Nothing Special   »   [go: up one dir, main page]

EP0692020A1 - Stable, bifunctional, phosphate-, metasilicate- and polymer-free low alkaline detergent tablets for dishwashing machines, and process for producing the same - Google Patents

Stable, bifunctional, phosphate-, metasilicate- and polymer-free low alkaline detergent tablets for dishwashing machines, and process for producing the same

Info

Publication number
EP0692020A1
EP0692020A1 EP94912526A EP94912526A EP0692020A1 EP 0692020 A1 EP0692020 A1 EP 0692020A1 EP 94912526 A EP94912526 A EP 94912526A EP 94912526 A EP94912526 A EP 94912526A EP 0692020 A1 EP0692020 A1 EP 0692020A1
Authority
EP
European Patent Office
Prior art keywords
weight
sodium
tablets
stable
phosphate
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.)
Granted
Application number
EP94912526A
Other languages
German (de)
French (fr)
Other versions
EP0692020B1 (en
Inventor
Hans Kruse
Hans-Josef Beaujean
Norbert Schäfer
Jürgen Härer
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Henkel AG and Co KGaA
Original Assignee
Henkel AG and Co KGaA
Priority date (The priority date 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 date listed.)
Filing date
Publication date
Application filed by Henkel AG and Co KGaA filed Critical Henkel AG and Co KGaA
Publication of EP0692020A1 publication Critical patent/EP0692020A1/en
Application granted granted Critical
Publication of EP0692020B1 publication Critical patent/EP0692020B1/en
Anticipated expiration legal-status Critical
Expired - Lifetime legal-status Critical Current

Links

Classifications

    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
    • C11D3/39—Organic or inorganic per-compounds
    • C11D3/3902—Organic or inorganic per-compounds combined with specific additives
    • C11D3/3905—Bleach activators or bleach catalysts
    • C11D3/3907—Organic compounds
    • C11D3/3917—Nitrogen-containing compounds
    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D1/00—Detergent compositions based essentially on surface-active compounds; Use of these compounds as a detergent
    • C11D1/66—Non-ionic compounds
    • C11D1/667—Neutral esters, e.g. sorbitan esters
    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D17/00—Detergent materials or soaps characterised by their shape or physical properties
    • C11D17/0047—Detergents in the form of bars or tablets
    • C11D17/0065—Solid detergents containing builders
    • C11D17/0073—Tablets
    • C11D17/0091—Dishwashing tablets
    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
    • C11D3/02—Inorganic compounds ; Elemental compounds
    • C11D3/04—Water-soluble compounds
    • C11D3/10—Carbonates ; Bicarbonates
    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
    • C11D3/16—Organic compounds
    • C11D3/20—Organic compounds containing oxygen
    • C11D3/2075—Carboxylic acids-salts thereof
    • C11D3/2086—Hydroxy carboxylic acids-salts thereof
    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
    • C11D3/16—Organic compounds
    • C11D3/38—Products with no well-defined composition, e.g. natural products
    • C11D3/386—Preparations containing enzymes, e.g. protease or amylase
    • C11D3/38609—Protease or amylase in solid compositions only

