EP0126963A1 - Process for the production of cleaning agent tablets - Google Patents
Process for the production of cleaning agent tablets Download PDFInfo
- Publication number
- EP0126963A1 EP0126963A1 EP84104535A EP84104535A EP0126963A1 EP 0126963 A1 EP0126963 A1 EP 0126963A1 EP 84104535 A EP84104535 A EP 84104535A EP 84104535 A EP84104535 A EP 84104535A EP 0126963 A1 EP0126963 A1 EP 0126963A1
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- tablets
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- Prior art date
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- 238000000034 method Methods 0.000 title claims description 13
- 238000004519 manufacturing process Methods 0.000 title claims description 7
- 239000012459 cleaning agent Substances 0.000 title description 4
- 239000000203 mixture Substances 0.000 claims abstract description 24
- 239000003599 detergent Substances 0.000 claims abstract description 15
- 235000019832 sodium triphosphate Nutrition 0.000 claims abstract description 12
- 238000002156 mixing Methods 0.000 claims abstract description 10
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 10
- NTHWMYGWWRZVTN-UHFFFAOYSA-N sodium silicate Chemical compound [Na+].[Na+].[O-][Si]([O-])=O NTHWMYGWWRZVTN-UHFFFAOYSA-N 0.000 claims abstract description 9
- 239000007844 bleaching agent Substances 0.000 claims abstract description 8
- RBLGLDWTCZMLRW-UHFFFAOYSA-K dicalcium;phosphate;dihydrate Chemical compound O.O.[Ca+2].[Ca+2].[O-]P([O-])([O-])=O RBLGLDWTCZMLRW-UHFFFAOYSA-K 0.000 claims abstract description 8
- 239000004115 Sodium Silicate Substances 0.000 claims abstract description 7
- 229910052911 sodium silicate Inorganic materials 0.000 claims abstract description 7
- VMHLLURERBWHNL-UHFFFAOYSA-M Sodium acetate Chemical compound [Na+].CC([O-])=O VMHLLURERBWHNL-UHFFFAOYSA-M 0.000 claims abstract description 5
- 239000001632 sodium acetate Substances 0.000 claims abstract description 5
- 235000017281 sodium acetate Nutrition 0.000 claims abstract description 5
- -1 tripolyphosphate hexahydrate Chemical class 0.000 claims abstract description 5
- 102000004190 Enzymes Human genes 0.000 claims abstract description 4
- 108090000790 Enzymes Proteins 0.000 claims abstract description 4
- 238000002425 crystallisation Methods 0.000 claims abstract description 3
- 230000036571 hydration Effects 0.000 claims abstract description 3
- 238000006703 hydration reaction Methods 0.000 claims abstract description 3
- 238000005507 spraying Methods 0.000 claims abstract description 3
- 239000008187 granular material Substances 0.000 claims description 11
- 238000003825 pressing Methods 0.000 claims description 5
- 238000004851 dishwashing Methods 0.000 claims description 4
- 239000000463 material Substances 0.000 claims description 2
- 239000011734 sodium Substances 0.000 claims description 2
- 239000008202 granule composition Substances 0.000 claims 2
- 229910004298 SiO 2 Inorganic materials 0.000 claims 1
- MOVRNJGDXREIBM-UHFFFAOYSA-N aid-1 Chemical compound O=C1NC(=O)C(C)=CN1C1OC(COP(O)(=O)OC2C(OC(C2)N2C3=C(C(NC(N)=N3)=O)N=C2)COP(O)(=O)OC2C(OC(C2)N2C3=C(C(NC(N)=N3)=O)N=C2)COP(O)(=O)OC2C(OC(C2)N2C3=C(C(NC(N)=N3)=O)N=C2)COP(O)(=O)OC2C(OC(C2)N2C(NC(=O)C(C)=C2)=O)COP(O)(=O)OC2C(OC(C2)N2C3=C(C(NC(N)=N3)=O)N=C2)COP(O)(=O)OC2C(OC(C2)N2C3=C(C(NC(N)=N3)=O)N=C2)COP(O)(=O)OC2C(OC(C2)N2C3=C(C(NC(N)=N3)=O)N=C2)COP(O)(=O)OC2C(OC(C2)N2C(NC(=O)C(C)=C2)=O)COP(O)(=O)OC2C(OC(C2)N2C3=C(C(NC(N)=N3)=O)N=C2)COP(O)(=O)OC2C(OC(C2)N2C3=C(C(NC(N)=N3)=O)N=C2)COP(O)(=O)OC2C(OC(C2)N2C3=C(C(NC(N)=N3)=O)N=C2)COP(O)(=O)OC2C(OC(C2)N2C(NC(=O)C(C)=C2)=O)COP(O)(=O)OC2C(OC(C2)N2C3=C(C(NC(N)=N3)=O)N=C2)COP(O)(=O)OC2C(OC(C2)N2C3=C(C(NC(N)=N3)=O)N=C2)COP(O)(=O)OC2C(OC(C2)N2C3=C(C(NC(N)=N3)=O)N=C2)CO)C(O)C1 MOVRNJGDXREIBM-UHFFFAOYSA-N 0.000 claims 1
- 239000006103 coloring component Substances 0.000 claims 1
- 239000000470 constituent Substances 0.000 abstract description 4
- BPQQTUXANYXVAA-UHFFFAOYSA-N Orthosilicate Chemical compound [O-][Si]([O-])([O-])[O-] BPQQTUXANYXVAA-UHFFFAOYSA-N 0.000 abstract description 3
- 238000004090 dissolution Methods 0.000 abstract description 3
- 238000005469 granulation Methods 0.000 abstract description 3
- 230000003179 granulation Effects 0.000 abstract description 3
- 230000015572 biosynthetic process Effects 0.000 abstract description 2
- 230000008025 crystallization Effects 0.000 abstract description 2
- KKCBUQHMOMHUOY-UHFFFAOYSA-N Na2O Inorganic materials [O-2].[Na+].[Na+] KKCBUQHMOMHUOY-UHFFFAOYSA-N 0.000 abstract 1
- 238000013019 agitation Methods 0.000 abstract 1
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 12
- 239000003795 chemical substances by application Substances 0.000 description 5
- 238000007906 compression Methods 0.000 description 4
- 230000006835 compression Effects 0.000 description 4
- 238000005260 corrosion Methods 0.000 description 4
- 230000007797 corrosion Effects 0.000 description 4
- 238000005187 foaming Methods 0.000 description 4
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 3
- 239000000460 chlorine Substances 0.000 description 3
- 229910052801 chlorine Inorganic materials 0.000 description 3
- 239000002736 nonionic surfactant Substances 0.000 description 3
- UNXRWKVEANCORM-UHFFFAOYSA-I triphosphate(5-) Chemical compound [O-]P([O-])(=O)OP([O-])(=O)OP([O-])([O-])=O UNXRWKVEANCORM-UHFFFAOYSA-I 0.000 description 3
- YRIZYWQGELRKNT-UHFFFAOYSA-N 1,3,5-trichloro-1,3,5-triazinane-2,4,6-trione Chemical compound ClN1C(=O)N(Cl)C(=O)N(Cl)C1=O YRIZYWQGELRKNT-UHFFFAOYSA-N 0.000 description 2
