EP0591282B1 - Method for the production of cleaning-agent tablets for machine dishwashing - Google Patents
Method for the production of cleaning-agent tablets for machine dishwashing Download PDFInfo
- Publication number
- EP0591282B1 EP0591282B1 EP92912460A EP92912460A EP0591282B1 EP 0591282 B1 EP0591282 B1 EP 0591282B1 EP 92912460 A EP92912460 A EP 92912460A EP 92912460 A EP92912460 A EP 92912460A EP 0591282 B1 EP0591282 B1 EP 0591282B1
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- EP
- European Patent Office
- Prior art keywords
- weight
- acrylic acid
- meth
- tablets
- builders
- 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.)
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Classifications
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- 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
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- 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
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- 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
- C11D3/37—Polymers
- C11D3/3746—Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds
- C11D3/3757—(Co)polymerised carboxylic acids, -anhydrides, -esters in solid and liquid compositions
- C11D3/3761—(Co)polymerised carboxylic acids, -anhydrides, -esters in solid and liquid compositions in solid compositions
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 detergent 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.
- 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 dissolving profile is understood to mean the weight ratio of portions of the tablet, dissolved under the conditions of the pre-rinse cycle, of conventional HGSM to the entire tablet.
- the known tablets still contain phosphates, which are known to be undesirable.
- phosphate-free detergent tablets for machine dishwashing on the market (eg Hui rinsing tabs from Roth GmbH, Bad Ems), 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 largely or completely even during the pre-rinse cycle, so that practically no detergent is available in the actual cleaning cycle. In addition, the stability of these tablets is unsatisfactory.
- German patent application DE-A-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 German patent application DE-A -39 37 469 in the form of a granular, alkaline cleaning additive consisting of sodium salts of at least one homopolymeric or copolymeric (meth) acrylic acid, sodium carbonate, sodium sulfate and water.
- the granular alkaline cleaning additives were mechanically mixed with the other mostly powdery recipe components and pressed in a manner known per se.
- the present invention was based on a market trend, the task of producing a stable, bifunctional, phosphate and metasilicate-free, low-alkaline detergent tablet with a broad dissolution profile for automatic dishwashing, which is at least 10% by weight to approximately 10% by weight of tap water in the pre-rinsing phase of an HGSM 50% by weight is dissolved, a pH value of at most about 10.5 is developed in the washing liquor and at least 50% by weight to about 90% by weight is still available for the cleaning cycle with good hot water solubility.
- the storage-stable tablets produced in accordance with 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 also remain stable during storage and within a short time Time can still increase significantly.
- the solid alkali salts of at least one homopolymeric or copolymeric (meth) acrylic acid can be used as commercially available powders or granules or as a so-called cleaning additive.
- Component (a) consists of homopolymeric or copolymeric carboxylic acids in the form of the sodium salts.
- Suitable homopolymers are polymethacrylic acid and preferably polyacrylic acid, for example those with a molecular weight of 800 to 150,000 (based on acid). If only homopolymeric polyacrylic acids (in salt form) are used, their molecular weight is preferably 1,000 to 80,000 (based on acid) in the interest of good flowability and storage stability.
- Suitable copolymers are those of acrylic acid with methacrylic acid and preferably copolymers of acrylic acid or methacrylic acid with maleic acid.
- Copolymers of acrylic acid with maleic acid as are characterized, for example, in EP-B-25 551, have proven to be particularly suitable. These are copolymers which contain 50 to 90% by weight of acrylic acid and 50 to 10% by weight of maleic acid. Copolymers in which 60 to 85% by weight of acrylic acid and 40 to 15% by weight of maleic acid are present are particularly preferred.
- Their molecular weight, based on free acids, is generally 5,000 to 200,000, preferably 10,000 to 120,000.
- Mixtures of different homopolymers and copolymers can also be used with advantage, in particular mixtures of homopolymeric acrylic acid and the copolymers of 50 to 90% by weight of acrylic acid and 50 to 10% of maleic acid described above.
- Such mixtures which are characterized by favorable grain properties and high storage stability, can be made, for example, from 10 to 50 wt % By weight of acrylic acid-maleic acid copolymers exist.
- Highly polymeric polyacrylic acids can also be used in these mixtures which, when used alone, have a slightly greater tendency to stick or melt than the low molecular weight polyacrylates.
- the polycarboxylates are used as powder, but preferably as granules.
- the usable polyacrylates include, for example, Sokalane R CP 10, PA 10 and PM 10 from BASF, Alcosperse R from Alco: Alcosperse R 102, 104, 106, 404, 406), Acrysole R from Norsohaas: Acrysole R A 1N , LMW 45 N, LMW 10 N, LMW 20 N, Degapas R from Degussa: Degapas R 4104 N, Good-Rite R from Goodrich: Good-Rite R K-XP 18, K 739 and K 7200 N.
- copolymers Polyacrylic acid and maleic acid
- Sokalane R from BASF: Sokalan R CP 5, CP 7, Acrysole R from Norsohaas: Acrysol R QR 1014 and SP O2N
- Alcosperse R from Alco: Alcosperse R 175.
- the sodium carbonate (b) and the sodium sulfate (c) are used in anhydrous form. With proportions of sodium carbonate of approx. 40% by weight and more, it is advisable to reduce the water content (d) of the additives to less than 6% by weight or to choose a somewhat higher proportion of sodium sulfate, for example in the range 8 to 15% by weight.
- the cleaning additives can contain minor components such as dyes and color pigments and can be colored uniformly or speckled.
- the proportion of such minor components is well below 1% by weight.
- sodium citrates, nitrilotriacetate, phosphonates and alkali disilicates can also serve as builders. You tie together with the polycarboxylate-containing cleaning additive component through complex formation or dispersion, hardness-forming agents such as calcium and magnesium ions from the water or from the food residues, 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. As alkali carbonate sodium carbonate of any quality is preferably used, such as. B. calcined soda, compressed soda and also sodium bicarbonate. Anhydrous trisodium citrate or trisodium citrate dihydrate are suitable as sodium citrate.
- the preferred phosphonate is the tetrasodium salt of 1-hydroxyethane-1,1-di-phosphonic acid (Turpinal R 4 NZ from Henkel).
- Extremely low-foaming nonionic compounds are preferably used as low-foaming surfactants, which serve to better remove fatty food residues and as pressing aids. These preferably include C12-C18 alkyl polyethylene glycol polypropylene glycol ethers, each with up to 8 moles of ethylene oxide and propylene oxide units in the molecule. Their share in the total weight of the finished tablets is generally 0.2 to 5, preferably 0.5 to 3% by weight. But you can also use other non-foaming surfactants known as low foams, such as. B.