Definitions

  • Machine dishwashing generally consists of a pre-rinse cycle, a cleaning cycle, one or more intermediate rinse cycles, a rinse cycle and a drying cycle. This applies to machine washing both in the home and in business.
  • HGSM HGSM
  • GGSM In the case of a commercial dishwasher, hereinafter referred to as GGSM, the so-called pre-clearing zone corresponds in principle to the pre-rinse cycle of an HGSM.
  • the cleaning agent metered into the cleaning zone is used by overflow in the pre-clearing zone to support the cleaning of the adhering food residues.
  • GGSM in which the pre-clearing zone is only operated with fresh water, but a pre-clearing zone with detergent additive is more effective than pre-clearing with fresh water alone.
  • pre-clearing zone cleaning from GGSM has also already been transferred to HGSM and dosing of cleaning agents has already been made possible for the pre-rinse cycle by dosing cleaning agents in tablet form and one or more suitable tablets, for example in a free part of the cutlery basket. but also positioned elsewhere in the machine, as a result of which they could act both in the pre-rinse cycle and in the actual cleaning cycle, that is to say bifunctionally.
  • Such tablet-shaped cleaning agents is described, for example, in DE-OS 3541 145.
  • These are uniform Compound cleaning agent tablets with a broad dissolving profile for machine dishwashing, which contain the usual alkaline components, in particular from the group of alkali metal silicates and pentaalkali metal triphosphates, active chlorine compounds and tabletting aids, and in which the alkali metal silicates are made from a mixture of "sodium metasilicate nonahydrate" (Na2 ) and anhydrous sodium metasilicate and the pentaalkali metal triphosphate consists of anhydrous pentasodium triphosphate, the weight ratio of anhydrous sodium metasilicate: sodium metasilicate nonahydrate being between 1: 0.3 and 1: 1.5 and the weight ratio of pentasodium triphosphate to sodium metasikate, each being water-free , 2: 1 to 1: 2, preferably 1: 1 to 1: 1.7.
  • Tablets of this type have such a broad dissolution profile that they are already dissolved in the tap water to at least 10% by weight in the pre-rinsing step of an HGSM, thereby developing a pH value of at least 10.0 in the rinsing liquor and with good hot water solubility at least 60% by weight, preferably at least 70% by weight, are still available for the cleaning process.
  • the dissolution profile is understood to mean the weight ratio of the proportions of the tablet to the entire tablet which are dissolved from the usual HGSM under the conditions of the pre-rinse cycle.
  • phosphate-free detergent tablets for machine dishwashing have also been on the market for some time and contain essentially silicates, nonionic surfactants, organic complexing agents and percarbonate. If these tablets are placed inside the machine (e.g. in the basket), they will dissolve as far as possible, even completely, during the pre-rinse cycle, so that the actual cleaning cycle table no more detergent is available. In addition, the stability of these tablets is unsatisfactory.
  • DE-OS 4010524 describes stable, bifunctional, phosphate-free detergent tablets for machine dishwashing containing silicate, low-foam nonionic surfactants, organic complexing agents, bleaches and water, the organic complexing agents according to DE-OS 39 37 469 in the form of a granular, alkaline cleaning additive consisting of sodium salts of at least one homopolymeric or copolymeric (meth) acrylic acid, sodium carbonate, sodium sulfate and water.
  • the granular alkaline cleaning additives were mechanically mixed with the other mostly powdery formulation components and pressed in a manner known per se.
  • the sodium carbonate serving as part of the builders was used in anhydrous form and initially in a mixing cycle, preferably alone or with the other builders such as sodium citrate and optionally sodium hydrogen carbonate and the solid alkali salts of at least one homopolymer or copolymer ( Meth-) acrylic acid together with the amount of water required for the partial hydration of the anhydrous sodium carbonate of about 5-40, preferably about 7-20% by weight, based on the anhydrous sodium carbonate used as the framework substance, added - The remaining substances were then added to the mixture and the mixture thus obtained was compressed on a conventional tablet press.
  • the other builders such as sodium citrate and optionally sodium hydrogen carbonate and the solid alkali salts of at least one homopolymer or copolymer ( Meth-) acrylic acid
  • the storage-stable tablets produced in this way have a high breaking strength (greater than 140 N with a diameter of approximately 30 to 40 mm and a density of approximately 1.4 to 1.7 g / cm 3), which also remains stable during storage and thereby changes within a short time Time can still increase significantly.
  • the present invention now relates to stable, bifunctional, phosphate-, etasilicate- and now also polymer-free, low-alkaline cleaning tablets for automatic dishwashing, which are characterized in that they contain sodium citrate, further builders, enzymes and optionally bleach activators, nonionic surfactants, color - and contain fragrances. They correspond to the following basic formulation:
  • Trisodium citrate dihydrate 5 - 50% 20 - 30%
  • Tetraacetylethylenediamine 0.5 - 4% 2 - 4% non-ionic surfactant 0 - 4% 0.5 - 2%
  • a process has been found in which such stable, bifunctional, phosphate-, metasilicate- and now also polymer-free, lower-alkaline detergent tablets for automatic dishwashing with a content of sodium citrate, other scaffold substances, low-foam surfactants, bleaches and optionally Enzymes, bleach activators, fragrances and dyes come when you first moisten sodium citrate dihydrate and / or sodium citrate with a small amount of water of about 3 - 10, preferably about 4 - 6 wt .-%, based on the total composition, then dusted with anhydrous sodium carbonate and then sodium hydrogen carbonate and the bleach activator are added, enzymes, non-ionic surfactants, fragrances / dyes and optionally paraffin oil are added, finally the active oxygen-releasing compound is mixed in with a low energy input and the total mixture obtained in this way on a conventional tablet press at a relative atmospheric humidity 15 to 60, preferably about 20 to 30% with a compression pressure of about 2 to 11, preferably about 4 to 6, MPa to tablets.
  • paraffin oil can also take place together with the addition of the sodium citrate, preferably in the form of a mixture which, in an advanced, separate mixed cut, preferably comprises 1 to 3% by weight, in particular approximately 2% by weight.
  • Paraffin oil based on the total detergent mixture and sodium citrate. Also advantageous is a hydrophobization of the sodium bicarbonate carried out in a preferred mixing step with paraffin oil.
  • a desired further delay in the dissolution in the pre-rinse cycle of an HGSM can take place if the water added at the beginning is already mixed with the nonionic surfactant, to which the fragrance can also be added, or with a glyceride mixture and sprayed onto the sodium citrate and then adding the residual substances.
  • a further preferred embodiment of the process according to the invention consists in first applying all liquid components of the composition to the sodium citrate, then dusting the anhydrous sodium carbonate and then in succession, each with a low energy input, sodium bicarbonate, the bleach activator and finally the active oxygen releasing compound are added and the total mixture thus obtained is pressed as indicated above.
  • Low energy input means gentle mixing without using the high-speed cutter heads with only short dwell times in the mixer.
  • the storage-stable tablets produced according to the invention have a high breaking strength (greater than 140 N with a diameter of about 30 to 40 m and a density of about 1.4 to 1.7 g / atß), which can increase significantly within a short time during storage , and which also remain stable.
  • alkali metal nitrilotriacetates, alkali phosphonates and alkali disilicates can also be used as builders. They bind hardening agents such as calcium and magnesium ions from the water or from the food residues through complex formation or dispersion and thus prevent the formation of limescale deposits in the dishwasher and on the dishes. They can be used as anhydrous and / or as hydrate salts. Water-free trisodium citrate or trisodium citrate dihydrate are suitable as sodium citrate. Sodium carbonate of any quality is preferably used as the alkali carbonate, such as. B. soda ash or compressed soda. Any origin can be used as sodium hydrogen carbonate.
  • Preferred alkali metal phosphonate is the tetrasodium salt of l-hydroxyethane-1,1-di-phosphonic acid (Turpinal ( R ) 4 NZ from Henkel).
  • Dried water glass with the module SiO 2 : Na2 ⁇ 1: 2-2.5, (for example Portil ( R ) A or AW from Henkel, Britesil ( R ) H 24 or C) is suitable as sodium disilicate 24 from Akzo).
  • Extremely low-foaming nonionic compounds are preferably used as low-foaming surfactants, which serve to better remove fatty food residues and as pressing aids. These preferably include C12-C18 alkyl polyethylene glycol polypropylene glycol ethers, each with up to 8 moles of ethylene oxide and propylene oxide units in the molecule. Their share in the total weight of the finished tablets is generally about 0.2 to 5, preferably about 0.5 to 3,% by weight. But you can also use other non-foaming surfactants known as low foams, such as. B.
  • Ci2-Ci8-Alkylpolyethy- lenglykol-polybutylene glycol ether each with up to 8 moles of ethylene oxide and butylene oxide units in the molecule and then optionally about 0.2 to 2, preferably about 0.2 to 1 wt .-%, based on the total Tablet, on defoaming agents such.
  • B. Add silicone oils, mixtures of silicone oil and hydrophobicized silica, paraffin oil / Guerbet alcohols and hydrophobicized silica.
  • Active oxygen carriers are now preferably bleaches which are customary constituents of cleaning agents for HGSM. These include primarily sodium perborate mono- and tetrahydrate as well as sodium percarbonate and sodium uearoat. Since active oxygen only develops its full effect on its own at elevated temperatures, so-called bleach activators are also expediently used to activate it at about 60 ° C., the temperatures of the cleaning process in the HGSM.
  • TAED tetraacetylenediamine
  • PAG penentaacetylglucose
  • DADHT 1,5-di-acetyl-2,4-dioxo-hexahydro-l, 3,5-triazine
  • ISA isatoic anhydride
  • Enzymes such as proteases and amylases can also be used to better remove protein or starch-containing food residues, for example proteins such as BLAP ( R ) from Henkel, Opitmase ( R ) -M-440, Optimase ( R ) - -M -330, Opticlean ( R ) -M-375, Opticlean ( R ) -M-250 from Solvay Enzy ⁇ mes, Maxacal ( R ) CX 450,000, Maxapem ( R ) from Ibis, Savinase ( R ) T from Novo or Esperase ( R ) T from Ibis and amylases such as Termamyl ( R ) 60 T, 90 T from Novo, Amylase-LT ( R ) from Solvay Enzymes or Maxamyl ( R ) P 5000 from Ibis.
  • proteins such as BLAP ( R ) from Henkel, Opitmase ( R ) -M-440, Optimase (
  • Customary oxidation-stable dyes and fragrances can also be added to the tablet mixtures.
  • the tablets can also be pressed in colored layers with otherwise the same composition.
  • tableting aids such as mold release agents, for example paraffin oil, or mixtures of mono-, di- and triglycerides of C12-C18, preferably Ci ⁇ -Ci ⁇ fatty acids, for example commercially available glyceride mixtures sold as baking agents, e.g. Boeson VP (Boehringer, Ingelheim) is not necessary for compressing the tablets according to the invention and can usually be omitted if the tablet mixtures contain nonionic surfactants which essentially take on this task.
  • the addition of paraffin oil and / or glyceride mixtures can nevertheless be expedient, as indicated, because it leads to a delay in dissolution of the tablets, so that a higher proportion of the tablet is available in the cleaning cycle.
  • the desired pH is preferably set via the sodium hydrogen carbonate portion.
  • the mixture produced as described would be pressed on conventional tablet presses with a pressure of about 2 to 11 MPa, preferably about 4 to 6 MPa.
  • the pressing could be carried out in known manner without die lubrication using commercially available eccentric presses, hydraulic presses or rotary presses. No caking of the tablet mixture was observed on the pressing tools. Tools coated with hard plastic as well as uncoated delivered tablets with smooth surfaces, so that in most cases it was also possible to dispense with coating the punches with soft plastic.
  • the pressing conditions were optimized with regard to the setting of the desired dissolution profile with sufficient tablet hardness.
  • the flexural strength can serve as a measure of the tablet hardness (method: compare Ritschel. Die Tablette, Ed. Cantor, 1966, p. 313). According to this, tablets with a bending strength greater than 100 N, preferably greater than 150 N, are sufficiently stable under simulated transport conditions.
  • the bending or breaking strength of the tablets can be controlled by the degree of compression, ie the compression pressure, regardless of their
  • the specific weight of the compacts was between about 1.2 and 2 g / cm 3, preferably between about 1.4 and 1.8 g / cm 3.
  • the compression during the pressing process caused changes in the density, which ranged from about 0.4 to 1.2 g / cm 3, preferably about 0.6 to 1.0 g / i 3 to about 1.2 to 2.0 g /, preferably about 1 .4 to 1.6 g / cm3 rose.
  • the shape of the tablet can also influence the breaking strength and the dissolving speed via the outer surface exposed to the H2O attack. For reasons of stability, cylindrical compacts with a diameter / height ratio of approximately 0.6 to 4.0: 1 were produced.
  • the breaking strength corresponds to the weight of the wedge-shaped load, which leads to the tablet breaking.
  • the amounts of the substance mixture to be compressed for the individual tablets can be varied as desired within technically reasonable limits. Depending on their size, 1 to 2 or even more tablets per machine filling are preferably used in order to provide the entire cleaning process with the necessary active substance content of cleaning agent. Tablets of about 20 to 40 g in weight and a diameter of about 35 to 40 mm are preferred, of which one must be used in each case. If sodium carbonate was not hydrated or used as a full hydrate, the quality of the tablets obtained from the mixture was unusable for the trade since, among other things, they had insufficient breaking strength. The tablets also caked on the mixtures on the upper ram of the presses.
  • a batch of 50 kg was prepared in a 130 l Lödige ploughshare mixer by first spraying 4 parts by weight of water onto 7.5 parts by weight of sodium carbonate and 48 parts by weight of sodium hydrogen carbonate and then with 30 parts by weight of sodium citrate dihydrate, 2 parts by weight of TAED granules and 1 part by weight of BLAP ( R ). 170 and 1 part by weight of Termamyl ( R ) 60 parts were mixed while spraying 0.9 parts by weight of Dehydol LS4 and 0.6 parts by weight of fragrance. 5 parts by weight of perborate onohydrate were then gently mixed into the mixture thus obtained. As can be seen from the table containing the pressing conditions and tablet properties, the mixture gave tablets with only limited resistance to breakage that dissolve too quickly in the pre-rinse cycle.
  • Example A With the same composition as described in Example A, the sodium citrate dihydrate was first sprayed with water in 130 l Lödige mixer according to the invention, followed by dusting with soda. Then TAED granules, sodium hydrogen carbonate, Blap 170, Termamyl 60 T and a mixture of perborate monohydrate, fragrance and dehydol LS4 were added. The much more favorable properties of the tablets obtained in this way can be seen from the tables below, as in the examples below.
  • the mixture was prepared as in Example 1, but after the addition of the dehydol LS4, the perborate monohydrate was finally mixed in separately.
  • Example 4 The mixture was prepared as described in Example 1, but 1% paraffin oil was additionally sprayed onto the mixture at the end.
  • Example 4
  • TAED tetraacetylethylenediamine
  • Boeson VP commercially available glyceride mixture Examples table