- 229910019142 PO4 Inorganic materials 0.000 description 2
- 239000005662 Paraffin oil Substances 0.000 description 2
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 2
- 229910052910 alkali metal silicate Inorganic materials 0.000 description 2
- 239000007864 aqueous solution Substances 0.000 description 2
- 238000004140 cleaning Methods 0.000 description 2
- 150000001875 compounds Chemical class 0.000 description 2
- 229940088598 enzyme Drugs 0.000 description 2
- 239000006260 foam Substances 0.000 description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-N hydrochloric acid Substances Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 2
- 239000004615 ingredient Substances 0.000 description 2
- 229910052816 inorganic phosphate Inorganic materials 0.000 description 2
- 239000011159 matrix material Substances 0.000 description 2
- 239000010452 phosphate Substances 0.000 description 2
- 229920001451 polypropylene glycol Polymers 0.000 description 2
- 229910052573 porcelain Inorganic materials 0.000 description 2
- 235000019353 potassium silicate Nutrition 0.000 description 2
- 239000000843 powder Substances 0.000 description 2
- 150000003839 salts Chemical class 0.000 description 2
- 239000000243 solution Substances 0.000 description 2
- 229950009390 symclosene Drugs 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
- 239000010457 zeolite Substances 0.000 description 2
- GLVYLTSKTCWWJR-UHFFFAOYSA-N 2-carbonoperoxoylbenzoic acid Chemical compound OOC(=O)C1=CC=CC=C1C(O)=O GLVYLTSKTCWWJR-UHFFFAOYSA-N 0.000 description 1
- 102000013142 Amylases Human genes 0.000 description 1
- 108010065511 Amylases Proteins 0.000 description 1
- IAYPIBMASNFSPL-UHFFFAOYSA-N Ethylene oxide Chemical compound C1CO1 IAYPIBMASNFSPL-UHFFFAOYSA-N 0.000 description 1
- 239000002202 Polyethylene glycol Substances 0.000 description 1
- UIIMBOGNXHQVGW-DEQYMQKBSA-M Sodium bicarbonate-14C Chemical compound [Na+].O[14C]([O-])=O UIIMBOGNXHQVGW-DEQYMQKBSA-M 0.000 description 1
- 241001122767 Theaceae Species 0.000 description 1
- 125000004036 acetal group Chemical group 0.000 description 1
- 239000012190 activator Substances 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 230000000996 additive effect Effects 0.000 description 1
- 150000001298 alcohols Chemical class 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- 150000001447 alkali salts Chemical class 0.000 description 1
- 235000019418 amylase Nutrition 0.000 description 1
- 229940025131 amylases Drugs 0.000 description 1
- 230000000844 anti-bacterial effect Effects 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 239000002585 base Substances 0.000 description 1
- 150000001558 benzoic acid derivatives Chemical class 0.000 description 1
- 150000001735 carboxylic acids Chemical class 0.000 description 1
- 239000000919 ceramic Substances 0.000 description 1
- 150000001860 citric acid derivatives Chemical class 0.000 description 1
- 238000005034 decoration Methods 0.000 description 1
- 239000000975 dye Substances 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- RTZKZFJDLAIYFH-UHFFFAOYSA-N ether Substances CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 1
- 125000001033 ether group Chemical group 0.000 description 1
- 238000007046 ethoxylation reaction Methods 0.000 description 1
- 150000004675 formic acid derivatives Chemical class 0.000 description 1
- 239000003205 fragrance Substances 0.000 description 1
- 235000015203 fruit juice Nutrition 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- 239000003112 inhibitor Substances 0.000 description 1
- 230000002401 inhibitory effect Effects 0.000 description 1
- 159000000003 magnesium salts Chemical class 0.000 description 1
- 150000003891 oxalate salts Chemical class 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 238000004806 packaging method and process Methods 0.000 description 1
- 150000004965 peroxy acids Chemical class 0.000 description 1
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 description 1
- IEQIEDJGQAUEQZ-UHFFFAOYSA-N phthalocyanine Chemical compound N1C(N=C2C3=CC=CC=C3C(N=C3C4=CC=CC=C4C(=N4)N3)=N2)=C(C=CC=C2)C2=C1N=C1C2=CC=CC=C2C4=N1 IEQIEDJGQAUEQZ-UHFFFAOYSA-N 0.000 description 1
- 239000000049 pigment Substances 0.000 description 1
- 229920001223 polyethylene glycol Polymers 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 230000002035 prolonged effect Effects 0.000 description 1
- 235000019795 sodium metasilicate Nutrition 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
- 239000004094 surface-active agent Substances 0.000 description 1
- 239000000375 suspending agent Substances 0.000 description 1
- 239000003826 tablet Substances 0.000 description 1
- 150000003892 tartrate salts Chemical class 0.000 description 1
- 239000012224 working solution Substances 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
- C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
- C11D7/00—Compositions of detergents based essentially on non-surface-active compounds
- C11D7/02—Inorganic compounds
- C11D7/04—Water-soluble compounds
- C11D7/10—Salts
- C11D7/16—Phosphates including polyphosphates
-
- 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
- C11D3/08—Silicates
-
- 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
- C11D7/00—Compositions of detergents based essentially on non-surface-active compounds