- C12-C18 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 0.2 to 2, preferably 0.2 to 1 wt .-%, based on the entire tablet, of defoaming agents such as B. silicone oils, mixtures of silicone oil and hydrophobicized silica, paraffin oil / Guerbet alcohols and hydrophobicized silica.
- Active oxygen carriers are now preferably bleaches which are customary constituents of cleaning agents for HGSM. These include primarily sodium perborate mono- and tetrahydrate as well as sodium percarbonate and sodium 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.
- bleach activators preferably 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 can also be used to better remove protein or starch-containing food residues, for example proteases such as BLAP R from Henkel, Opitmase R -M-440, Optimase R -M-330, 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, Opticlean R -M-375 , Opticlean R -M-250 from Solvay Enzymes, Maxacal R CX 450,000
- 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
- mold release agents for example paraffin oil
- paraffin oil 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.
- Na-hydrogen carbonate is preferably used to set the desired pH.
- the average grain size of the granular cleaning additives is usually 0.2 to 1.2 mm, the proportion of the grains below 0.1 mm advantageously not more than 2% by weight and above 2 mm not more than 20% by weight.
- at least 80% by weight, in particular at least 90% by weight, of the grains have a size of 0.2 to 1.6 mm, the proportion of the grains between 0.1 and 0.05 mm not more than 3% by weight .-%, in particular not more than 1% by weight and the proportion of the grains between 1.6 and 2.4 mm is not more than 20% by weight, in particular not more than 10% by weight.
- the bulk weight is about 350 to 550 g / l.
- the granular cleaning additives are produced by spray drying an aqueous slurry.
- the slurry concentration is between 50 and 68% by weight (non-aqueous fraction), preferably between 55 and 60% by weight, the viscosity of the paste being decisive, which should not exceed 10,000 mPa ⁇ s and advantageously 2,500 to 6,000 mPa ⁇ s.
- the temperature of the slurry is usually between 50 and 100 ° C.
- the pressure at the spray nozzles is generally 30 to 80 bar, preferably 40 to 70 bar.
- the temperature of the counter-current dry gases in the entrance zone of the spray tower, ie in the so-called ring channel is advantageously between 200 and 320 ° C, in particular between 220 and 300 ° C.
- the drying is preferably conducted so that the water binding to less is reduced as 1 mole of H2O per mole of sodium carbonate.
- Conventional spray drying systems spray towers
- spray drying can be used for spray drying, it being possible for the spray nozzles to be arranged in one or more levels.
- the spray material leaving the tower was mixed with the other tablet components as described, if necessary after cooling with flowing air, and then in total on conventional tablet presses with a compression pressure of 200 to 1500. 105, preferably 300 to 1000. 105 Pa pressed.
- 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 / cm3, preferably between about 1.4 to 1.8 g / cm3.
- the compression during the pressing process caused changes in the density, which from about 0.4 to 1.2 g / cm3, preferably about 0.6 to 1.0 g / cm3 to about 1.2 to 2.0 g / cm3, preferably about 1.4 to 1.6 g / cm3 rose.
- the shape of the tablet can also influence the breaking strength and the rate of dissolution via the outer surface exposed to the H2O attack. For reasons of stability, cylindrical compacts with a diameter / height ratio of approximately 0.6 to 4.0: 1 were produced.
- the 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.
- Nonionic surfactants are nonionic surfactants:
- a 50 kg batch was prepared in a 130 l Lödige ploughshare mixer.
- 6.8 parts by weight of sodium carbonate anhydrous, 32.0 parts by weight of sodium bicarbonate and 4.0 parts by weight of water were first mixed with the chopper running and then immediately further with 20.0 parts by weight of a granular alkaline cleaning additive , consisting of 40.8% by weight sodium carbonate anhydrous, 5.0% by weight sodium sulfate, 50.0% by weight of the sodium salt of the copolymer of maleic acid and acrylic acid with a molecular weight of 70,000 (Sokalan CP 5 from BASF) and 4.2% by weight of water, 20.0 parts by weight of sodium citrate dihydrate, 2.0 parts by weight of Plurafac R LF 403 and 0.2 part by weight of fragrance.
- a granular alkaline cleaning additive consisting of 40.8% by weight sodium carbonate anhydrous, 5.0% by weight sodium sulfate, 50.0% by weight of the sodium salt of the copolymer of male
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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 zu laufenden Leitungswasser betrieben.So far, it has been common practice in household dishwashers, hereinafter referred to as HGSM, to store the detergent in a metering 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 before is operated without any active substance, i.e. exclusively with the tap water that is to be run.
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 detergent 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 the pre-clearing zone cleaning from GGSM has already been transferred to HGSM and the addition of cleaning agents to the pre-rinse cycle has been made possible by dosing cleaning agents in tablet form and one or more suitable tablets For example, positioned in a free part of the cutlery basket, but also elsewhere 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-A-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-A-35 41 145. These are uniformly composed 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 tabletting aids, and in which the alkali metal silicates are made from a mixture of "sodium metasilicate nohydrate" .8H₂O) 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: 1 to anhydrous 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 dissolving profile is understood to mean the weight ratio of portions of the tablet, dissolved under the conditions of the pre-rinse cycle, of conventional HGSM to the entire tablet.
Die bekannten Tabletten enthalten jedoch noch Phosphate, die wie man weiß unerwünscht sind.However, the known tablets still contain phosphates, which are known to be undesirable.
Es sind aber 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.There are also phosphate-free detergent tablets for machine dishwashing on the market (eg Hui rinsing tabs from Roth GmbH, Bad Ems), 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 largely or completely even during the pre-rinse cycle, so that practically no detergent is available in the actual cleaning cycle. In addition, the stability of these tablets is unsatisfactory.
In der deutschen Patentanmeldung DE-A-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 deutschen Patentanmeldung DE-A-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.German patent application DE-A-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 German patent application DE-A -39 37 469 in the form of a granular, alkaline cleaning additive consisting of sodium salts of at least one homopolymeric or copolymeric (meth) acrylic acid, sodium carbonate, sodium sulfate and water. 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.