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)
  • Health & Medical Sciences (AREA)
  • Emergency Medicine (AREA)
  • Detergent Compositions (AREA)

Abstract

PCT No. PCT/EP94/00932 Sec. 371 Date Oct. 2, 1995 Sec. 102(e) Date Oct. 2, 1995 PCT Filed Mar. 23, 1994 PCT Pub. No. WO94/23011 PCT Pub. Date Oct. 13, 1994A stable, dual-function, phosphate-, metasilicate- and polymer-free low alkali detergent tablet containing: (a) from 5 to 50% by weight of a sodium citrate; (b) from 1 to 60% by weight of anhydrous sodium carbonate; (c) from 1 to 60% by weight of sodium hydrogen carbonate; (d) a bleaching agent selected from the group consisting of sodium perborate monohydrate, sodium percarbonate and mixtures thereof; (e) from 0.5 to 4% by weight of tetraacetyl ethylenediamine; (f) from 0.1 to 2% by weight of protease; (g) from 0.1 to 2% by weight of amylase; and (h) from 3 to 10% by weight of water, all weights being based on the weight of the tablet.

Description

"Stabile, bifunktionelle, phosphat-, etasilikat- und polymerfreie nieder¬ alkalische Reinigungsmitteltabletten für das maschinelle Geschirrspülen und Verfahren zu ihrer Herstellung""Stable, bifunctional, phosphate, etasilicate and polymer-free lower-alkaline detergent tablets for automatic dishwashing and process for their manufacture"
Maschinelles Geschirrspülen besteht im allgemeinen aus einem Vorspülgang, einem Reinigungsgang, einem oder mehreren Zwischenspülgängen, einem Klar¬ spülgang 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 Dosierkäst¬ chen zu bevorraten, das sich meist in der Tür der Maschine befindet und sich zu Beginn des Reinigungsganges automatisch öffnet. Der zuvor ablau¬ fende Vorspülgang wird dabei ohne Wirksubstanz, also ausschließlich mit dem zulaufenden Leitungswasser betrieben.So far, it has been predominant in household dishwashers, hereinafter referred to as HGSM, to store the detergent in a dosing box, which is usually located in the door of the machine and opens automatically at the beginning of the cleaning cycle. The pre-rinse cycle which is carried out beforehand is operated without any active substance, that is to say exclusively with the incoming tap water.
Bei einer gewerblichen Geschirrspülmaschine, im folgenden als GGSM be¬ zeichnet, entspricht die sogenannte Vorabräumzone im Prinzip dem Vorspül¬ gang einer HGSM. Beim maschinellen Spülen in Großküchen wird das der Rei¬ nigungszone zudosierte Reinigungsmittel durch Überlauf schon in der Vor¬ abräumzone zur unterstützenden Reinigung der anhaftenden Speisereste ein¬ gesetzt. 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 the case of a commercial dishwasher, hereinafter referred to as GGSM, the so-called pre-clearing zone corresponds in principle to the pre-rinse cycle of an HGSM. In machine rinsing in canteen kitchens, the cleaning agent metered into the cleaning zone is used by overflow in the pre-clearing zone to support the cleaning of the adhering food residues. 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 be¬ reits zum Vorspülgang ermöglicht, indem man die Dosierung von Reinigungs¬ mitteln in Tablettenform vornahm und eine oder mehrere geeignete Tabletten beispielsweise in einem freien Teil des Besteckkorbes, aber auch an ande¬ rer Stelle in der Maschine positionierte, wodurch sie sowohl im Vorspül¬ gang als auch im eigentlichen Reinigungsgang, also bifunktionell, wirken konnten.The principle of action of pre-clearing zone cleaning from GGSM has also already been transferred to HGSM and dosing of cleaning agents has already been made possible for the pre-rinse cycle by dosing cleaning agents in tablet form and one or more suitable tablets, for example in a free part of the cutlery basket. but also positioned elsewhere in the machine, as a result of which they could act both in the pre-rinse cycle and in the actual cleaning cycle, that is to say bifunctionally.
Der Einsatz solcher tablettenförmiger Reinigungsmittel ist beispielsweise in der DE-OS 3541 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 Pentaalkalitriphos- phate, Aktivchlorverbindungen und Tablettierhilfsmittel enthalten, und bei denen die Alkalimetasilikate aus einem Gemisch aus "Natriummetasilikat- nonahydrat" (Na2H2Siθ4.8H2θ) und wasserfreiem Natriummetasilikat und das Pentaalkalitriphosphat aus wasserfreiem Pentanatriumtriphosphat besteht, wobei das Gewichtsverhältnis von wasserfreiem Natriummetasilikat : Natri- ummetasilikatnonahydrat zwischen 1 : 0,3 und 1 : 1,5 liegt und das Ge¬ wichtsverhältnis von Pentanatriumtriphosphat zu Natriummetas likat, je¬ weils wasserfrei, 2 : 1 bis 1 : 2, vorzugsweise 1 : 1 bis 1 : 1,7 beträgt.The use of such tablet-shaped cleaning agents is described, for example, in DE-OS 3541 145. These are uniform Compound cleaning agent tablets with a broad dissolving profile for machine dishwashing, which contain the usual alkaline components, in particular from the group of alkali metal silicates and pentaalkali metal triphosphates, active chlorine compounds and tabletting aids, and in which the alkali metal silicates are made from a mixture of "sodium metasilicate nonahydrate" (Na2 ) and anhydrous sodium metasilicate and the pentaalkali metal triphosphate consists of anhydrous pentasodium triphosphate, the weight ratio of anhydrous sodium metasilicate: sodium metasilicate nonahydrate being between 1: 0.3 and 1: 1.5 and the weight ratio of pentasodium triphosphate to sodium metasikate, each being water-free , 2: 1 to 1: 2, preferably 1: 1 to 1: 1.7.
Derartige Tabletten besitzen ein solches breites Löseprofil, daß sie be¬ reits im Vorspülgang einer HGSM vom zulaufenden Leitungswasser zu minde¬ stens 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 Reini¬ gungsgang zu Verfügung stehen.Tablets of this type have such a broad dissolution profile that they are already dissolved in the tap water to at least 10% by weight in the pre-rinsing step of an HGSM, thereby developing a pH value of at least 10.0 in the rinsing liquor and with good hot water solubility at least 60% by weight, preferably at least 70% by weight, are still available for the cleaning process.
Unter Löseprofil wird das GewichtsVerhältnis von unter den Bedingungen des Vorspülganges von üblichen HGSM gelösten Anteilen der Tablette zur gesam¬ ten Tablette verstanden.The dissolution profile is understood to mean the weight ratio of the proportions of the tablet to the entire tablet which are dissolved from the usual HGSM under the conditions of the pre-rinse cycle.
Diese bekannten Tabletten enthielten jedoch noch Phosphate, die wie man weiß unerwünscht sind.However, these known tablets still contained phosphates, which are known to be undesirable.
Es sind aber seit einiger Zeit auch schon phosphatfreie Reinigungsmittel¬ tabletten für das maschinelle Geschirrspülen im Handel (z. b. Hui Spül- Tabs der Firma Roth GmbH, Bad Ems), die im wesentlichen Silikate, nicht¬ ionische Tenside, organische Komplexbildner und Percarbonat enthalten. Bei einer Placierung dieser Tabletten innerhalb der Maschine (z. B. im Be¬ steckkorb) lösen sie sich jedoch schon während des Vorspülganges weitest- gehend bis vollständig auf, so daß im eigentlichen Reinigungsgang prak- tisch kein Reinigungsmittel mehr zur Verfügung steht. Darüber hinaus ist die Stabilität dieser Tabletten nicht befriedigend.However, phosphate-free detergent tablets for machine dishwashing (for example Hui Flushing Tabs from Roth GmbH, Bad Ems) have also been on the market for some time and contain essentially silicates, nonionic surfactants, organic complexing agents and percarbonate. If these tablets are placed inside the machine (e.g. in the basket), they will dissolve as far as possible, even completely, during the pre-rinse cycle, so that the actual cleaning cycle table no more detergent is available. In addition, the stability of these tablets is unsatisfactory.