- C11D7/02—Inorganic compounds
- C11D7/04—Water-soluble compounds
- C11D7/10—Salts
- C11D7/14—Silicates
Landscapes
- Chemical & Material Sciences (AREA)
- Life Sciences & Earth Sciences (AREA)
- Engineering & Computer Science (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Oil, Petroleum & Natural Gas (AREA)
- Wood Science & Technology (AREA)
- Organic Chemistry (AREA)
- Inorganic Chemistry (AREA)
- Detergent Compositions (AREA)
Abstract
a) Partielles Hydratisieren von 10 bis 60 Gewichtsteilen eines wasserfreien Natriumtripolyphosphats bis zur Ausbildung von 30 bis weniger als 80 Molprozent Tripolyphosphat-Hexahydrat, b) Vermischen des Teilhydrats mit 20 bis 70 Gewichtsteilen eines pulverförmigen und im wesentlichen wasserfreien Natriumsilikats (Na2O : Sio2 = 1 : 1 bis 1 : 4), c) Besprüchen des Gemisches mit Wasser oder wäßriger Silikatlösung, d) Granulierung durch Bewegen mit anschließender Durchkristallisation, wobei gegebenenfalls weitere Reinigungsmittelbestandteile, Bleichmittel oder Enzyme zugemischt werden können, sowie Zusatz von 1 bis 5 Gewichtsprozent Natriumacetat oder 0, 5 bis 3 Gewichtsprozent Dicalciumphosphat-dihydrat bzw. einem Gemisch davon als Tablettierungshilfsmittel führt durch Verpressen unter einem Druck von mehr als 70 kp/cm² zu mechanisch festen Reinigungsmitteltabletten hoher Auflösungsgeschwindigkeit.a) partial hydration of 10 to 60 parts by weight of an anhydrous sodium tripolyphosphate until the formation of 30 to less than 80 mol percent tripolyphosphate hexahydrate, b) mixing of the partial hydrate with 20 to 70 parts by weight of a powdery and essentially anhydrous sodium silicate (Na2O: Sio2 = 1: 1 to 1: 4), c) spraying the mixture with water or aqueous silicate solution, d) granulation by agitation with subsequent crystallization, where further detergent constituents, bleaching agents or enzymes can be admixed, and addition of 1 to 5 percent by weight sodium acetate or 0, 5 to 3% by weight of dicalcium phosphate dihydrate or a mixture thereof as tabletting aid leads to mechanically strong detergent tablets of high dissolution rate when compressed under a pressure of more than 70 kp / cm².
Description
Die vorliegende Erfindung betrifft ein Verfahren zur Herstellung von Reinigungsmitteltabletten, insbesondere zur Verwendung zum maschinellen Geschirrspülen.The present invention relates to a method for producing detergent tablets, in particular for use in automatic dishwashing.
Pulver-, granulat- oder tablettenförmige Reinigungsmittel für Geschirr in Geschirrspülmaschinen bestehen im wesentlichen aus Natriumtripolyphosphat, Alkalisilikat, meist Alkalimetasilikat, und gegebenenfalls aus einem schwach schäumenden, vorzugsweise chlorstabilen, nichtionischen Tensid sowie Bleichmitteln, vorzugsweise solchen, die in wäßriger Lösung Chlor abgeben. Sie dienen vor allem der Erleichterung der Entfernung von Flecken von Tee, Kaffee oder Obstsäften.Powder, granule or tablet detergents for dishes in dishwashers essentially consist of sodium tripolyphosphate, alkali silicate, mostly alkali metasilicate, and optionally a low-foaming, preferably chlorine-stable, nonionic surfactant and bleaching agents, preferably those that release chlorine in aqueous solution. They are mainly used to facilitate the removal of stains from tea, coffee or fruit juices.
Die Mittel sind wegen ihres hohen Gehaltes an Alkalisilikaten und Natriumtripolyphosphat stark alkalisch. Ihre Gebrauchslösungen haben einen pH-Wert von etwa 11 bis 12. Dabei ist ein Zusatz von Natriumhydroxid nicht vorgesehen, weil bei den in Haushaltsgeschirrspülmaschinen üblichen Kontaktzeiten die dann zu hohe Alkalinität Porzellan, Aufglasurdekors und Gläser angreifen würde. Man bezeichnet diesen Angriff als Korrosion. Silikat dagegen unterstützt die Reinigungskraft des Tripolyphosphats synergistisch und hemmt in bestimmten Konzentrationen im Gesamtgemisch Tripolyphosphat/Silikat die Korrosion.The agents are strongly alkaline due to their high content of alkali silicates and sodium tripolyphosphate. Their working solutions have a pH value of around 11 to 12. An addition of sodium hydroxide is not provided, because with the contact times customary in household dishwashers, the excessive alkalinity would then attack porcelain, frosting decorations and glasses. This attack is called corrosion. Silicate, on the other hand, synergistically supports the cleaning power of the tripolyphosphate and inhibits corrosion in certain concentrations in the total tripolyphosphate / silicate mixture.
Die Herstellung der bekannten Mittel erfolgt im allgemeinen nach üblichen Herstellungsverfahren, wie Mischen oder Granulieren. Die Anwendung`erfolgt in Pulver- oder Granulatform in ebenfalls üblichen Konzentrationen, d. h. in Mengen von etwa 30 bis 50 g pro Maschinenfüllung.The known agents are generally produced by customary production processes, such as mixing or granulating. The application takes place in powder or Granules in the usual concentrations, ie in amounts of about 30 to 50 g per machine filling.
Derartige pulver- oder granulatförmige Mittel sind beispielsweise in den deutschen Offenlegungsschriften 23 50 295, 23 58 249 und 29 13 145 sowie in den deutschen Auslegeschriften 24 34 309 und 26 02 357 beschrieben.Such powdered or granular compositions are described, for example, in German Offenlegungsschriften 23 50 295, 23 58 249 and 29 13 145 and in German patent specifications 24 34 309 and 26 02 357.