Der vorliegenden Erfindung lag nun einem Markttrend folgend die Aufgabe zugrunde, eine stabile, bifunktionelle, phosphat- und metasilikatfreie niederalkalische Reinigungsmitteltablette mit breitem Löseprofil für das maschinelle Geschirrspülen herzustellen, die bereits im Vorspülgang einer HGSM vom zulaufenden Leitungswasser zu mindestens 10 Gew.-% bis etwa 50 Gew.-% aufgelöst wird, dabei in der Spülflotte einen pH-Wert von höchstens etwa 10,5 entwickelt und bei guter Warmwasserlöslichkeit zu noch mindestens 50 Gew.-% bis etwa 90 Gew.-% für den Reinigungsgang zur Verfügung steht.The present invention was based on a market trend, the task of producing a stable, bifunctional, phosphate and metasilicate-free, low-alkaline detergent tablet with a broad dissolution profile for automatic dishwashing, which is at least 10% by weight to approximately 10% by weight of tap water in the pre-rinsing phase of an HGSM 50% by weight is dissolved, a pH value of at most about 10.5 is developed in the washing liquor and at least 50% by weight to about 90% by weight is still available for the cleaning cycle with good hot water solubility.
Zur Herstellung der bekannten Reinigungsmitteltabletten wurden Pulvergemische verpreßt, die neben Hydratwasser enthaltendem Natriummetasilikatnonahydrat noch wasserfreies Natriummetasilikat enthielten. Diese Kombination aus Wasser enthaltenden Substanzen und Substanzen, die Wasser aufnehmen können, führte zu einer Steigerung der Bruchstabilität der Tabletten bei Lagerung. Da die erfindungsgemäßen Tabletten wegen der geforderten geringen Alkalität keinen der vorstehend genannten Rohstoffe enthalten können, sind sie nach dem Verpressen gemaß dem Stand der Technik aus Pulvergemischen oder auch Pulvergemischen mit granularem Anteil nicht bruchstabil genug.To produce the known detergent tablets, powder mixtures were pressed which, in addition to sodium metasilicate non-hydrate containing hydrate water, also contained anhydrous sodium metasilicate. This combination of water-containing substances and substances that can absorb water led to an increase in the breaking stability of the tablets during storage. Since the tablets of the invention because of the required low alkalinity can not contain any of the raw materials mentioned above, they are not stable enough after breaking according to the prior art from powder mixtures or powder mixtures with a granular content.
Es wurde nun gefunden, daß man zu stabilien, bifunktionellen, phosphat- und metasilikatfreien, niederalkalischen Reinigungsmitteltabletten, die in der Spülflotte einen pH-Wert von höchstens etwa 10,5 entwickeln, für das maschinelle Geschirrspülen mit einem Gehalt an festen Alkalisalzen mindestens einer homopolymeren bzw. copolymeren (Meth-)Acrylsäure, Gerüstsubstanzen, schaumarmen Tensiden, Bleichmitteln, gegebenenfalls Enzymen, Bleichaktivatoren, Duft- und Farbstoffen kommt, wenn man das als Teil der Gerüstsubstanzen dienende Natriumcarbonat in wasserfreier Form einsetzt, es zunächst in einem Mischgang, vorzugsweise allein oder mit den anderen Gerüstsubstanzen 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 die restlichen Stoffe der Mischung zufügt und das so erhaltene Gemisch auf einer üblichen Tablettenpresse verpreßt. 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 bei Lagerung ebenfalls stabil bleiben und sich dabei innerhalb kurzer Zeit noch deutlich erhöhen kann.It has now been found that stable, bifunctional, phosphate- and metasilicate-free, low-alkaline detergent tablets, which develop a pH value of at most about 10.5 in the washing liquor, for automatic dishwashing with a content of solid alkali salts of at least one homopolymer or copolymeric (meth) acrylic acid, builders, low-foam surfactants, bleaching agents, optionally enzymes, bleach activators, fragrances and dyes, if the sodium carbonate serving as part of the builders is used in anhydrous form, first in a mixing cycle, preferably alone or with the other builders and the solid alkali salts of at least one homopolymeric or copolymeric (meth) acrylic acid together with the amount of water required for the partial hydration of the anhydrous sodium carbonate of about 5-40, preferably about 7-20 wt .-%, based on the as Anhydrous sodium carbonate used as framework at, added, then the remaining substances are added to the mixture and the mixture thus obtained is compressed on a conventional tablet press. The storage-stable tablets produced in accordance with 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 also remain stable during storage and within a short time Time can still increase significantly.
Die festen Alkalisalze der mindestens einen homopolymeren bzw. copolymeren (Meth-)Acrylsäure können als handelsübliche Pulver bzw. Granulate oder als sogenanntes Reinigungsadditiv eingesetzt werden.The solid alkali salts of at least one homopolymeric or copolymeric (meth) acrylic acid can be used as commercially available powders or granules or as a so-called cleaning additive.
Das Reinigungsadditiv und seine Herstellung sowie seine Verwendung in Geschirrspülmitteln ist Gegenstand der nicht vorveröffentlichten deutschen Patentanmeldung DE-A-39 37 469. Der Einsatz in Tabletten wird dort nicht genannt. Es besteht aus
- (a) 35 bis 60 Gew.-% an Natriumsalzen mindestens einer homopolymeren bzw. copolymeren (Meth-)Acrylsäure,
- (b) 25 bis 50 Gew.-% Natriumcarbonat (wasserfrei gerechnet),
- (c) 4 bis 20 Gew.-% Natriumsulfat (wasserfrei gerechnet) und
- (d) 1 bis 7 Gew.-% Wasser,
- (a) 40 bis 55 Gew.-%, insbesondere 45 bis 52 Gew.-%,
- (b) 30 bis 45 Gew.-%, insbesondere 30 bis 40 Gew.-%,
- (c) 5 bis 15 Gew.-%, insbesondere 5 bis 10 Gew.-%, und
- (d) 2 bis 6 Gew.-%, insbesondere 3 bis 5 Gew.-% der genannten Verbindungen.
- (a) 35 to 60% by weight of sodium salts of at least one homopolymeric or copolymeric (meth) acrylic acid,
- (b) 25 to 50% by weight of sodium carbonate (calculated as anhydrous),
- (c) 4 to 20% by weight sodium sulfate (calculated as anhydrous) and
- (d) 1 to 7% by weight of water,
- (a) 40 to 55% by weight, in particular 45 to 52% by weight,
- (b) 30 to 45% by weight, in particular 30 to 40% by weight,
- (c) 5 to 15% by weight, in particular 5 to 10% by weight, and
- (d) 2 to 6% by weight, in particular 3 to 5% by weight, of the compounds mentioned.