In der DE-OS 4010524 werden stabile, bifunktionelle, phosphatfreie Rei¬ nigungsmitteltabletten für das maschinelle Geschirrspülen mit einem Gehalt an Silikat, schaumarmen nichtionischen Tensiden, organischen Komplexbild¬ nern, Bleichmitteln und Wasser beschrieben, die organische Komplexbildner gemäß der DE-OS 39 37 469 in Form eines granulären, alkalischen Reini¬ gungsadditivs, bestehend aus Natriumsalzen mindestens einer homopolymeren bzw. copoly eren (Meth-)Acrylsäure, Natriumcarbonat, Natriumsulfat und Wasser enthalten. Bei der Herstellung der Tabletten wurden die granulären alkalischen Reinigungsadditive mit den übrigen meist pulverför igen Re¬ zepturbestandteilen mechanisch gemischt und in an sich bekannter Weise verpreßt.DE-OS 4010524 describes stable, bifunctional, phosphate-free detergent tablets for machine dishwashing containing silicate, low-foam nonionic surfactants, organic complexing agents, bleaches and water, the organic complexing agents according to DE-OS 39 37 469 in the form of a granular, alkaline cleaning additive consisting of sodium salts of at least one homopolymeric or copolymeric (meth) acrylic acid, sodium carbonate, sodium sulfate and water. In the manufacture of the tablets, the granular alkaline cleaning additives were mechanically mixed with the other mostly powdery formulation components and pressed in a manner known per se.
Einem weiteren Markttrend folgend wurden unter anderem gemäß der DE-OS 41 21 307 stabile, bifunktionelle, phosphat- und metasilikatfreie niederal¬ kalische Reinigungsmitteltablette mit breitem Löseprofil für das maschi¬ nelle Geschirrspülen zur Verfügung gestellt, die ebenfalls bereits im Vor¬ spülgang einer HGSM vom zulaufenden Leitungswasser zu mindestens 10 Gew.-% bis etwa 50 Gew.-% aufgelöst werden, dabei in der Spülflotte einen pH-Wert von höchstens etwa 10,5 entwickeln und bei guter Warmwasserlöslichkeit zu noch mindestens 50 Gew.-% bis etwa 90 Gew.-% für den Reinigungsgang zur Verfügung stehen. Sie enthalten als Komplexbildner organische Polymere.Following a further market trend, stable, bifunctional, phosphate- and metasilicate-free, low-alkaline detergent tablets with a broad dissolution profile for machine dishwashing were made available, among other things, according to DE-OS 41 21 307, which are also already in the pre-wash cycle of an HGSM from tap water to be dissolved in at least 10% by weight to about 50% by weight, thereby developing a pH value of at most about 10.5 in the rinsing liquor and at least 50% by weight to about 90% by weight if the hot water is soluble .-% are available for the cleaning cycle. They contain organic polymers as complexing agents.
Zur Herstellung dieser bekannten Reinigungsmitteltabletten wurde das als Teil der Gerüstsubstanzen dienende Natriumcarbonat in wasserfreier Form eingesetzt und zunächst in einem Mischgang, vorzugsweise allein oder mit den anderen Gerüstsubstanzen wie Natriumeitrat und gegebenenfalls Natrium- hydrogencarbonat und den festen Alkalisalzen mindestens einer homopoly¬ meren bzw. copolymeren (Meth-)Acrylsäure zusammen mit der für die Teil- hydratisation des wasserfreien Natriumcarbonats erforderlichen Menge Was¬ ser von etwa 5-40, vorzugsweise etwa 7-20 Gew.-%, bezogen auf das als Ge¬ rüstsubstanz eingesetzte wasserfreie Natriumcarbonat, versetzt, anschlies- send wurden die restlichen Stoffe der Mischung zufügt und das so erhaltene Gemisch auf einer üblichen Tablettenpresse verpreßt. Die so hergestellten lagerstabilen Tabletten besitzen eine hohe Bruchfestigkeit (größer 140 N bei einem Durchmesser von etwa 30 bis 40 mm und einer Dichte von etwa 1,4 bis 1,7 g/cm3), die bei Lagerung ebenfalls stabil bleibt und sich dabei innerhalb kurzer Zeit noch deutlich erhöhen kann.To produce these known detergent tablets, the sodium carbonate serving as part of the builders was used in anhydrous form and initially in a mixing cycle, preferably alone or with the other builders such as sodium citrate and optionally sodium hydrogen carbonate and the solid alkali salts of at least one homopolymer or copolymer ( Meth-) acrylic acid together with the amount of water required for the partial hydration of the anhydrous sodium carbonate of about 5-40, preferably about 7-20% by weight, based on the anhydrous sodium carbonate used as the framework substance, added - The remaining substances were then added to the mixture and the mixture thus obtained was compressed on a conventional tablet press. The storage-stable tablets produced in this way have a high breaking strength (greater than 140 N with a diameter of approximately 30 to 40 mm and a density of approximately 1.4 to 1.7 g / cm 3), which also remains stable during storage and thereby changes within a short time Time can still increase significantly.
Bei dem Versuch, ohne organische Komplexbildner auszukommen und dafür etwa die Anteile an Natriumeitrat und Natriumhydrogencarbonat zu erhöhen, konn¬ ten zunächst keine bruchstabilen Tabletten erhalten werden. Außerdem waren die Tabletten zu "gut" löslich, d.h. sie lösten sich bereits fast voll¬ ständig im Vorspülgang, so daß für den eigentlichen Reinigungsprozeß prak¬ tisch kein Reinigungsmittel mehr zur Verfügung stand.In an attempt to get by without organic complexing agents and to increase the proportions of sodium citrate and sodium bicarbonate, for example, initially no break-stable tablets could be obtained. In addition, the tablets were too "well" soluble, i.e. they already dissolved almost completely in the pre-rinse cycle, so that there was practically no more cleaning agent available for the actual cleaning process.
Gegenstand der vorliegenden Erfindung sind nun stabile, bifunktionelle, phosphat-, etasilikat- und nunmehr auch polymerfreie, niederalkalische Reinigungstabletten für das maschinelle Geschirrspülen, die dadurch ge¬ kennzeichnet sind, daß sie Natriumeitrat, weitere Gerüstsubstanzen, Enzyme sowie gegebenenfalls Bleichaktivatoren, nichtionische Tenside, Färb- und Duftstoffe enthalten. Sie entsprechen folgender Rahmenrezeptur: The present invention now relates to stable, bifunctional, phosphate-, etasilicate- and now also polymer-free, low-alkaline cleaning tablets for automatic dishwashing, which are characterized in that they contain sodium citrate, further builders, enzymes and optionally bleach activators, nonionic surfactants, color - and contain fragrances. They correspond to the following basic formulation:
Bestandteile Bereich bevorzugter BereichComponents area preferred area
Trinatriumcitratdihydrat 5 - 50 % 20 - 30 %Trisodium citrate dihydrate 5 - 50% 20 - 30%
Nitri1otrinatriumacetat 0 - 25 % 0 - 20 %Nitriotrisodium acetate 0 - 25% 0 - 20%
Natriumphosphonat 0 - 10 % 0 - 5 %Sodium phosphonate 0 - 10% 0 - 5%
Natriumcarbonat, wasserfrei 1 - 60 % 1 - 20 %Sodium carbonate, anhydrous 1 - 60% 1 - 20%
Natriumdisilikat 0 - 60 % 2 - 30 %Sodium disilicate 0 - 60% 2 - 30%
Natriumhydrogencarbonat 1 - 60 % 30 - 50 %Sodium bicarbonate 1 - 60% 30 - 50%
Natriu perborat onohydrat urid/oder 0 15 % 5 - 12 %Natriu perborate onohydrate uride / or 0 15% 5 - 12%
Natriumpercarbonat 0 - 20 % 5 - 15 %Sodium percarbonate 0 - 20% 5 - 15%
Tetraacetylethylendiamin 0,5 - 4 % 2 - 4 % nichtionisches Tensid 0 - 4 % 0,5 - 2 %Tetraacetylethylenediamine 0.5 - 4% 2 - 4% non-ionic surfactant 0 - 4% 0.5 - 2%
Protease 0,1 - 2 % 0,5 - 1,5 %Protease 0.1-2% 0.5-1.5%
Amylase 0,1 - 2 % 0,5 - 1,5 %Amylase 0.1-2% 0.5-1.5%
Duftstoff 0 - 1 % 0,1 - 0,6 %Fragrance 0 - 1% 0.1 - 0.6%
Paraffinöl 0 - 3 % 0 - 1,5 %Paraffin oil 0 - 3% 0 - 1.5%
Glyceridgemisch 0 - 6 % 1 - 4 %Glyceride mixture 0 - 6% 1 - 4%
Wasser 3 - 10 % 4 - 6 %Water 3 - 10% 4 - 6%