Nach der französischen Patentschrift 1 472 680 hat man aus einfachen Mischungen der bekannten Reinigungsmittelbestandteile unter Zusatz eines Tablettierungshilfsmittels und unter Anwendung eines Preßdruckes von etwa 70 bis 1000 kg/cm2 scheibenähnliche Tabletten, beispielsweise mit einem Durchmesser von 3 cm, einer Dicke von 1,2 cm und einem Gewicht von etwa 12 g, woraus sich eine Dichte von mehr als 1,4 g/cm3 errechnen läßt, hergestellt. Mit etwa 4 dieser Tabletten erreicht man praktisch den gleichen Erfolg wie mit einer pulverförmigen Reinigungsmittelfüllung von 50 g pro Maschinenlauf.According to French patent specification 1,472,680, simple mixtures of the known cleaning agent components with the addition of a tabletting aid and using a compression pressure of about 70 to 1000 kg / cm 2 have disk-like tablets, for example with a diameter of 3 cm, a thickness of 1.2 cm and a weight of about 12 g, from which a density of more than 1.4 g / cm 3 can be produced. With about 4 of these tablets you can achieve practically the same success as with a powdered detergent filling of 50 g per machine run.
Tabletten der vorstehend genannten Art sind auch in den deutschen Offenlegungsschrift 28 57 001 beschrieben. Sie werden ebenfalls durch Verpressen der bloßen Mischungen der Bestandteile unter Anwendung entsprechender Drucke hergestellt. Anstelle des pH-Wertes wird dort die Alkalinität dadurch bestimmt, daß man feststellt, wieviel n-Salzsäure erforderlich ist, um den pH-Wert einer Lösung von 100 g des Reinigungsmittels in Wasser auf pH zu senken und vergleicht, für welche Menge Natriumhydroxid, in der gleichen Menge Wasser gelöst, die gleiche Menge n-Salzsäure benötigt wird. Das Ergebnis wird als "Alkalinitätsäquivalent" bezeichnet. Die Werte liegen wie bei den bekannten Geschirreinigungsmitteln im allgemeinen über 15 g NaOH, bezogen auf 100 g Reinigungsmittel.Tablets of the type mentioned above are also described in German Offenlegungsschrift 28 57 001. They are also produced by pressing the mere mixtures of the components using appropriate pressures. Instead of the pH value, the alkalinity is determined by determining how much n-hydrochloric acid is required to reduce the pH of a solution of 100 g of the cleaning agent in water to pH and comparing the amount of sodium hydroxide in dissolved in the same amount of water, the same amount of n-hydrochloric acid is required. The result is called the "alkalinity equivalent". As with the known dishwashing detergents, the values are generally above 15 g of NaOH, based on 100 g of detergent.
Die jeweilige Druckhöhe und die daraus resultierende Dichte der Tabletten wird stets durch den erforderlichen Kompromiß zwischen Festigkeit und Auflösungsgeschwindigkeit der Tabletten bestimmt. Weitere auf diese Eigenschaften Einfluß nehmende Faktoren sind die Natur der Bestandteile selbst und geeignete Tablettierungshilfsmittel.The respective pressure level and the resulting density of the tablets is always determined by the necessary compromise between the strength and the dissolution rate of the tablets. Other factors influencing these properties are the nature of the constituents themselves and suitable tabletting aids.
Es wurde nun überraschend gefunden, daß man zu Reinigungsmitteltabletten für das maschinelle Geschirrspülen kommt, die nicht nur eine gute mechanische Festigkeit, sondern vor allem eine hohe Auflösungsgeschwindigkeit besitzen, wenn man bei ihrer Herstellung die alkalisch reagierenden Bestandteile zunächst granuliert und erst dann unter Zusatz von Tablettierungshilfsmitteln, gegebenenfalls in Mischung mit weiteren Bestandteilen verpreßt. Dabei werden Preßdrucke von mehr als 70 kp/cm2 angewendet.It has now surprisingly been found that detergent tablets for automatic dishwashing are obtained which not only have good mechanical strength, but above all have a high dissolution rate, if the alkaline-reacting constituents are first granulated in their preparation and only then with the addition of tabletting aids , optionally pressed in a mixture with other constituents. Press pressures of more than 70 kp / cm 2 are used.
Ein besonders gut geeignetes Verfahren zum Granulieren und Mischen, das das erfindungsgemäße Verfahren zur Herstellung der Tabletten einleitet, ist in allen Einzelheiten in der deutschen Offenlegungsschrift 29 13 145 beschrieben.A particularly well-suited method for granulating and mixing, which initiates the method for producing the tablets according to the invention, is described in all details in German Offenlegungsschrift 29 13 145.
Die vorliegende Erfindung betrifft daher bevorzugt ein Verfahren zur Herstellung von zur Verwendung in Geschirrspülmaschinen geeigneten alkalischen Reinigungsmitteltabletten an sich bekannter Zusammensetzung unter Anwendung von Preßdrucken von mehr als 70 kp/cm2, das dadurch gekennzeichnet ist, daß man ein vollständig auskristallisiertes Granulat mit einem Schüttgewicht von 800 bis 1200, vorzugsweise 850 bis 1100 g/l, gewonnen durch (a) partielles Hydratisieren von 10 bis 60, vorzugsweise 25 bis 40 Gewichtsteilen,eines wasserfreien Natriumtripolyphosphats, das zu 60 bis 100 % aus einem solchen der Phase II besteht und eine mittlere Korngröße von 0,05 bis 0,5 mm aufweist, in einem kontinuierlich arbeitenden Mischer (1. Mischstufe) innerhalb einer mittleren Verweilzeit von 0,2 bis 5 Sekunden mit einer solchen Wassermenge, wie zur Ausbildung von 30 bis weniger als 80 Mol-% Tripolyphosphat-Hexahydrat erforderlich ist und gleichzeitig solchem mechanischen Bearbeiten des Mischguts, daß mindestens 85 Gew.-% davon eine Korngröße von über 0,2 mm und weniger als 2 Gew.