Die Komponente (a) besteht aus homopolymeren bzw. copolymeren Carbonsäuren in Form der Natriumsalze. Geeignete Homopolymere sind Polymethacrylsäure und bevorzugt Polyacrylsäure, beispielsweise solche mit einem Molekulargewicht von 800 bis 150 000 (auf Säure bezogen). Werden ausschließlich homopolymere Polyacrylsäuren (in Salzform) verwendet, beträgt deren Molekulargewicht im Interesse einer guten Rieselfähigkeit und Lagerbeständigkeit vorzugsweise 1 000 bis 80 000 (auf Säure bezogen).Component (a) consists of homopolymeric or copolymeric carboxylic acids in the form of the sodium salts. Suitable homopolymers are polymethacrylic acid and preferably polyacrylic acid, for example those with a molecular weight of 800 to 150,000 (based on acid). If only homopolymeric polyacrylic acids (in salt form) are used, their molecular weight is preferably 1,000 to 80,000 (based on acid) in the interest of good flowability and storage stability.
Geeignete Copolymere sind solche der Acrylsäure mit Methacrylsäure und vorzugsweise Copolymere der Acrylsäure oder Methacrylsäure mit Maleinsäure. Als besonders geeignet haben sich Copolymere der Acrylsäure mit Maleinsäure erwiesen, wie sie beispielsweise in EP-B-25 551 charakterisiert sind. Es handelt sich dabei um Copolymerisate, die 50 bis 90 Gew.-% Acrylsäure und 50 bis 10 Gew.-% Maleinsäure enthalten. Besonders bevorzugt sind solche Copolymere, in denen 60 bis 85 Gew.-% Acrylsäure und 40 bis 15 Gew.-% Maleinsäure vorliegen. Ihr Molekulargewicht, bezogen auf freie Säuren, beträgt im allgemeinen 5 000 bis 200 000, vorzugsweise 10 000 bis 120 000.Suitable copolymers are those of acrylic acid with methacrylic acid and preferably copolymers of acrylic acid or methacrylic acid with maleic acid. Copolymers of acrylic acid with maleic acid, as are characterized, for example, in EP-B-25 551, have proven to be particularly suitable. These are copolymers which contain 50 to 90% by weight of acrylic acid and 50 to 10% by weight of maleic acid. Copolymers in which 60 to 85% by weight of acrylic acid and 40 to 15% by weight of maleic acid are present are particularly preferred. Their molecular weight, based on free acids, is generally 5,000 to 200,000, preferably 10,000 to 120,000.
Mit Vorteil lassen sich auch Gemische verschiedener Homo- und Copolymerer einsetzen, insbesondere Gemische aus homopolymerer Acrylsäure und den vorstehend beschriebenen Copolymeren aus 50 bis 90 Gew.-% Acrylsäure und 50 bis 10 % Maleinsäure. Derartige Gemische, die sich durch günstige Korneigenschaften und hohe Lagerbeständigkeit auszeichnen, können zum Beispiel aus 10 bis 50 Gew.-% homopolymerer Acrylsäure und 90 bis 50 Gew.-% Acrylsäure-Maleinsäure-Copolymeren bestehen. In diesen Gemischen können auch hochpolymere Polyacrylsäuren mitverwendet werden, die bei alleinigem Einsatz etwas mehr zum Kleben bzw. Zerfließen der Körner neigen als niedermolekulare Polyacrylate.Mixtures of different homopolymers and copolymers can also be used with advantage, in particular mixtures of homopolymeric acrylic acid and the copolymers of 50 to 90% by weight of acrylic acid and 50 to 10% of maleic acid described above. Such mixtures, which are characterized by favorable grain properties and high storage stability, can be made, for example, from 10 to 50 wt % By weight of acrylic acid-maleic acid copolymers exist. Highly polymeric polyacrylic acids can also be used in these mixtures which, when used alone, have a slightly greater tendency to stick or melt than the low molecular weight polyacrylates.
Die Polycarboxylate werden als Pulver, vorzugsweise aber als Granulat eingesetzt. Zu den brauchbaren Polyacrylaten gehören beispielsweise die Sokalane R CP 10, PA 10 und PM 10 der Firma BASF, Alcosperse R der Firma Alco: Alcosperse R 102, 104, 106, 404, 406), Acrysole R der Firma Norsohaas: Acrysole R A 1N, LMW 45 N, LMW 10 N, LMW 20 N, Degapas R der Firma Degussa: Degapas R 4104 N, Good-Rite R der Firma Goodrich: Good-Rite R K-XP 18, K 739 und K 7200 N. Auch Copolymere (Polyacrylsäure und Maleinsäure) können eingesetzt werden, beispielsweise Sokalane R der Firma BASF: Sokalan R CP 5, CP 7, Acrysole R der Firma Norsohaas: Acrysol R QR 1014 und SP O2N, Alcosperse R der Firma Alco: Alcosperse R 175. Das Natriumcarbonat (b) und das Natriumsulfat (c) werden in wasserfreier Form eingesetzt. Bei Anteilen an Natriumcarbonat von ca. 40 Gew.-% und mehr empfiehlt es sich, den Wassergehalt (d) der Additive auf weniger als 6 Gew.-% zu senken oder den Anteil an Natriumsulfat etwas höher zu wählen, beispielsweise im Bereich 8 bis 15 Gew.-%. Anteile an Natriumsulfat von über 10 Gew.-%, vorzugsweise 15 bis 20 Gew.-%, verbessern grundsätzlich die Korneigenschaften und die Lagerbeständigkeit der Additive. Andererseits ist Natriumsulfat bei der Anwendung der Additive unwirksamer Ballaststoff, weshalb sein Anteil möglichst gering sein sollte. Es ist sehr überraschend, daß bereits Anteile von 5 bis 6 Gew.-% (c) ausreichen, um Additive mit einem Gehalt von ca. 50 Gew.-% (a), ca. 40 Gew.-% (b) und ca. 4 Gew.-% (d) zu stabilisieren und gute Rieseleigenschaften zu gewährleisten.The polycarboxylates are used as powder, but preferably as granules. The usable polyacrylates include, for example, Sokalane R CP 10, PA 10 and PM 10 from BASF, Alcosperse R from Alco: Alcosperse R 102, 104, 106, 404, 406), Acrysole R from Norsohaas: Acrysole R A 1N , LMW 45 N, LMW 10 N, LMW 20 N, Degapas R from Degussa: Degapas R 4104 N, Good-Rite R from Goodrich: Good-Rite R K-XP 18, K 739 and K 7200 N. Also copolymers (Polyacrylic acid and maleic acid) can be used, for example Sokalane R from BASF: Sokalan R CP 5, CP 7, Acrysole R from Norsohaas: Acrysol R QR 1014 and SP O2N, Alcosperse R from Alco: Alcosperse R 175. The sodium carbonate (b) and the sodium sulfate (c) are used in anhydrous form. With proportions of sodium carbonate of approx. 40% by weight and more, it is advisable to reduce the water content (d) of the additives to less than 6% by weight or to choose a somewhat higher proportion of sodium sulfate, for example in the range 8 to 15% by weight. Sodium sulfate contents of more than 10% by weight, preferably 15 to 20% by weight, fundamentally improve the grain properties and the shelf life of the additives. On the other hand, sodium sulfate is ineffective fiber when using the additives, which is why its proportion should be as low as possible. It is very surprising that fractions of 5 to 6% by weight (c) are sufficient to add additives with a content of approx. 50% by weight (a), approx. 40% by weight (b) and approx Stabilize 4% by weight (d) and ensure good pouring properties.