Es wurde ein Verfahren gefunden, bei dem man zu solchen stabilen, bifunk- tionellen, phosphat-, metasilikat- und nunmehr auch polymerfreien, nieder¬ alkalischen Reinigungsmitteltabletten für das maschinelle Geschirrspülen mit einem Gehalt an Natriumeitrat, weiteren GerüstSubstanzen, schaumarmen Tensiden, Bleichmitteln und gegebenenfalls Enzymen, Bleichaktivatoren, Duft- und Farbstoffen kommt, wenn man zunächst Natriumcitratdihydrat und/oder Natriumeitrat mit einer geringen Menge Wasser von etwa 3 - 10, vorzugsweise etwa 4 - 6 Gew.-%, bezogen auf die Gesamtzusammensetzung, befeuchtet, anschließend wasserfreies Natriumcarbonat aufstäubt und dann Natriumhydrogencarbonat und den Bleichaktivator zumischt, Enzyme, nicht- ionische Tenside, Duft-/Farbstoffe und gegebenenfalls Paraffinöl zugibt, zum Schluß mit geringem Energieeintrag die Aktivsauerstoff abspaltende Verbindung zumischt und das so erhaltene Gesamtgemisch auf einer üblichen Tablettenpresse bei einer relativen Luftfeuchtigkeit von etwa 15 bis 60, vorzugsweise etwa 20 bis 30 % mit einem Preßdruck von etwa 2 bis 11, vor¬ zugsweise etwa 4 bis 6 MPa zu Tabletten verpreßt. Die - fakultative - Zugabe des Paraffinöls kann auch bereits gemeinsam mit der Zugabe des Natriumeitrats erfolgen, vorzugsweise in Form eines Gemi¬ sches, das in einem vorgezogenen, separaten Mischschnitt aus vorzugsweise 1 - 3 Gew.-%, insbesondere ca. 2 Gew.-% Paraffinöl, bezogen auf die gesam¬ te Reinigungsmittelmischung und Natriumeitrat hergestellt wird. Vorteil¬ haft ist auch eine in einem vorgezogenen Mischschritt mit Paraffinöl durch¬ geführte Hydrophobierung des Natriumhydrogencarbonates.A process has been found in which such stable, bifunctional, phosphate-, metasilicate- and now also polymer-free, lower-alkaline detergent tablets for automatic dishwashing with a content of sodium citrate, other scaffold substances, low-foam surfactants, bleaches and optionally Enzymes, bleach activators, fragrances and dyes come when you first moisten sodium citrate dihydrate and / or sodium citrate with a small amount of water of about 3 - 10, preferably about 4 - 6 wt .-%, based on the total composition, then dusted with anhydrous sodium carbonate and then sodium hydrogen carbonate and the bleach activator are added, enzymes, non-ionic surfactants, fragrances / dyes and optionally paraffin oil are added, finally the active oxygen-releasing compound is mixed in with a low energy input and the total mixture obtained in this way on a conventional tablet press at a relative atmospheric humidity 15 to 60, preferably about 20 to 30% with a compression pressure of about 2 to 11, preferably about 4 to 6, MPa to tablets. The - optional - addition of the paraffin oil can also take place together with the addition of the sodium citrate, preferably in the form of a mixture which, in an advanced, separate mixed cut, preferably comprises 1 to 3% by weight, in particular approximately 2% by weight. % Paraffin oil, based on the total detergent mixture and sodium citrate. Also advantageous is a hydrophobization of the sodium bicarbonate carried out in a preferred mixing step with paraffin oil.
Eine erwünschte weitere Verzögerung der Auflösung im Vorspülgang einer HGSM kann erfolgen, wenn man das eingangs zugegebene Wasser bereits mit dem nichtionischen Tensid, dem auch der Duftstoff zugefügt werden kann, oder mit einem Glyceridgemisch vermischt und auf das Natriumeitrat düst und dann die Restsubstanzen zufügt.A desired further delay in the dissolution in the pre-rinse cycle of an HGSM can take place if the water added at the beginning is already mixed with the nonionic surfactant, to which the fragrance can also be added, or with a glyceride mixture and sprayed onto the sodium citrate and then adding the residual substances.
Eine weitere bevorzugte Ausführungsform des erfindungsgemäßen Verfahrens besteht darin, daß zuerst alle flüssigen Komponenten der Zusammensetzung auf das Natriumeitrat aufgetragen werden, dann das wasserfreie Natrium¬ carbonat aufgestäubt wird und anschließend nacheinander, jeweils mit ge¬ ringem Energieeintrag, Natriumhydrogencarbonat, der Bleichaktivator und abschließend die Aktivsauerstoff abspaltende Verbindung zugegeben werden und das so erhaltene Gesamtgemisch wie vorstehend angegeben verpreßt wird. Unter "geringen Energieeintrag" versteht man eine schonende Vermischung ohne Einsatz der hochtourig laufenden Messerköpfe bei nur kurzen Verweil¬ zeiten im Mischer.A further preferred embodiment of the process according to the invention consists in first applying all liquid components of the composition to the sodium citrate, then dusting the anhydrous sodium carbonate and then in succession, each with a low energy input, sodium bicarbonate, the bleach activator and finally the active oxygen releasing compound are added and the total mixture thus obtained is pressed as indicated above. "Low energy input" means gentle mixing without using the high-speed cutter heads with only short dwell times in the mixer.
Die erfindungsgemäß hergestellten lagerstabilen Tabletten besitzen eine hohe Bruchfestigkeit (größer 140 N bei einem Durchmesser von etwa 30 bis 40 m und einer Dichte von etwa 1,4 bis 1,7 g/atß) , die sich bei Lagerung innerhalb kurzer Zeit noch deutlich erhöhen kann, und die ebenfalls stabil bleiben.The storage-stable tablets produced according to the invention have a high breaking strength (greater than 140 N with a diameter of about 30 to 40 m and a density of about 1.4 to 1.7 g / atß), which can increase significantly within a short time during storage , and which also remain stable.
Als Gerüstsubstanzen können neben Natriumeitrat und Alkalihydrogencarbo- naten und/oder Alkalicarbonaten noch Alkalinitrilotriacetate, Alkaliphos- phonate und Alkalidisilikate dienen. Sie binden durch Komplexbildung bzw. Dispergierung Härtebildner wie Calcium- und Magnesiumionen aus dem Wasser bzw. aus den Speiseresten und verhindern damit die Bildung von Kalkbelägen in der Spülmaschine und auf dem Geschirr. Sie können als wasserfreie und/- oder als Hydratsalze eingesetzt werden. Als Natriumeitrat kommen wasser¬ freies Trinatriumcitrat bzw. Trinatriu citrat-dihydrat in Betracht. Als Alkalicarbonat wird vorzugsweise Natriumcarbonat beliebiger Qualität ein¬ gesetzt, wie z. B. calcinierte Soda oder verdichtete Soda. Als Natriumhy- drogencarbonat kann solches beliebiger Herkunft verwendet werden. Bevor¬ zugtes Alkaliphosphonat ist das Tetranatriumsalz der l-Hydroxyethan-1,1- di-phosphonsäure (Turpinal (R) 4 NZ der Firma Henkel). Als Natriumdisili- kat eignet sich getrocknetes Wasserglas mit dem Modul SiO 2 : Na2θ = 1 : 2-2,5, (z. B. Portil (R) A bzw. AW der Firma Henkel, Britesil (R) H 24 bzw. C 24 der Firma Akzo).In addition to sodium citrate and alkali hydrogen carbonates and / or alkali carbonates, alkali metal nitrilotriacetates, alkali phosphonates and alkali disilicates can also be used as builders. They bind hardening agents such as calcium and magnesium ions from the water or from the food residues through complex formation or dispersion and thus prevent the formation of limescale deposits in the dishwasher and on the dishes. They can be used as anhydrous and / or as hydrate salts. Water-free trisodium citrate or trisodium citrate dihydrate are suitable as sodium citrate. Sodium carbonate of any quality is preferably used as the alkali carbonate, such as. B. soda ash or compressed soda. Any origin can be used as sodium hydrogen carbonate. Preferred alkali metal phosphonate is the tetrasodium salt of l-hydroxyethane-1,1-di-phosphonic acid (Turpinal ( R ) 4 NZ from Henkel). Dried water glass with the module SiO 2 : Na2θ = 1: 2-2.5, (for example Portil ( R ) A or AW from Henkel, Britesil ( R ) H 24 or C) is suitable as sodium disilicate 24 from Akzo).
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 Gesamt¬ gewicht der fertigen Tabletten beträgt im allgemeinen etwa 0,2 bis 5, vor¬ zugsweise etwa 0,5 bis 3 Gew.-%. Man kann aber auch andere als schaumarm bekannte nichtionische Tenside verwenden, wie z. B. Ci2-Ci8-Alkylpolyethy- lenglykol-polybutylenglykolether mit jeweils bis zu 8 Mol Ethylenoxid- und Butylenoxideinheiten im Molekül und dann gegebenenfalls noch etwa 0,2 bis 2, vorzugsweise etwa 0,2 bis 1 Gew.-%, bezogen auf die gesamte Tablette, an Entschäumungsmitteln wie z. B. Silikonöle, Gemische aus Silikonöl und hydrophobierter Kieselsäure, Paraffinöl/Guerbetalkoholen und hydrophobier- ter 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 about 0.2 to 5, preferably about 0.5 to 3,% by weight. But you can also use other non-foaming surfactants known as low foams, such as. B. Ci2-Ci8-Alkylpolyethy- lenglykol-polybutylene glycol ether, each with up to 8 moles of ethylene oxide and butylene oxide units in the molecule and then optionally about 0.2 to 2, preferably about 0.2 to 1 wt .-%, based on the total Tablet, on defoaming agents such. B. Add silicone oils, mixtures of silicone oil and hydrophobicized silica, paraffin oil / Guerbet alcohols and hydrophobicized silica.