-% eine Korngröße von weniger als 0,1 mm aufweisen, (b) Vermischen des Teilhydrates nach einer Verweilzeit außerhalb des Mischers von 5 bis 60 Sekunden in einem Granulationsmischer (2. Mischstufe), gegebenenfalls zusammen mit bis zu 25 Gewichtsteilen eines Granulierhilfsmittels mit 20 bis 70, vorzugsweise 30 bis 50 Gewichtsteilen eines pulverförmigen, im wesentlichen wasserfreien Natriumsilikats der Zusammensetzung Na2O : Si02 = 1 : 1 bis 1 : 4 und anschließendes Besprühen mit Wasser oder einer wäßrigen Lösung von 0,5 bis 5 Gewichtsteilen Natriumsilikat-Lösung in 2 bis 12, vorzugsweise 5 bis 12 Gewichtsteilen Wasser und (c) Granulieren durch Bewegen des Behandlungsgutes mit anschließender Durchkristallisation, wobei man (d) gegebenenfalls weitere Reinigungsmittelbestandteile, Bleichmittel oder Enzyme zumischt, danach (e) Tablettierhilfsmittel zusetzt, (f) in Tablettiermaschinenmatrizenbohrungen füllt und verpreßt.The present invention therefore preferably relates to a process for the production of alkaline detergent tablets suitable for use in dishwashers and known composition using pressure of more than 70 kp / cm 2 characterized in that a completely crystallized granulate with a bulk density of 800 to 1200, preferably 850 to 1100 g / l, obtained by (a) partial hydration of 10 to 60, preferably 25 to 40 parts by weight of an anhydrous sodium tripolyphosphate, the 60 up to 100% consists of one of phase II and has an average grain size of 0.05 to 0.5 mm, in a continuously operating mixer (1st mixing stage) within an average residence time of 0.2 to 5 seconds with such an amount of water , as is necessary for the formation of 30 to less than 80 mol% tripolyphosphate hexahydrate and at the same time mechanical processing of the mixture such that at least 85% by weight thereof has a grain size of more than 0.2 mm and less than 2% by weight have a grain size of less than 0.1 mm, (b) mixing the partial hydrate after a residence time outside the mixer of 5 to 60 seconds in a granulation mixer (2nd mixing stage), counter also together with up to 25 parts by weight of a granulating aid with 20 to 70, preferably 30 to 50 parts by weight of a powdery, essentially anhydrous sodium silicate of the composition Na 2 O: Si0 2 = 1: 1 to 1: 4 and subsequent spraying with water or an aqueous solution (c) granulating admixed sodium silicate solution in from 2 to 12, preferably 5 to 12 parts by weight of water and from 0.5 to 5 parts by moving the material to be treated, followed by crystallization to give (d) optionally further R agreement ingredients, bleaching agents or enzymes, thereafter (e) adds tabletting aids, (f) fills in tablet machine matrix bores and compresses.
Gleichzeitig mit der Zugabe des festen Natriumsilikats oder im Anschluß daran können weitere Granulierhilfsmittel wie wasserfreies Natriumcarbonat, -bicarbonat, Natriumhydroxid oder Wasserglas, aber auch Wasser, Paraffinöl, das gleichzeitig als Schaumunterdrücker dienen kann, und/oder schwachschäumende nichtionische Tenside zugesetzt werden. Die Menge des Tensidzusatzes ist jedoch auf 0,1 bis 2, vorzugsweise 0,2 bis 0,5 Gew.-% zu beschränken, da sonst bei Einsatz der Tabletten in die Geschirrspülmaschinen in Verbindung mit den Geschirranschmutzungen unerwünschtes Schäumen auftreten kann.Simultaneously with the addition of the solid sodium silicate or afterwards, further granulation aids can be added agents such as anhydrous sodium carbonate, bicarbonate, sodium hydroxide or water glass, but also water, paraffin oil, which can simultaneously serve as a foam suppressant, and / or low-foaming nonionic surfactants can be added. However, the amount of the surfactant additive should be limited to 0.1 to 2, preferably 0.2 to 0.5% by weight, since otherwise undesired foaming can occur when the tablets are used in the dishwashers in connection with the soiling of the dishes.
Als schwachschäumende nichtionische Tenside eignen sich die bekannten Ethoxylierungsprodukte von langkettigen Alkoholen und Alkylphenolen, wobei zur Verminderung der Schaumneigung die freie Hydroxylgruppe des Polyethylenglykoletherrestes durch Ether- oder Acetalgruppen bzw. durch Polypropylenglykoletherreste substituiert sind. Geeignet sind ferner die Blockpolymere des Ethylenoxids mit Polypropylenoxid.Suitable low-foaming nonionic surfactants are the known ethoxylation products of long-chain alcohols and alkylphenols, the free hydroxyl group of the polyethylene glycol ether radical being substituted by ether or acetal groups or by polypropylene glycol ether radicals to reduce the tendency to foam. The block polymers of ethylene oxide with polypropylene oxide are also suitable.
Als Bleichmittel kommen die Aktivsauerstoff abspaltenden Verbindungen wie Perborate, vorzugsweise in Verbindung mit Bleichaktivatoren wie z. B. Tetraacetylethylendiamin (TAED) oder Tetraacetylglykoluril (TAGU) oder Persäuren bzw. ihre Salze, z. B. das Magnesiumsalz der Monoperphthalsäure in Betracht. Bevorzugt werden jedoch Aktivchlor abspaltende Verbindungen wie die Salze von chlorsubstituierten Isocyanursäuren, insbesondere die reine Trichlorisocyanursäure selbst. Sie werden gegebenenfalls in Mengen von 0,5 bis 5, vorzugsweise 1 bis 3,5 Gew.-%, bezogen auf das zu verpressende Gemisch, zugemischt.As bleaching agents come the active oxygen-releasing compounds such as perborates, preferably in conjunction with bleach activators such as. B. tetraacetylethylenediamine (TAED) or tetraacetylglycoluril (TAGU) or peracids or their salts, e.g. B. the magnesium salt of monoperphthalic acid. However, compounds which release active chlorine, such as the salts of chlorine-substituted isocyanuric acids, in particular pure trichloroisocyanuric acid itself, are preferred. If appropriate, they are mixed in amounts of 0.5 to 5, preferably 1 to 3.5,% by weight, based on the mixture to be pressed .
Sofern keine Bleichmittel zugemischt werden, können zur Verbesserung der Reinigungsleistung Enzyme eingesetzt werden, bevorzugt handelsübliche Amylasen in Mengen von 0,2 bis 2, vorzugsweise 0,5 bis 1 Gew.-%.If no bleaching agents are added, enzymes can be used to improve the cleaning performance, preferably commercial amylases in amounts of 0.2 to 2, preferably 0.5 to 1% by weight.
Zur weiteren Verbesserung des äußeren Erscheinungsbildes der Reinigungsmittel kann man einen Teil des bleichmittelfreien Granulates mit bleichmittelstabilen Farbstoffen oder Farbpigmenten wie z. B. Phthalocyanin, anfärben und dann etwa zusammen mit den Bleichmitteln, zumischen. Auch Duftstoffe, bekannte bakterizide und schmutzsuspendierende Mittel und Korrosionsinhibitoren können zugesetzt werden.To further improve the external appearance of the detergents, part of the bleach-free granules can be bleached with stable dyes or pigments such as. As phthalocyanine, stain and then mix together with the bleaching agents. Fragrances, known bactericidal and dirt-suspending agents and corrosion inhibitors can also be added.