Weiterhin können die Reinigungsadditive noch Minderbestandteile wie Farbstoffe und Farbpigmente enthalten und einheitlich oder gesprenkelt angefärbt sein. Der Anteil derartiger Minderbestandteile liegt deutlich unter 1 Gew.-%.Furthermore, the cleaning additives can contain minor components such as dyes and color pigments and can be colored uniformly or speckled. The proportion of such minor components is well below 1% by weight.
Als Gerüstsubstanzen können neben den Alkalcarbonaten noch Natriumcitrate, Nitrilotriacetat, Phosphonate und Alkalidisilikate dienen. Sie binden zusammen mit dem polycarboxylathaltigen Reinigungsadditivanteil durch Komplexbildung bzw. Dispergierung Härtebildner wie Calcium- und Magnesiumionen aus dem Wasser bzw. aus den Speiseresten, und sie verhindern damit die Bildung von Kalkbelägen in der Spülmaschine und auf dem Geschirr. Sie können als wasserfreie und/oder als Hydratsalze eingesetzt werden. Als Alkalicarbonat wird vorzugsweise Natriumcarbonat beliebiger Qualität eingesetzt, wie z. B. calcinierte Soda, verdichtete Soda und auch Na-Hydrogencarbonat. Als Natriumcitrat kommen wasserfreies Trinatriumcitrat bzw. Trinatriumcitratdihydrat in Betracht. Bevorzugtes Phosphonat ist das Tetranatriumsalz der 1-Hydroxyethan-1,1-di-phosphonsäure (Turpinal R 4 NZ der Firma Henkel). Als Disilikat 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 the alkali carbonates, sodium citrates, nitrilotriacetate, phosphonates and alkali disilicates can also serve as builders. You tie together with the polycarboxylate-containing cleaning additive component through complex formation or dispersion, hardness-forming agents such as calcium and magnesium ions from the water or from the food residues, 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. As alkali carbonate sodium carbonate of any quality is preferably used, such as. B. calcined soda, compressed soda and also sodium bicarbonate. Anhydrous trisodium citrate or trisodium citrate dihydrate are suitable as sodium citrate. The preferred 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 SiO₂: Na₂O = 1: 2-2.5 is suitable as a disilicate (e.g. Portil R A or AW from Henkel, Britesil R H 24 or C 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 0,2 bis 5, vorzugsweise 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 0,2 bis 2, vorzugsweise 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 C₁₂-C₁₈ alkyl polyethylene glycol polypropylene glycol ethers, each with up to 8 moles of ethylene oxide and propylene oxide units in the molecule. Their share in the total weight of the finished tablets is generally 0.2 to 5, preferably 0.5 to 3% by weight. But you can also use other non-foaming surfactants known as low foams, such as. B. C₁₂-C₁₈ 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 0.2 to 2, preferably 0.2 to 1 wt .-%, based on the entire tablet, of defoaming agents such as 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. Serve as bleach activators preferably 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 can also be used to better remove protein or starch-containing food residues, for example proteases such as BLAP R from Henkel, Opitmase R -M-440, Optimase R -M-330, 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, 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. Zwecks Einstellung des gewünschten pH-Wertes wird vorzugsweise Na-hydrogencarbonat verwendet.The use of tabletting aids, such as mold release agents, for example paraffin oil, 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. Na-hydrogen carbonate is preferably used to set the desired pH.
Für Rahmenrezepturen der erfindungsgemäß hergestellten Reinigungsmitteltabletten kommen etwa folgende Bereiche in Betracht:
Die mittlere Korngröße der granularen Reinigungsadditive beträgt üblicherweise 0,2 bis 1,2 mm, wobei der Anteil der Körner unterhalb 0,1 mm zweckmäßig nicht mehr als 2 Gew.-% und oberhalb 2 mm nicht mehr als 20 Gew.-% beträgt. Vorzugsweise weisen mindestens 80 Gew.-%, insbesondere mindestens 90 Gew.-% der Körner eine Größe von 0,2 bis 1,6 mm auf, wobei der Anteil der Körner zwischen 0,1 und 0,05 mm nicht mehr als 3 Gew.-%, insbesondere nicht mehr als 1 Gew.-% und der Anteil der Körner zwischen 1,6 und 2,4 mm nicht mehr als 20 Gew.-%, insbesondere nicht mehr als 10 Gew.-% beträgt. Das Schüttgewicht beträgt etwa 350 bis 550 g/l.The average grain size of the granular cleaning additives is usually 0.2 to 1.2 mm, the proportion of the grains below 0.1 mm advantageously not more than 2% by weight and above 2 mm not more than 20% by weight. Preferably, at least 80% by weight, in particular at least 90% by weight, of the grains have a size of 0.2 to 1.6 mm, the proportion of the grains between 0.1 and 0.05 mm not more than 3% by weight .-%, in particular not more than 1% by weight and the proportion of the grains between 1.6 and 2.4 mm is not more than 20% by weight, in particular not more than 10% by weight. The bulk weight is about 350 to 550 g / l.