Als Bleichmittel sind nunmehr vorzugsweise Aktivsauerstoffträger übliche Bestandteile von Reinigungsmitteln für HGSM. Dazu gehören in erster Linie Natriumperboratmono- und -tetrahydrat sowie Natriumpercarbonat und Natri- u earoat. 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 so¬ genannte Bleichaktivatoren eingesetzt. Als Bleichaktivatoren dienen bevor¬ zugt TAED (Tetraacetylendiamin), PAG (Pentaacetylglucose), DADHT (1,5-Di- acetyl-2,4-dioxo-hexahydro-l,3,5-triazin) und ISA (Isatosäureanhydrid). Zur besseren Ablösung Eiweiß- bzw. Stärke-haltiger Speisereste können noch Enzyme wie Proteasen und Amylasen eingesetzt werden, beispielsweise Prote- asen 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 Enzy¬ mes, 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 Ter- mamyl (R) 60 T, 90 T der Firma Novo, Amylase-LT (R) der Firma Solvay Enzy¬ mes oder Maxamyl (R) P 5000 der Firma Ibis.Active oxygen carriers are now preferably bleaches which are customary constituents of cleaning agents for HGSM. These include primarily sodium perborate mono- and tetrahydrate as well as sodium percarbonate and sodium uearoat. Since active oxygen only develops its full effect on its own at elevated temperatures, so-called bleach activators are also expediently used to activate it at about 60 ° C., the temperatures of the cleaning process in the HGSM. TAED (tetraacetylenediamine), PAG (pentaacetylglucose), DADHT (1,5-di-acetyl-2,4-dioxo-hexahydro-l, 3,5-triazine) and ISA (isatoic anhydride) are preferably used as bleach activators. Enzymes such as proteases and amylases can also be used to better remove protein or starch-containing food residues, for example proteins such as BLAP ( R ) from Henkel, Opitmase ( R ) -M-440, Optimase ( R ) - -M -330, Opticlean ( R ) -M-375, Opticlean ( R ) -M-250 from Solvay Enzy¬ mes, Maxacal ( R ) CX 450,000, Maxapem ( R ) from Ibis, Savinase ( R ) T from Novo or Esperase ( R ) T from Ibis and amylases such as Termamyl ( R ) 60 T, 90 T from Novo, Amylase-LT ( R ) from Solvay Enzymes or Maxamyl ( R ) P 5000 from Ibis.
Den Tablettenmischungen können auch übliche oxidationsstabile Färb- und Duftstoffe zugefügt werden. Aus ästhetischen Gründen kann man die Tablet¬ ten bei sonst gleicher Zusammensetzung auch in farbigen Schichten verpres- sen.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, bei¬ spielsweise Paraffinöl, oder Gemischen aus Mono-, Di- und Triglyceriden von C12-C18-, vorzugsweise Ciδ-Ciβ-Fettsäuren etwa handelsüblichen als Backmittel vertriebenen Glyceridgemischen wie z.B. Boeson VP (Boehringer, Ingelheim) ist zum Verpressen der erfindungsgemäßen Tabletten nicht erfor¬ derlich und kann meist weggelassen werden, wenn die Tablettenmischungen nichtionische Tenside enthalten, die diese Aufgabe im wesentlichen über¬ nehmen. Ein Zusatz von Paraffinöl und/oder Glyceridgemischen kann dennoch wie angegeben zweckmäßig sein, weil er zu einer Lösungsverzögerung der Tabletten führt, so daß ein höherer Anteil der Tablette im Reinigungsgang zur Verfügung steht. Die Einstellung des gewünschten pH-Wertes erfolgt vorzugsweise über den Natriu hydrogencarbonatanteil.The use of tableting aids, such as mold release agents, for example paraffin oil, or mixtures of mono-, di- and triglycerides of C12-C18, preferably Ciδ-Ciβ fatty acids, for example commercially available glyceride mixtures sold as baking agents, e.g. Boeson VP (Boehringer, Ingelheim) is not necessary for compressing the tablets according to the invention and can usually be omitted if the tablet mixtures contain nonionic surfactants which essentially take on this task. The addition of paraffin oil and / or glyceride mixtures can nevertheless be expedient, as indicated, because it leads to a delay in dissolution of the tablets, so that a higher proportion of the tablet is available in the cleaning cycle. The desired pH is preferably set via the sodium hydrogen carbonate portion.
Das wie beschrieben hergestellte Gemisch würde auf herkömmlichen Tablet¬ tenpressen mit einem Preßdruck von etwa 2 bis 11 MPa, vorzugsweise etwa 4 bis 6 MPa verpreßt. Das Verpressen konnte ohne Matrizenschmierung in be¬ kannter Weise mit Hilfe von handelsüblichen Excenterpressen, hydraulischen Pressen oder Rundlauferpressen 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 Beschich¬ tung der Stempel mit weichem Kunststoff verzichtet werden konnte. 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: ver¬ gleiche 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 mixture produced as described would be pressed on conventional tablet presses with a pressure of about 2 to 11 MPa, preferably about 4 to 6 MPa. The pressing could be carried out in known manner without die lubrication using commercially available eccentric presses, hydraulic presses or rotary presses. No caking of the tablet mixture was observed on the pressing tools. Tools coated with hard plastic as well as uncoated delivered tablets with smooth surfaces, so that in most cases it was also possible to dispense with coating the punches with soft plastic. The pressing conditions were optimized with regard to the setting of the desired dissolution profile with sufficient tablet hardness. The flexural strength can serve as a measure of the tablet hardness (method: compare Ritschel. Die Tablette, Ed. Cantor, 1966, p. 313). According to this, tablets with a bending strength greater than 100 N, preferably greater than 150 N, are sufficiently stable under simulated transport conditions. The bending or breaking strength of the tablets can be controlled by the degree of compression, ie the compression pressure, regardless of their format.
Entsprechende Tablettenhärten wurden bei den vorstehend angegebenen Pre߬ drücken erreicht. Löslichkeitsdifferenzen können bei unterschiedlichen Zusammensetzungen durch Varianten des Preßdrucks in Grenzen ausgeglichen werden.Corresponding tablet hardnesses were achieved at the press 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/cm^. 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/ iß auf etwa 1,2 bis 2,0 g/ , vorzugsweise etwa 1,4 bis 1,6 g/cm3 stieg.The specific weight of the compacts was between about 1.2 and 2 g / cm 3, preferably between about 1.4 and 1.8 g / cm 3. The compression during the pressing process caused changes in the density, which ranged from about 0.4 to 1.2 g / cm 3, preferably about 0.6 to 1.0 g / i 3 to about 1.2 to 2.0 g /, preferably about 1 .4 to 1.6 g / cm3 rose.
Auch die Form der Tablette kann die Bruchfestigkeit und die Lösegeschwin¬ digkeit über die dem H2θ-Angriff ausgesetzte äußere Oberfläche beeinflus¬ sen. Aus Stabilitätsgründen wurden zylindrische Preßlinge mit einem Durch¬ messer/Höhe-Verhältnis von etwa 0,6 bis 4,0 : 1 hergestellt.The shape of the tablet can also influence the breaking strength and the dissolving speed via the outer surface exposed to the H2O attack. For reasons of stability, cylindrical compacts with a diameter / height ratio of approximately 0.6 to 4.0: 1 were produced.
Zur Messung der Bruchfestigkeit wurde die Tablette durch einen Keil bela¬ stet. Die Bruchfestigkeit entspricht dem Gewicht der keilförmigen Bela¬ stung, das zum Bruch der Tablette führt.To measure the breaking strength, the tablet was loaded with a wedge. The breaking strength corresponds to the weight of the wedge-shaped load, which leads to the tablet breaking.
