaft Auf Aktien | Mildly alkaline dishwashing detergents |
| DE4408718A1 (en) * | 1994-03-15 | 1995-09-21 | Henkel Kgaa | Breakage and storage stable, polyfunctional cleaning tablets, process for their preparation and their use |
| GB2303635A (en) * | 1995-07-25 | 1997-02-26 | Procter & Gamble | Detergent compositions in compacted solid form |
| DE19606765A1 (en) * | 1996-02-23 | 1997-08-28 | Henkel Kgaa | Process for the production of dishwasher tablets |
| US5900395A (en) * | 1996-12-23 | 1999-05-04 | Lever Brothers Company | Machine dishwashing tablets containing an oxygen bleach system |
| EP0960188B1 (en) * | 1997-11-26 | 2002-06-05 | The Procter & Gamble Company | Dishwashing method |
| EP1184450B1 (en) * | 1997-11-26 | 2006-02-01 | The Procter & Gamble Company | Detergent tablet |
| US6399564B1 (en) * | 1997-11-26 | 2002-06-04 | The Procter & Gamble Company | Detergent tablet |
| DE19752601C1 (en) * | 1997-11-28 | 1998-12-10 | Henkel Kgaa | Production of dishwasher detergent tablet with good breaking strength |
| DE19758180A1 (en) * | 1997-12-30 | 1999-07-01 | Henkel Kgaa | Detergent tablets with bleach activators |
| DE19919443A1 (en) * | 1999-04-29 | 2000-11-02 | Henkel Kgaa | Effervescent tablets with tableting aids and process for their preparation |
| DE60040317D1 (en) * | 1999-06-30 | 2008-11-06 | Kao Corp | Germicidal detergent composition |
| GB2367830A (en) * | 2000-10-12 | 2002-04-17 | Procter & Gamble | Process for preparing tablets |
| US7153820B2 (en) | 2001-08-13 | 2006-12-26 | Ecolab Inc. | Solid detergent composition and method for solidifying a detergent composition |
| GB2390853A (en) * | 2002-07-16 | 2004-01-21 | Reckitt Benckiser Nv | Cleaning composition containing hydrophobic component |
| US20080188392A1 (en) * | 2002-12-02 | 2008-08-07 | Diamond Chemical Company, Inc. | Laundry Compositions |
| US7368418B2 (en) * | 2002-12-02 | 2008-05-06 | Diamond Chemical Company, Inc. | Laundry compositions |
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| US20060234900A1 (en) * | 2005-04-13 | 2006-10-19 | Ecolab Inc. | Composition and process for preparing a phosphonate and phosphate-free automatic dishwashing powder |
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| WO2008095554A2 (en) * | 2007-02-06 | 2008-08-14 | Henkel Ag & Co. Kgaa | Detergents |
| 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 |
| DE102013100195A1 (en) * | 2013-01-10 | 2014-07-24 | Budich International Gmbh | Cleaner tablet with integrated pre-cleaner |
| CN108816005A (en) * | 2018-06-29 | 2018-11-16 | 上海衡元高分子材料有限公司 | composition for regulating environmental humidity |
| US11261409B2 (en) * | 2019-04-19 | 2022-03-01 | One Home Brands, Inc. | Tablet production |
| CA3145901A1 (en) * | 2019-04-19 | 2020-10-22 | One Home Brands, Inc. | Stable anhydrous dish soap and method of making same |
| WO2024129938A1 (en) * | 2022-12-14 | 2024-06-20 | Colgate-Palmolive Company | Home care compositions |
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| GB8328075D0 (en) * | 1983-10-20 | 1983-11-23 | Unilever Plc | Dishwashing compositions |