Die Herstellung der granularen Reinigungsadditive erfolgt durch Sprühtrocknung eines wäßrigen Slurries. Die Slurrykonzentration liegt zwischen 50 und 68 Gew.-% (nichtwäßriger Anteil), vorzugsweise zwischen 55 und 60 Gew.-%, wobei die Viskosität der Paste maßgebend ist, die 10 000 mPa·s nicht überschreiten sollte und vorteilhaft 2 500 bis 6 000 mPa·s beträgt. Die Temperatur des Slurries liegt üblicherweise zwischen 50 und 100 °C. Der Druck an den Sprühdüsen beträgt im allgemeinen 30 bis 80 bar, vorzugsweise 40 bis 70 bar. Die Temperatur der im Gegenstrom geführten Trockengase in der Eingangszone des Sprühturms, d. h. im sogenannten Ringkanal, liegt vorteilhaft zwischen 200 und 320 °C, insbesondere zwischen 220 und 300 °C. Im Bereich des Turmaustritts soll sie zwischen 100 und 130 °C, vorzugsweise zwischen 110 und 125 °C liegen. Derart vergleichsweise hohe Betriebstemperaturen sind für die Herstellung eines einwandfreien Produktes von Vorteil und trotz des hohen Anteils an brennbarer organischer Substanz im Sprühprodukt nicht kritisch, da die Selbstentzündungstemperatur oberhalb 330 °C liegt. Im Interesse günstiger Korneigenschaften wird die Trocknung vorzugsweise so geleitet, daß die Wasserbindung auf weniger als 1 Mol H₂O pro Mol Natriumcarbonat gesenkt wird. Zur Sprühtrocknung können übliche Sprühtrocknungsanlagen (Sprühtürme) eingesetzt werden, wobei die Sprühdüsen in einer oder mehreren Ebenen angeordnet sein können.The granular cleaning additives are produced by spray drying an aqueous slurry. The slurry concentration is between 50 and 68% by weight (non-aqueous fraction), preferably between 55 and 60% by weight, the viscosity of the paste being decisive, which should not exceed 10,000 mPa · s and advantageously 2,500 to 6,000 mPa · s. The temperature of the slurry is usually between 50 and 100 ° C. The pressure at the spray nozzles is generally 30 to 80 bar, preferably 40 to 70 bar. The temperature of the counter-current dry gases in the entrance zone of the spray tower, ie in the so-called ring channel, is advantageously between 200 and 320 ° C, in particular between 220 and 300 ° C. In the area of the tower outlet it should be between 100 and 130 ° C, preferably between 110 and 125 ° C. Such comparatively high operating temperatures are advantageous for the production of a perfect product and, despite the high proportion of combustible organic substance in the spray product, are not critical, since the self-ignition temperature is above 330 ° C. In the interest of favorable grain properties, the drying is preferably conducted so that the water binding to less is reduced as 1 mole of H₂O per mole of sodium carbonate. Conventional spray drying systems (spray towers) can be used for spray drying, it being possible for the spray nozzles to be arranged in one or more levels.
Das den Turm verlassende Sprühgut wurde, gegebenenfalls nach Kühlung mit strömender Luft, mit den übrigen Tablettenbestandteilen wie beschrieben gemischt und dann insgesamt auf herkömmlichen Tablettenpressen mit einem Preßdruck von 200 bis 1 500 . 10⁵, vorzugsweise 300 bis 1000 . 10⁵ Pa 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 spray material leaving the tower was mixed with the other tablet components as described, if necessary after cooling with flowing air, and then in total on conventional tablet presses with a compression pressure of 200 to 1500. 10⁵, preferably 300 to 1000. 10⁵ Pa pressed. 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 / cm³, preferably between about 1.4 to 1.8 g / cm³. The compression during the pressing process caused changes in the density, which from about 0.4 to 1.2 g / cm³, preferably about 0.6 to 1.0 g / cm³ to about 1.2 to 2.0 g / cm³, preferably about 1.4 to 1.6 g / cm³ rose.
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 rate of dissolution via the outer surface exposed to the H₂O attack. For reasons of stability, cylindrical compacts with a diameter / height ratio of approximately 0.6 to 4.0: 1 were produced.
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, since it could. a. had an insufficient breaking strength. The tablets also caked on the mixtures on the upper ram of the presses.
Für die Bestandteile der nachfolgenden Beispiele gilt als Legende:The following applies to the components of the following examples:
Fettalkoholethoxylate der Firma BASF:
Plurafac LF 221
Plurafac LF 223: Alkyl (C₁₂C₁₈)-polyethylenglykol (< 8 EO)-polybutylenglykol(< 8 BuO)-ether
Plurafac LF 403: Alkyl (C₁₂C₁₈)-polyethylenglykol (< 8 EO)-polypropylenglykol-(< 8 PO)-ether
Fettalkoholethoxylate der Firma Henkel:
Dehypon LT 104: Fettalkohol (C₁₂C₁₈)*9EO-butylether
Dehypon LS 54: Fettalkohol (C₁₂C₁₄)*5EO*4PO
* = umgesetzt mit
Turpinal R 4 N-Z = Tetranatriumsalz der 1-Hydroxyethan-1,1-di-phosphonsäure der Firma Henkel
TAED = Tetraacethylethylendiamin
NTA = Nitrilotrinatriumacetat
h = Stunden
Die Mengenangaben in den nachfolgenden Beispielen sind Gewichtsprozente.Fatty alcohol ethoxylates from BASF:
Plurafac LF 221
Plurafac LF 223: alkyl (C₁₂C₁₈) polyethylene glycol (<8 EO) polybutylene glycol (<8 BuO) ether
Plurafac LF 403: alkyl (C₁₂C₁₈) polyethylene glycol (<8 EO) polypropylene glycol - (<8 PO) ether
Fatty alcohol ethoxylates from Henkel:
Dehypon LT 104: fatty alcohol (C₁₂C₁₈) * 9EO-butyl ether
Dehypon LS 54: fatty alcohol (C₁₂C₁₄) * 5EO * 4PO
* = implemented with
Turpinal R 4 NZ = tetrasodium salt of 1-hydroxyethane-1,1-di-phosphonic acid from Henkel
TAED = tetraacethylethylenediamine
NTA = nitrilotrine sodium acetate
h = hours
The amounts in the examples below are percentages by weight.
In einem 130 l-Lödige-Pflugscharmischer wurde eine 50 kg Gemischcharge hergestellt. Hierzu wurden zunächst 6,8 Gew.-Teile Natriumcarbonat wasserfrei, 32,0 Gew.-Teile Natriumhydrogencarbonat und 4,0 Gew.-Teile Wasser bei laufendem Zerhacker gemischt und gleich anschließend weiter mit 20,0 Gew.-Teilen eines granularen alkalischen Reinigungsadditivs, bestehend aus 40,8 Gew.-% Natriumcarbonat wasserfrei, 5,0 Gew.-% Natriumsulfat, 50,0 Gew.-% des Natriumsalzes des Copolymerisats aus Maleinsäure und Acrylsäure mit einer Molmasse von 70 000 (Sokalan CP 5 der BASF) und 4,2 Gew.-% Wasser, 20,0 Gew.-Teilen Natriumcitrat-dihydrat, 2,0 Gew.-Teilen Plurafac R LF 403 und 0,2 Gew.-Teilen Duftstoff vermischt. Ohne Zerhackereinsatz wurden dann 2,0 Gew.-Teile TAED, 7,0 Gew.-Teile Natriumperboratmonohydrat, 0,5 Gew.-Teile BLAP R 140 und 0,5 Gew.-Teile Termamyl R 60 T zugemischt. Die Verpressung des Gemisches erfolgte zu 25 g-Tabletten mit einem Durchmesser von 38 mm unter Verwendung einer Rundlaufpresse vom Typ "Korsch PH 423". Die Einfüllhöhe in die Matritzen betrug 31 - 33 mm. Eine Verdichtung erfolgte auf eine Tablettenhöhe von 12,3 als auch von 15 mm.