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. Wurde Na-carbonat nicht hydratisiert oder als Vollhydrat eingesetzt, war die Qualität der aus der Mischung gewonnenen Tabletten für den Handel un¬ brauchbar, da sie u. a. eine zu geringe Bruchfestigkeit aufwiesen. Auch kam es beim Tablettieren zum Anbacken der Mischungen am Oberstempel der Pressen. The amounts of the substance mixture to be compressed for the individual tablets can be varied as desired within technically reasonable limits. Depending on their size, 1 to 2 or even more tablets per machine filling are preferably used in order to provide the entire cleaning process with the necessary active substance content of cleaning agent. Tablets of about 20 to 40 g in weight and a diameter of about 35 to 40 mm are preferred, of which one must be used in each case. If sodium carbonate was not hydrated or used as a full hydrate, the quality of the tablets obtained from the mixture was unusable for the trade since, among other things, they had insufficient breaking strength. The tablets also caked on the mixtures on the upper ram of the presses.
BeispieleExamples
Beispiel AExample A
In einem 130 1 Lödige-Pflugscharmischer wurde eine 50 kg Gemischcharge hergestellt, indem zunächst auf 7,5 Gewichtsteilen Natriumcarbonat und 48 Gewichtsteilen Natriumhydrogencarbonat 4 Gewichtsteile Wasser aufgedüst wurden und anschließend mit 30 Gewichtsteilen Natriumcitratdihydrat, 2 Gewichtsteilen TAED-Granulat, 1 Gewichtsteil BLAP(R) 170 und 1 Gewichts¬ teil Termamyl(R) 60 Teile unter Aufdüsung von 0,9 Gewichtsteilen Dehydol LS4 und 0,6 Gewichtsteilen Duftstoff gemischt wurde. Dem so erhaltenen Gemisch wurden nun schonend 5 Gewichtsteile Perborat onohydrat zugemischt. , Wie der die Preßbedingungen und Tabletteneigenschaften enthaltenden Ta¬ belle zu ersehen ist, ließen sich mit dem Gemisch nur bedingt bruchstabile Tabletten mit einer zu schnellen Auflösung im Vorspülgang erhalten.A batch of 50 kg was prepared in a 130 l Lödige ploughshare mixer by first spraying 4 parts by weight of water onto 7.5 parts by weight of sodium carbonate and 48 parts by weight of sodium hydrogen carbonate and then with 30 parts by weight of sodium citrate dihydrate, 2 parts by weight of TAED granules and 1 part by weight of BLAP ( R ). 170 and 1 part by weight of Termamyl ( R ) 60 parts were mixed while spraying 0.9 parts by weight of Dehydol LS4 and 0.6 parts by weight of fragrance. 5 parts by weight of perborate onohydrate were then gently mixed into the mixture thus obtained. As can be seen from the table containing the pressing conditions and tablet properties, the mixture gave tablets with only limited resistance to breakage that dissolve too quickly in the pre-rinse cycle.
Beispiel 1example 1
Bei gleicher Zusammensetzung wie im Beispiel A beschrieben, wurde im 130 1 Lödigemischer zunächst erfindungsgemäß das Natriumcitratdihydrat mit Was¬ ser bedüst, anschließend wurde mit Soda bestäubt. Dann erfolgte die Zumi- schung von TAED-Granulat, Natriumhydrogencarbonat, Blap 170, Termamyl 60 T und eines Gemisches aus Perboratmonohydrat, Duftstoff und Dehydol LS4. Die wesentlich günstigeren Eigenschaften der so erhaltenen Tabletten sind wie auch bei den folgenden Beispielen nach nachfolgenden Tabellen zu entneh¬ men.With the same composition as described in Example A, the sodium citrate dihydrate was first sprayed with water in 130 l Lödige mixer according to the invention, followed by dusting with soda. Then TAED granules, sodium hydrogen carbonate, Blap 170, Termamyl 60 T and a mixture of perborate monohydrate, fragrance and dehydol LS4 were added. The much more favorable properties of the tablets obtained in this way can be seen from the tables below, as in the examples below.
Beispiel 2Example 2
Die Gemischherstellung erfolgte wie im Beispiel 1, jedoch wurde nach Zu¬ gabe der Dehydol LS4 zum Schluß das Perboratmonohydrat gesondert zuge¬ mischt.The mixture was prepared as in Example 1, but after the addition of the dehydol LS4, the perborate monohydrate was finally mixed in separately.
Beispiel 3Example 3
Die Gemischherstellung erfolgte wie im Beispiel 1 beschrieben, es wurden jedoch zusätzlich zum Schluß noch 1 % Paraffinöl auf das Gemisch aufge¬ düst. Beispiel 4The mixture was prepared as described in Example 1, but 1% paraffin oil was additionally sprayed onto the mixture at the end. Example 4
Auf das im Lödige-Pflugscharmiseher vorgelegte Natriumcitratdihydrat wurde ein Gemisch aus Wasser, Dehydol LS4 und Duftstoff aufgetragen, dann wurde mit Soda bestäubt und im Anschluß daran die Restkomponenten zugemischt.A mixture of water, Dehydol LS4 and fragrance was applied to the sodium citrate dihydrate presented in the Lödige ploughshare, then dusted with soda and then the remaining components were added.
Beispiel 5Example 5
Auf das im Lödige-Pflugscharmiseher vorgelegte Natriumcitratdihydrat wurde eine Suspension aus jeweils 4 Teilen Wasser und Glyceridgemisch (Boeson VP) aufgetragen, anschließend wurde mit Soda bestäubt und entsprechend Beispiel 3 aufgemischt.A suspension of 4 parts water and glyceride mixture (Boeson VP) was applied to each of the sodium citrate dihydrate presented in the Lödige ploughshare, then dusted with soda and mixed in accordance with Example 3.
Beispiel 6Example 6
Gemischherstellung entsprechend Beispiel 2, jedoch wurde Boeson VP zumMixture preparation according to Example 2, but Boeson VP became
Schluß zugemischt.Finally mixed.
Zusammensetzunσ der BeispieleComposition of the examples
Rohstoff A,l,2,4 3 5 + 6Raw material A, l, 2.4 3 5 + 6
Trinatriumciträtelihydrat 30,0 30,0 30,0Trisodium citrate telihydrate 30.0 30.0 30.0
Natriumcarbonat, wasserfrei 7,5 7,5 7,5Sodium carbonate, anhydrous 7.5 7.5 7.5
Natriumhydrogencarbonat 48,0 47,0 44,0Sodium bicarbonate 48.0 47.0 44.0
Natriumperboratmonohydrat 5,0 5,0 5,0Sodium perborate monohydrate 5.0 5.0 5.0
TAED-Granulat 2,0 2.0 2,0TAED granules 2.0 2.0 2.0
Dehydol LS 4 0,9 0,9 0,9Dehydol LS 4 0.9 0.9 0.9
BLAP 170 1,0 1,0 1,0BLAP 170 1.0 1.0 1.0
Termamyl(R) 60 T 1,0 1,0 1,0Termamyl ( R ) 60 T 1.0 1.0 1.0
Beoson VP - - 4,0Beoson VP - - 4.0
Duftstoff 0,6 0,6 0,6Perfume 0.6 0.6 0.6
Paraffinöl - 1,0 -Paraffin oil - 1.0 -
Wasser 6,4 4,0Water 6.4 4.0
TAED = TetraacetylethylendiaminTAED = tetraacetylethylenediamine
Dehydol(R) LS 4 = Fettalkohol C12-C14-4 E0Dehydol ( R ) LS 4 = fatty alcohol C12-C14-4 E0
BLAP(R) 170 = ProteaseBLAP ( R ) 170 = protease
Termamyl(R) 60 = A ylaseTermamyl ( R ) 60 = A ylase
Boeson VP = handelsübliches Glyceridgemisch Tabelle zu den BeispielenBoeson VP = commercially available glyceride mixture Examples table
Beispiel A 1 2 3 4 5 6Example A 1 2 3 4 5 6
Tablettengewicht g 25 25 25 25 25 25 25Tablet weight g 25 25 25 25 25 25 25
Tablettendurchmesser mm 38 38 38 38 38 38 38Tablet diameter mm 38 38 38 38 38 38 38
Tablettendichte g/cm3 1,6 1,58 1,58 1,62 1,62 1,62 1,61Tablet density g / cm 3 1.6 1.58 1.58 1.62 1.62 1.62 1.61
Preßkraft KN 60 60 60 60 60 60 60Pressing force KN 60 60 60 60 60 60 60
Bruchfestigkeit nach Herstellung N 110 140 140 140 140 140 140 nach 24 Stunden N 210 220 360 200 440 420 155Breaking strength after manufacture N 110 140 140 140 140 140 140 after 24 hours N 210 220 360 200 440 420 155
Tablettenreste nach Vorspülgang g 11 18 15 20 18 19 19 nach Hauptspülgang g O O O O O O OTablet residues after pre-rinse g 11 18 15 20 18 19 19 after main rinse g O O O O O O O
Wie sich zeigte, wurden in bezug auf die Bruchfestigkeit und das ge¬ wünschte Löseprofil die besten Ergebnisse erhalten, wenn man zuerst flüs¬ sige Gemische oder Suspensionen von Rezepturbestandteilen auf das Natri- umcitrat aufbrachte und dann die restlichen Feststoffbestandteile zu¬ mischte. As was shown, the best results were obtained with regard to the breaking strength and the desired dissolution profile if liquid mixtures or suspensions of formulation constituents were first applied to the sodium citrate and then the remaining solid constituents were mixed in.