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| SE468092B (en) * | 1990-11-14 | 1992-11-02 | Eka Nobel Ab | ALKALIMETAL SILICATE IN SOLID FORM CONTAINING SODIUM AND POTASSIUM, PREPARED FOR ITS PREPARATION AND ITS USE IN CLEANING COMPOSITIONS |
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| DE4112075A1 (en) * | 1991-04-12 | 1992-10-15 | Henkel Kgaa | METHOD FOR PRODUCING STABLE, BIFUNCTIONAL, PHOSPATE AND METASILICATE-FREE LOW-ALKALINE DETERGENT TABLETS FOR THE MACHINE DISHWASHER |
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- 1993-04-01 DE DE4315048A patent/DE4315048A1/en not_active Withdrawn
-
1994
- 1994-03-23 AT AT94912526T patent/ATE160169T1/en active
- 1994-03-23 DE DE59404581T patent/DE59404581D1/en not_active Expired - Lifetime
- 1994-03-23 DK DK94912526T patent/DK0692020T3/en active
- 1994-03-23 EP EP94912526A patent/EP0692020B1/en not_active Expired - Lifetime
- 1994-03-23 HU HU9502850A patent/HUT72020A/en unknown
- 1994-03-23 CZ CZ19952531A patent/CZ286894B6/en unknown
- 1994-03-23 PL PL94310951A patent/PL177250B1/en unknown
- 1994-03-23 US US08/530,114 patent/US5691293A/en not_active Expired - Fee Related
- 1994-03-23 ES ES94912526T patent/ES2110742T3/en not_active Expired - Lifetime
- 1994-03-23 WO PCT/EP1994/000932 patent/WO1994023011A1/en active IP Right Grant
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| US7879154B2 (en) | 2007-02-06 | 2011-02-01 | Henkel Ag & Co. Kgaa | Phosphate-free dishwashing detergents comprising builder, bleaching agent, nonionic surfactant, copolymer and a phosphonate |
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| US8303721B2 (en) | 2007-02-06 | 2012-11-06 | Henkel Ag & Co. Kgaa | Detergent comprising a builder, a bleaching agent, and a copolymer |
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| DE102009046216A1 (en) | 2009-10-30 | 2011-05-12 | Henkel Ag & Co. Kgaa | Machine dishwashing detergent |
| WO2012143315A1 (en) | 2011-04-19 | 2012-10-26 | Henkel Ag & Co. Kgaa | Phosphate-free dishwashing detergent |
| DE102011007695A1 (en) | 2011-04-19 | 2012-10-25 | Henkel Ag & Co. Kgaa | Phosphate-free dishwashing detergent |
| DE102016212248A1 (en) | 2016-07-05 | 2018-01-11 | Henkel Ag & Co. Kgaa | Dishwashing detergent containing sugar acid and aminocarboxylic acid |
| WO2018007298A1 (en) | 2016-07-05 | 2018-01-11 | Henkel Ag & Co. Kgaa | Dishwasher agent containing saccharic acid and amino carboxylic acid |
| EP3431575A1 (en) | 2017-07-21 | 2019-01-23 | Henkel AG & Co. KGaA | Dishwashing detergent compositions containing citrate dihydrate and anhydrate |
| DE102017212561A1 (en) | 2017-07-21 | 2019-01-24 | Henkel Ag & Co. Kgaa | Dishwashing detergent containing citrate dihydrate and anhydrate |
Also Published As
| Publication number | Publication date |
|---|---|
| ATE160169T1 (en) | 1997-11-15 |
| DK0692020T3 (en) | 1998-07-27 |
| PL310951A1 (en) | 1996-01-08 |
| US5691293A (en) | 1997-11-25 |
| WO1994023011A1 (en) | 1994-10-13 |
| EP0692020A1 (en) | 1996-01-17 |
| CZ253195A3 (en) | 1996-05-15 |
| DE59404581D1 (en) | 1997-12-18 |
| PL177250B1 (en) | 1999-10-29 |
| HU9502850D0 (en) | 1995-11-28 |
| ES2110742T3 (en) | 1998-02-16 |
| HUT72020A (en) | 1996-03-28 |
| DE4315048A1 (en) | 1994-10-06 |
| CZ286894B6 (en) | 2000-07-12 |
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