Eine Verpressung mit abgelagerter Mischung erbrachte weniger stabile Tabletten.Compression with a deposited mixture resulted in less stable tablets.
Analog zu Beispiel 1 wurden Tabletten mit unterschiedlichen Gehalten an Natriumcarbonat und Natriumhydrogencarbonat bei gleichem Wassergehalt hergestellt (vgl. Tabelle 1), die ähnlich gute Ergebnisse aufwiesen. Mit Sokalan R CP 5-Pulver wurden ebenfalls gut nachhärtende stabile Tabletten erhalten.
Auch bei Einsatz von vorhydratisiertem Natriumcarbonatdekahydrat wurden zwar nachhärtende bruchfeste Tabletten erhalten, aber Natriumcarbonatdekahydrat ist wegen seines niedrigen Schmelzpunktes von 32°C nur schwierig zu verarbeiten. Im Lagerbehälter kam es zum Verbacken und Verklumpen. Hierbei wurde das Dekahydrat zusammen mit den restlichen Komponenten in einem Lödige-Pflugscharmischer vermischt. Die so erhaltene Mischung wurde auf einer Exzenterpresse "Korsch EK IV" zu 26 g schweren Tabletten verpreßt. Bei Verwendung von 38 mm Tablettierwerkzeugen und einer Einfüllhöhe von 33 mm in der Matritze erfolgte die Verdichtung auf eine Tablettenhöhe von ca. 15 mm. Die benötigten Preßkräfte betrugen 70 bis 75 KN für den Oberstempel und 50 bis 55 KN für den Unterstempel. Ergebnisse siehe Tabelle 2.
Enthielten die Rezepturen außer Natriumcarbonat noch Natriumdisilikat als weiteren Alkaliträger, kam man ebenfalls zu nachhärtenden bruchstabilen Tabletten (vgl. Tabelle 3).
Claims (3)
- A process for the production of stable, dual-function phosphate- and metasilicate-free, low-alkali detergent tablets, which develop a pH value of at most about 10.5 in the wash liquor, for dishwashing machines containing solid alkali metal salts of at least one homopolymeric or copolymeric (meth)acrylic acid, builders, low-foaming detergents, bleaching agents and optionally enzymes, bleach activators, fragrances and dyes, characterized in that the sodium carbonate serving as part of the builders is used in anhydrous form and is first mixed in a mixing step preferably on its own or with the other builders and the solid alkali metal salt of at least one homopolymeric or copolymeric (meth)acrylic acid together with water in the quantity necessary for partial hydration of the anhydrous sodium carbonate, i.e. in a quantity of around 5 to 40% by weight, based on the anhydrous sodium carbonate used as builder, after which the remaining constituents of the mixture are added and the mixture obtained is tabletted in a standard tablet press.
- A process as claimed in claim 1, characterized in that the solid alkali metal salts of the at least one homopolymeric or copolymeric (meth)acrylic acid are used in powder or granular form.
- A process as claimed in claim 1, characterized in that the solid alkali metal salts of the at least one homopolymeric or copolymeric (meth)acrylic acid are used as granular detergent additives in accordance with German patent application DE-A-39 37 469.
Applications Claiming Priority (3)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| DE4121307A DE4121307A1 (en) | 1991-06-27 | 1991-06-27 | METHOD FOR THE PRODUCTION OF STABLE, BIFUNCTIONAL, PHOSPHATE AND METASILICATE-FREE LOW-ALKALINE DETERGENT TABLETS FOR THE MACHINE DISHWASHER |
| DE4121307 | 1991-06-27 | ||
| PCT/EP1992/001387 WO1993000419A1 (en) | 1991-06-27 | 1992-06-19 | Method for the production of cleaing-agent tablets for machine dishwashing |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| EP0591282A1 EP0591282A1 (en) | 1994-04-13 |
| EP0591282B1 true EP0591282B1 (en) | 1995-09-13 |
Family
ID=6434910
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| EP92912460A Expired - Lifetime EP0591282B1 (en) | 1991-06-27 | 1992-06-19 | Method for the production of cleaning-agent tablets for machine dishwashing |
Country Status (6)
| Country | Link |
|---|---|
| EP (1) | EP0591282B1 (en) |
| AT (1) | ATE127835T1 (en) |
| DE (2) | DE4121307A1 (en) |
| DK (1) | DK0591282T3 (en) |
| ES (1) | ES2076768T3 (en) |
| WO (1) | WO1993000419A1 (en) |
Families Citing this family (33)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5898025A (en) * | 1992-09-25 | 1999-04-27 | Henkel Kommanditgesellschaft Auf Aktien | Mildly alkaline dishwashing detergents |
| DE4232170C2 (en) * | 1992-09-25 | 1999-09-16 | Henkel Kgaa | Weakly alkaline dish detergent |
| DE4315048A1 (en) * | 1993-04-01 | 1994-10-06 | Henkel Kgaa | Process for the production of stable, bifunctional, phosphate, metasilicate and polymer-free, low-alkaline detergent tablets for automatic dishwashing |
| DE69408530T2 (en) * | 1993-04-01 | 1998-05-28 | Unilever Nv | SOLID DETERGENT BRIQUETTES |
| US5698504A (en) * | 1993-07-01 | 1997-12-16 | The Procter & Gamble Company | Machine dishwashing composition containing oxygen bleach and paraffin oil and benzotriazole compound silver tarnishing inhibitors |
| WO1995001416A1 (en) * | 1993-07-01 | 1995-01-12 | The Procter & Gamble Company | Machine dishwashing composition containing oxygen bleach and paraffin oil and benzotriazole compound silver tarnishing inhibitors |
| US5824630A (en) * | 1993-07-16 | 1998-10-20 | The Procter & Gamble Company | Machine dishwashing composition containing oxygen bleach and paraffin oil and nitrogen compound silver tarnishing inhibitors |