Das Mischen des vorgefertigten Granulats.mit den übrigen Reinigungsmittelbestandteilen erfolgt in bekannten Mischvorrichtungen wie beispielsweise einem Lödigemischer.The mixing of the prefabricated granules with the other detergent components takes place in known mixing devices such as a Lödige mixer.
Dem fertigen, granulathaltigen Gemisch werden als Tablettierungshilfsmittel bevorzugt Natriumacetat in Mengen von 1 bis 5, vorzugsweise 2 bis 3 Gew.-% und/oder Dicaicium- phosphat-dihydrat in Mengen von 0,5 bis 3, vorzugsweise 0,8 bis 1,2 Gew.-%, jeweils bezogen auf 100 % des gesamten Tablettengranulatgemisches, zugesetzt. Aber auch andere bekannte Mittel, die die Verpreßbarkeit der Mittel und den Zerfall der Tabletten bei der Anwendung verbessern, können zugesetzt werden. Dazu gehören nicht-oberflächenaktive Alkalisalze ein- bis dreibasiger organischer Carbonsäuren, z. B. Citrate, Formiate, Benzoate, Tartrate, Oxalate und dergleichen.The finished granule-containing mixture will be as tableting preferably sodium acetate in amounts from 1 to 5, preferably 2 to 3 wt .-% and / or Dicaicium- phosphate di h ydrat in amounts of from 0.5 to 3, preferably 0.8 to 1 , 2 wt .-%, based in each case on 100% of the total tablet granulate mixture. However, other known agents which improve the compressibility of the agents and the disintegration of the tablets during use can also be added. These include non-surface-active alkali salts of one to three-base organic carboxylic acids, e.g. As citrates, formates, benzoates, tartrates, oxalates and the like.
Das so vorbereitete Granulatgemisch läßt sich störungsfrei zu jeder gewünschten Form verpressen. Bevorzugt werden prismatische Preßlinge mit hexagonalem Querschnitt. Ihr Volumen wird durch das gewünschte Tablettengewicht von etwa 20 g bestimmt.The granulate mixture prepared in this way can be pressed into any desired shape without problems. Prismatic compacts with a hexagonal cross section are preferred. Their volume is determined by the desired tablet weight of approximately 20 g.
Anbackungen an den Preßwerkzeugen treten nicht auf. Die erhaltenen Tabletten zerfallen auch nach längerer Lagerung einwandfrei.Caking on the pressing tools does not occur. The tablets obtained disintegrate perfectly even after prolonged storage.
Zum Verpressen des Granulatgemisches sind alle bekannten Excenter- und Rundläuferpressen geeignet, die zur Herstellung von Tabletten mit Durchmessern von etwa 1,0 cm und mehr eingesetzt werden können. Der Preßdruck muß bei vorgegebener Zusammensetzung so optimiert werden, daß die erhaltenen Tabletten bei vorgegebenem Gewicht einerseits stabil genug sind, um beim Verpacken und Transport nicht beschädigt zu werden, andererseits bei der Anwendung aber schnell genug zerfallen. Dieses Optimum wird vom Fachmann üblicherweise durch routinemäßiges Ausprobieren ermittelt. Die Dichte der Tabletten ist dann - bei vorgegebener Mischung - eine Folge des angewendeten Preßdrucks. Beim Verpressen der erfindungsgemäßen Tablettenbestandteile hat sich ein Preßdruck von 800 bis 1500, vorzugsweise 950 bis 1050 kp/cm2 als optimal erwiesen.All known eccentric and rotary presses, which can be used for the production of tablets with diameters of approximately 1.0 cm and more, are suitable for pressing the granulate mixture. The compression pressure must be optimized for a given composition so that the tablets obtained are stable enough for a given weight on the one hand so that they are not damaged during packaging and transport, but on the other hand disintegrate quickly enough during use. This optimum is usually determined by the person skilled in the art by routine trial and error. The density of the tablets is then - for a given mixture - a consequence of the pressure applied. The compression of the tablet ingredients according to the invention has a pressing pressure of 800 to 1500, preferably 950 to 1 0 5 0 kgf / cm 2 proved to be optimal.
Die nach diesem Verfahren erhaltenen Tabletten weisen eine Dichte von durchschnittlich 1,6 g/cm3 auf, besitzen neben einer hohen mechanischen Stabilität eine gleichmäßige poröse Struktur mit großer innerer Oberfläche. Sie zerfallen daher bei der Anwendung in der'Geschirrspülma- schine besonders schnell und lassen sich schneller in die Maschinen einspülen als das zur Tablettierung verwendete granulatförmige Reinigungsmittel.The tablets obtained by this process have an average density of 1.6 g / cm 3 and, in addition to high mechanical stability, have a uniform porous structure with a large inner surface. They therefore disintegrate particularly quickly when used in the dishwasher and can be washed into the machine faster than the granular detergent used for tabletting.
Die erfindungsgemäßen Tabletten können in Kombination mit dem eingesetzten Phosphat noch andere anorganische Phosphataustauschstoffe enthalten. Zu den bevorzugten anorganischen Phosphataustauschstoffen gehören die synthetisch hergestellten Zeolithe vom Typ NaA oder NaX, wie sie beispielsweise in den US-amerikanischen Patentschriften 2,882,243 und 2,882,244 beschrieben sind. Sie werden in Mengen von 3 bis 30, vorzugsweise von 5 bis 10 Gew.-% eingesetzt und in der 2. Mischstufe zugegeben. Neben ihrer reinigungsverstärkenden Wirkung zeigen die Zeolithe eine zusätzliche korrosionsinhibierende Wirkung in bezug auf Dekorglasuren auf Porzellan oder Keramik, die über die der bekannten Tripolyphosphat/Metasilikat-Mischungen hinausgeht. Die erfindungsgemäßen Tabletten besitzen neben der mechanischen Stabilität auch eine ausgezeichnete Chlorstabilität, obgleich der Wassergehalt der Tabletten ca. 10 Gew.-% beträgt.In combination with the phosphate used, the tablets according to the invention can also contain other inorganic phosphate substitutes. Among the preferred Inorganic phosphate substitutes include the synthetically produced zeolites of the NaA or NaX type, as are described, for example, in US Pat. Nos. 2,882,243 and 2,882,244. They are used in amounts of 3 to 30, preferably 5 to 10,% by weight and are added in the second mixing stage. In addition to their cleaning-enhancing effect, the zeolites have an additional corrosion-inhibiting effect with regard to decorative glazes on porcelain or ceramic, which goes beyond that of the known tripolyphosphate / metasilicate mixtures. In addition to the mechanical stability, the tablets according to the invention also have excellent chlorine stability, although the water content of the tablets is approximately 10% by weight.
41,7 Gew.-% wasserfreies Natriummetasilikat und 38,6 Gew.-% Natriumtripolyphosphat wurden in Gegenwart von 6,7 Gew.-% wasserfreiem Natriumcarbonat mit 4,0 Gew.-% Wasserglas 37/40 und 0,2 Gew.-% weißem Paraffinöl mit einem Flammpunkt von 210 0C nach dem in der deutschen Auslegeschrift 29 13 145 ausführlich beschriebenen Verfahren granuliert, in einem Lödigemischer mit 3,0 Gew.-% eines durch Phthalocyaninzusatz blau gefärbten gleichen Granulats ("Blausprenkel"), 1,0 Gew.-% Trichlorisocyanursäure und 2,0 Gew.-% Natriumacetat sowie 1,0 Gew.-% Dicalciumphosphat-dihydrat vermischt. Jeweils 20 g dieser Mischung wurden über einen Vorratstrichter kontinuierlich nacheinander in eine regelmäßige Sechseckmatrizenbohrung einer Excenter-Tablettiermaschine vom Typ Exakta 31 der Firma Fette eingefüllt und mit einem Preßdruck von 1000 kp/cm 2 zu Preßlingen (= Tabletten) mit einer Dichte von rund 1,4 g/cm3 verpreßt.41.7% by weight of anhydrous sodium metasilicate and 38.6% by weight of sodium tripolyphosphate were mixed in the presence of 6.7% by weight of anhydrous sodium carbonate with 4.0% by weight of 37/40 water glass and 0.2% by weight. % white paraffin oil granulated with a flash point of 210 0 C according to the method in German Auslegeschrift described in detail 29 13 145, in a Lodige mixer with 3.0 wt .-% of a blue colored by Phthalocyaninzusatz same granules ( "Blausprenkel"), 1 0% by weight of trichloroisocyanuric acid and 2.0% by weight of sodium acetate and 1.0% by weight of dicalcium phosphate dihydrate are mixed. In each case 20 g of this mixture were poured continuously in succession into a regular hexagon matrix bore in an excenter tableting machine of the type Exakta from Fette and with a compression pressure of 1000 kp / cm 2 to form tablets (= tablets) with a density of around 1 . 4 g / cm 3 pressed.
Sie waren von feiner und gleichmäßig gekörnter Struktur und von großer Stabilität. Ihre Einspülzeit über einen mit einem Gitter versehenen Dosierkasten in einer Haushaltsgeschirrspülmaschine vom Typ Miele G 5035 betrug 25 Minuten und damit zwei Minuten weniger als die Einspülzeit der gleichen Gewichtsmenge des unverpreßten Reinigungsmittels gleicher Zusammensetzung, jedoch ohne Tablettierungshilfsmittel.They were of fine and evenly grained structure and of great stability. Their washing-in time via a grating metering box in a Miele G 5035 household dishwasher was 25 minutes, two minutes less than the washing-in time of the same amount by weight of the uncompressed cleaning agent of the same composition, but without tableting aids.
In entsprechender Weise wie in Beispiel 1 angegeben, wurden weitere Tabletten hergestellt, deren Zusammensetzung, Kenndaten und Eigenschaften in der nachfolgenden Tabelle wiedergegeben sind.
Claims (8)
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| AT84104535T ATE24547T1 (en) | 1983-05-02 | 1984-04-21 | PROCESS FOR THE MANUFACTURE OF DETERGENT TABLETS. |
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| DE3315950 | 1983-05-02 | ||
| DE3315950A DE3315950A1 (en) | 1983-05-02 | 1983-05-02 | METHOD FOR PRODUCING DETERGENT TABLETS |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| EP0126963A1 true EP0126963A1 (en) | 1984-12-05 |
| EP0126963B1 EP0126963B1 (en) | 1986-12-30 |
Family
ID=6197931
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| EP84104535A Expired EP0126963B1 (en) | 1983-05-02 | 1984-04-21 | Process for the production of cleaning agent tablets |
Country Status (4)
| Country | Link |
|---|---|
| US (1) | US4587031A (en) |
| EP (1) | EP0126963B1 (en) |
| AT (1) | ATE24547T1 (en) |
| DE (2) | DE3315950A1 (en) |
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| EP0264701A1 (en) * | 1986-10-13 | 1988-04-27 | Henkel Kommanditgesellschaft auf Aktien | Cleaning agent tablets for the automatic dishwashing |
| WO1994005768A1 (en) * | 1992-09-04 | 1994-03-17 | Henkel Kommanditgesellschaft Auf Aktien | Process for producing detergent tablets |
| WO1997026317A1 (en) * | 1996-01-19 | 1997-07-24 | Henkel Kommanditgesellschaft Auf Aktien | Process for the preparation of moulded bodies consisting of a washing or cleaning agent |
| WO1999024545A2 (en) * | 1997-11-11 | 1999-05-20 | Henkel Kommanditgesellschaft Auf Aktien | Method for producing stable, rapidly decomposing shaped bodies of detergent |
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| US5998345A (en) * | 1999-03-25 | 1999-12-07 | Colgate Palmolive Company | Automatic dishwashing tablets |
| EP1190029A1 (en) * | 1999-06-25 | 2002-03-27 | Unilever Plc | Dish washing process and compositions relating thereto |
| GB9918505D0 (en) * | 1999-08-05 | 1999-10-06 | Unilever Plc | Water-softening and detergent compositions |
| US6638902B2 (en) | 2001-02-01 | 2003-10-28 | Ecolab Inc. | Stable solid enzyme compositions and methods employing them |
| US6632291B2 (en) | 2001-03-23 | 2003-10-14 | Ecolab Inc. | Methods and compositions for cleaning, rinsing, and antimicrobial treatment of medical equipment |