| ATE193056T1 (en) * | 1993-07-16 | 2000-06-15 | Procter & Gamble | DETERGENT COMPOSITIONS FOR DISHWASHERS |
| US5759976A (en) * | 1993-09-13 | 1998-06-02 | Diversey Lever, Inc. | Process for forming tableted high-caustic detergent |
| ES2112558T3 (en) * | 1993-09-13 | 1998-04-01 | Unilever Nv | DETERGENT IN THE FORM OF TABLETS, MANUFACTURING PROCEDURE AND METHOD OF USE. |
| CA2180433C (en) † | 1994-01-25 | 2000-04-25 | Francois Delwel | Co-granules and detergent tablets formed therefrom |
| DE4408718A1 (en) * | 1994-03-15 | 1995-09-21 | Henkel Kgaa | Breakage and storage stable, polyfunctional cleaning tablets, process for their preparation and their use |
| US6063747A (en) * | 1995-07-25 | 2000-05-16 | The Procter & Gamble Company | Detergent compositions in compacted solid form |
| GB2303635A (en) * | 1995-07-25 | 1997-02-26 | Procter & Gamble | Detergent compositions in compacted solid form |
| US5726142A (en) * | 1995-11-17 | 1998-03-10 | The Dial Corp | Detergent having improved properties and method of preparing the detergent |
| US5962389A (en) * | 1995-11-17 | 1999-10-05 | The Dial Corporation | Detergent having improved color retention properties |
| DE19605688A1 (en) * | 1996-02-16 | 1997-08-21 | Henkel Kgaa | Transition metal complexes as activators for peroxygen compounds |
| WO1997036986A1 (en) | 1996-04-01 | 1997-10-09 | Henkel Kommanditgesellschaft Auf Aktien | Cleaning agent with oligoammine activator complexes for peroxide compounds |
| DE19620411A1 (en) | 1996-04-01 | 1997-10-02 | Henkel Kgaa | Transition metal amine complexes as activators for peroxygen compounds |
| DE19616693A1 (en) * | 1996-04-26 | 1997-11-06 | Henkel Kgaa | Enol esters as bleach activators for detergents and cleaning agents |
| US5837663A (en) * | 1996-12-23 | 1998-11-17 | Lever Brothers Company, Division Of Conopco, Inc. | Machine dishwashing tablets containing a peracid |
| US5900395A (en) * | 1996-12-23 | 1999-05-04 | Lever Brothers Company | Machine dishwashing tablets containing an oxygen bleach system |
| DE19713852A1 (en) | 1997-04-04 | 1998-10-08 | Henkel Kgaa | Activators for peroxygen compounds in detergents and cleaning agents |
| DE19714657C1 (en) * | 1997-04-09 | 1999-01-07 | Benckiser Nv | Water soluble, water softening builder |
| DE19824743A1 (en) * | 1998-06-03 | 1999-12-09 | Henkel Kgaa | Fracture-stable and quick-dissolving detergent tablets |
| EP1043388B1 (en) * | 1999-03-29 | 2001-12-19 | DALLI-WERKE WÄSCHE-UND KÖRPERPFLEGE GmbH & Co.KG. | Machine dishwashing tablets containing a granular disintegrant |
| EP1491621B2 (en) * | 2003-06-28 | 2014-10-01 | Dalli-Werke GmbH & Co. KG | Alpha-olefin and alpha-olefin-cellulose granulates as disintegrants |
| US7893012B2 (en) * | 2007-05-04 | 2011-02-22 | Ecolab Inc. | Solidification matrix |
| CA2699537C (en) * | 2007-05-04 | 2015-06-16 | Ecolab Inc. | Pressed, self-solidifying, solid cleaning compositions and methods of making them |
| US8889048B2 (en) | 2007-10-18 | 2014-11-18 | Ecolab Inc. | Pressed, self-solidifying, solid cleaning compositions and methods of making them |
| DE102008060469A1 (en) * | 2008-12-05 | 2010-06-10 | Henkel Ag & Co. Kgaa | Automatic dishwashing tablet |
| FR3047741B1 (en) * | 2016-02-11 | 2019-06-07 | S.A. Gerlon | PROCESS FOR MANUFACTURING UNI-DOSE TABLETS |
| DE102017212561A1 (en) | 2017-07-21 | 2019-01-24 | Henkel Ag & Co. Kgaa | Dishwashing detergent containing citrate dihydrate and anhydrate |
Family Cites Families (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CA1120819A (en) * | 1977-06-01 | 1982-03-30 | Jurgen W.K. Gromer | Detergent tablet |
| DE3541145A1 (en) * | 1985-11-21 | 1987-05-27 | Henkel Kgaa | UNIFORMED DETERGENT TABLETS FOR MACHINE DISHWASHER |
| DE3634813A1 (en) * | 1986-10-13 | 1988-04-14 | Henkel Kgaa | DETERGENT TABLETS FOR MACHINE DISHWASHER |
| DE3827895A1 (en) * | 1988-08-17 | 1990-02-22 | Henkel Kgaa | PROCESS FOR PREPARING PHOSPHATE-REDUCED DETERGENT TABLETS |
| AU647736B2 (en) * | 1989-04-24 | 1994-03-31 | Unilever Plc | Detergent compositions |
| GB2234980A (en) * | 1989-07-25 | 1991-02-20 | Unilever Plc | Detergent composition for machine dishwashers |
| DE3937469A1 (en) * | 1989-11-10 | 1991-05-16 | Henkel Kgaa | GRANULAR, ALKALINE, PHOSPHATE-FREE CLEANING ADDITIVE |
| DE4010524A1 (en) * | 1990-04-02 | 1991-10-10 | Henkel Kgaa | STABLE, BIFUNCTIONAL, PHOSPHATE-FREE DETERGENT TABLETS FOR THE MACHINE DISHWASHER |
-
1991
- 1991-06-27 DE DE4121307A patent/DE4121307A1/en not_active Withdrawn
-
1992
- 1992-06-19 EP EP92912460A patent/EP0591282B1/en not_active Expired - Lifetime
- 1992-06-19 AT AT92912460T patent/ATE127835T1/en not_active IP Right Cessation
- 1992-06-19 WO PCT/EP1992/001387 patent/WO1993000419A1/en active IP Right Grant
- 1992-06-19 ES ES92912460T patent/ES2076768T3/en not_active Expired - Lifetime
- 1992-06-19 DK DK92912460.0T patent/DK0591282T3/en active
- 1992-06-19 DE DE59203697T patent/DE59203697D1/en not_active Expired - Fee Related
Also Published As
| Publication number | Publication date |
|---|---|
| DK0591282T3 (en) | 1996-01-08 |
| DE59203697D1 (en) | 1995-10-19 |
| ES2076768T3 (en) | 1995-11-01 |
| EP0591282A1 (en) | 1994-04-13 |
| ATE127835T1 (en) | 1995-09-15 |
| WO1993000419A1 (en) | 1993-01-07 |
| DE4121307A1 (en) | 1993-01-07 |
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