| PL2388309T3 (en) * | 2010-05-17 | 2017-07-31 | Dalli-Werke Gmbh & Co. Kg | Detergent tablets having more than four side surfaces |
| EP3181671A1 (en) | 2015-12-17 | 2017-06-21 | The Procter and Gamble Company | Automatic dishwashing detergent composition |
| EP3181676B1 (en) | 2015-12-17 | 2019-03-13 | The Procter and Gamble Company | Automatic dishwashing detergent composition |
| EP3181675B2 (en) | 2015-12-17 | 2022-12-07 | The Procter & Gamble Company | Automatic dishwashing detergent composition |
| EP3181679A1 (en) * | 2015-12-17 | 2017-06-21 | The Procter and Gamble Company | Process for making an automatic dishwashing product |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3417024A (en) * | 1963-12-31 | 1968-12-17 | Lever Brothers Ltd | Treated phosphates |
| EP0002293A1 (en) * | 1977-11-29 | 1979-06-13 | THE PROCTER & GAMBLE COMPANY | Detergent tablet having a hydrated salt coating and process for preparing the tablet |
| DE2857001A1 (en) * | 1977-06-01 | 1979-10-31 | Procter & Gamble | CLEANING TABLET |
| DE2913145A1 (en) * | 1979-04-02 | 1980-10-23 | Henkel Kgaa | Continuous dish-washing cleanser granulate prepn. - by hydrating sodium tri:poly:phosphate and granulating with sodium silicate, surfactant and opt. soda |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US2882244A (en) * | 1953-12-24 | 1959-04-14 | Union Carbide Corp | Molecular sieve adsorbents |
| US2882243A (en) * | 1953-12-24 | 1959-04-14 | Union Carbide Corp | Molecular sieve adsorbents |
| US3390092A (en) * | 1965-03-30 | 1968-06-25 | Fmc Corp | Dishwashing detergent preparations containing sodium or potassium dichloroisocyanurate |
| FR1472680A (en) * | 1965-03-30 | 1967-03-10 | Fmc Corp | Detergent for dishwashing machines based on chlorinated isocyanurates |
| US3816320A (en) * | 1972-11-24 | 1974-06-11 | Fmc Corp | Stable dishwashing compositions containing sodium dichloroisocyanurate dihydrate |
| US3957967A (en) * | 1973-07-27 | 1976-05-18 | Blendax-Werke R. Schneider & Co. | Agent for the care and the cleaning of teeth and dentures |
| US3933670A (en) * | 1973-11-12 | 1976-01-20 | Economic Laboratories, Inc. | Process for making agglomerated detergents |
| FR2298599A2 (en) * | 1975-01-24 | 1976-08-20 | Sifrance | NEW SOLID NON-CORROSIVE DETERGENT COMPOSITIONS |
| GB2041966A (en) * | 1977-11-29 | 1980-09-17 | Procter & Gamble | Detergent tablet having a hydrated salt coating and process for preparing the tablet |
-
1983
- 1983-05-02 DE DE3315950A patent/DE3315950A1/en not_active Withdrawn
-
1984
- 1984-04-10 US US06/598,626 patent/US4587031A/en not_active Expired - Fee Related
- 1984-04-21 EP EP84104535A patent/EP0126963B1/en not_active Expired
- 1984-04-21 DE DE8484104535T patent/DE3461830D1/en not_active Expired
- 1984-04-21 AT AT84104535T patent/ATE24547T1/en not_active IP Right Cessation
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3417024A (en) * | 1963-12-31 | 1968-12-17 | Lever Brothers Ltd | Treated phosphates |
| DE2857001A1 (en) * | 1977-06-01 | 1979-10-31 | Procter & Gamble | CLEANING TABLET |
| EP0002293A1 (en) * | 1977-11-29 | 1979-06-13 | THE PROCTER & GAMBLE COMPANY | Detergent tablet having a hydrated salt coating and process for preparing the tablet |
| DE2913145A1 (en) * | 1979-04-02 | 1980-10-23 | Henkel Kgaa | Continuous dish-washing cleanser granulate prepn. - by hydrating sodium tri:poly:phosphate and granulating with sodium silicate, surfactant and opt. soda |
Cited By (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP0224128A2 (en) * | 1985-11-21 | 1987-06-03 | Henkel Kommanditgesellschaft auf Aktien | Multilayered detergent tablets for mechanical dish-washing |
| EP0224128A3 (en) * | 1985-11-21 | 1988-03-09 | Henkel Kommanditgesellschaft Auf Aktien | Multilayered detergent tablets for mechanical dish-washing |
| US4828749A (en) * | 1985-11-21 | 1989-05-09 | Henkel Kommanditgesellschaft Auf Aktien | Multilayer detergent tablets for dishwashing machines |
| EP0264701A1 (en) * | 1986-10-13 | 1988-04-27 | Henkel Kommanditgesellschaft auf Aktien | Cleaning agent tablets for the automatic dishwashing |
| WO1994005768A1 (en) * | 1992-09-04 | 1994-03-17 | Henkel Kommanditgesellschaft Auf Aktien | Process for producing detergent tablets |
| WO1997026317A1 (en) * | 1996-01-19 | 1997-07-24 | Henkel Kommanditgesellschaft Auf Aktien | Process for the preparation of moulded bodies consisting of a washing or cleaning agent |
| WO1999024545A2 (en) * | 1997-11-11 | 1999-05-20 | Henkel Kommanditgesellschaft Auf Aktien | Method for producing stable, rapidly decomposing shaped bodies of detergent |
| WO1999024545A3 (en) * | 1997-11-11 | 1999-07-15 | Henkel Kgaa | Method for producing stable, rapidly decomposing shaped bodies of detergent |
| EP1384772A1 (en) * | 2002-07-17 | 2004-01-28 | Unilever N.V. | Detergent tablet |
Also Published As
| Publication number | Publication date |
|---|---|
| DE3461830D1 (en) | 1987-02-05 |
| ATE24547T1 (en) | 1987-01-15 |
| US4587031A (en) | 1986-05-06 |
| EP0126963B1 (en) | 1986-12-30 |
| DE3315950A1 (en) | 1984-11-15 |
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