Claims

Patentansprüche Claims
1. Stabile, bifunktionelle, phosphat-, metasilikat- und nunmehr auch po¬ lymerfreie, niederalkalische Reinigungstabletten für das maschinelle Geschirrspülen, dadurch gekennzeichnet, daß sie Natriumeitrat, weitere Gerüstsubstanzen, Bleichmittel und Enzyme sowie gegebenenfalls Bleich¬ aktivatoren, nichtionische Tenside, Färb- und Duftstoffe enthalten.1. Stable, bifunctional, phosphate, metasilicate and now also polymer-free, lower-alkaline cleaning tablets for automatic dishwashing, characterized in that they contain sodium citrate, other builders, bleaching agents and enzymes and optionally bleach activators, nonionic surfactants, coloring and Contain fragrances.
2. Stabile, bifunktionelle, phosphat-, metasilikat- und polymerfreie, niederalkalische Reinigungsmitteltabletten für das maschinelle Ge¬ schirrspülen, dadurch gekennzeichnet, daß sie 5 - 50 Gew.-% Trinatri- umeitrat, bis zu 25 Gew.- Nitrilotrinatriumacetat, bis zu 10 Gew.-% Natriumphosphonat, 1 bis 60 Gew.-% Natriumcarbonat, wasserfrei, bis zu 60 Gew.-% NatriumdiSilikat, 1 bis 60 Gew.-% Natriumhydrogencarbonat, bis zu 15 Gew.-% Natriumperboratmonohydrat und/oder bis zu 20 Gew.-% Natriumpercarbonat, 0,5 bis 4 Gew.-% Tetraacetylethylendia in, bis zu 4 Gew.-% nichtionisches Tensid, 0,1 bis 2 Gew.-% Protease, 0,1 bis 2 Gew.-% A ylase, bis zu 1 Gew.-% Duftstoff, bis zu 3 Gew.-% Paraffinöl, bis zu 6 Gew.-% Glyceridgemisch und 3 bis 10 Gew.-% Wasser enthalten.2. Stable, bifunctional, phosphate-, metasilicate- and polymer-free, low-alkaline detergent tablets for machine dishwashing, characterized in that they contain 5-50% by weight trisodium citrate, up to 25% by weight nitrilotrine sodium acetate, up to 10 % By weight of sodium phosphonate, 1 to 60% by weight of sodium carbonate, anhydrous, up to 60% by weight of sodium disilicate, 1 to 60% by weight of sodium hydrogen carbonate, up to 15% by weight of sodium perborate monohydrate and / or up to 20% by weight % Sodium percarbonate, 0.5 to 4% by weight tetraacetylethylenedia in, up to 4% by weight nonionic surfactant, 0.1 to 2% by weight protease, 0.1 to 2% by weight aylase, contain up to 1% by weight of fragrance, up to 3% by weight of paraffin oil, up to 6% by weight of glyceride mixture and 3 to 10% by weight of water.
3. Tabletten nach Anspruch 1, dadurch gekennzeichnet, daß sie 20 - 30 Gew.-% Trinatriumcitratdihydrat, bis zu 20 Gew.-% Nitrilotrinatrium¬ acetat, bis zu 5 Gew.-% Natriumphosphonat, 1 bis 20 Gew.-% Natriumcar¬ bonat, wasserfrei, 2 bis 30 Gew.-% Natriumdisilikat, 30 bis 50 Gew.-% Natriumhydrogencarbonat, 5 bis 12 Gew.-% Natriumperboratmonohydrat und/oder 5 - 15 Gew.-% Natriumpercarbonat, 2 bis 4 Gew.-% Tetraacetyl¬ ethylendiamin, 0,5 bis 2 Gew.-% nichtionisches Tensid, 0,5 bis 1,5 Gew.-% Protease, 0,5 bis 1,5 Gew.-% Amylase, 0,1 bis 0,6 Gew.-% Duft¬ stoff, bis zu 1,5 Gew.-% Paraffinöl, 1 bis 4 Gew.-% Glyceridgemisch und 4 - 6 Gew.-% Wasser enthalten.3. Tablets according to claim 1, characterized in that they contain 20-30% by weight of trisodium citrate dihydrate, up to 20% by weight of Nitrilotrinatrium¬ acetate, up to 5% by weight of sodium phosphonate, 1 to 20% by weight of sodium car¬ bonate, anhydrous, 2 to 30% by weight sodium disilicate, 30 to 50% by weight sodium bicarbonate, 5 to 12% by weight sodium perborate monohydrate and / or 5 to 15% by weight sodium percarbonate, 2 to 4% by weight tetraacetyl ¬ ethylenediamine, 0.5 to 2 wt .-% nonionic surfactant, 0.5 to 1.5 wt .-% protease, 0.5 to 1.5 wt .-% amylase, 0.1 to 0.6 wt. % Perfume, up to 1.5% by weight paraffin oil, 1 to 4% by weight glyceride mixture and 4 to 6% by weight water.
4. Verfahren zur Herstellung stabiler, bifunktioneller, phosphat-, meta¬ silikat- und polymerfreier, niederalkalischer Reinigungsmitteltablet- ten für das maschinelle Geschirrspülen nach Anspruch 1 und 2 mit einem Gehalt an Natriumeitrat, weiteren Gerüstsubstanzen, schaumarmen Tensi- den, Bleichmitteln und gegebenenfalls Enzymen, Bleichaktivatoren, Duft- und Farbstoffen, dadurch gekennzeichnet, daß man zunächst Natri¬ umcitratdihydrat und/oder Natriumeitrat mit einer geringen Menge Was¬ ser von etwa 3 - 10, vorzugsweise etwa 4 - 6 Gew.-%, bezogen auf die Gesamtzusammensetzung, befeuchtet, anschließend wasserfreies Natrium¬ carbonat aufstäubt und dann mit Natriumhydrogencarbonat und den Bleichaktivator zumischt, Enzyme, nichtionische Tenside, Duft-/Farb- stoffe und gegebenenfalls Paraffinöl zugibt, zum Schluß mit geringem Energieeintrag die Aktivsauerstoff abspaltende Verbindung zumischt und das so erhaltene Gesamtgemisch auf einer üblichen Tablettenpresse bei einer relativen Luftfeuchtigkeit von etwa 15 bis 60, vorzugsweise etwa 20 bis 30 % mit einem Preßdruck von etwa 2 bis 11, vorzugsweise etwa 4 bis 6 MPa zu Tabletten verpreßt.4. A process for producing stable, bifunctional, phosphate-, meta-silicate and polymer-free, low-alkaline detergent tablets for automatic dishwashing according to claim 1 and 2 with one Content of sodium citrate, other builders, low-foaming tensides, bleaching agents and, if appropriate, enzymes, bleach activators, fragrances and dyes, characterized in that sodium citrate dihydrate and / or sodium citrate are first mixed with a small amount of water of about 3-10. preferably about 4 - 6 wt .-%, based on the total composition, moistened, then dusted with anhydrous sodium carbonate and then mixed with sodium hydrogen carbonate and the bleach activator, adding enzymes, nonionic surfactants, fragrances / colorants and optionally paraffin oil, at the end admixing the active oxygen-releasing compound with low energy input and the resulting mixture in a conventional tablet press at a relative atmospheric humidity of about 15 to 60, preferably about 20 to 30% with a compression pressure of about 2 to 11, preferably about 4 to 6 MPa to tablets pressed.
5. Verfahren nach Anspruch 4, dadurch gekennzeichnet, daß man an Stelle eines ParaffinölZusatzes das der Befeuchtung des Natriumeitrat die¬ nende Wasser mit Gemischen aus Mono-, Di- und Triglyceriden von C12- Ci8-, vorzugsweise Cχ6-Ci8-Fettsäuren versetzt.5. The method according to claim 4, characterized in that instead of adding a paraffin oil to the moistening of the sodium citrate, the water containing mixtures of mono-, di- and triglycerides of C12-Ci8-, preferably Cχ6-Ci8-fatty acids are added.
6. Verfahren nach Anspruch 4, dadurch gekennzeichnet, daß man in einem vorgezogenen Mischschritt das Natriumhydrogencarbonat mit Paraffinöl hydrophobiert.6. The method according to claim 4, characterized in that in a preferred mixing step, the sodium bicarbonate with paraffin oil.
7. Verfahren nach Anspruch 4, dadurch gekennzeichnet, daß man zuerst alle flüssigen Komponenten der Zusammensetzung auf das Natriumeitrat auf¬ trägt, dann das wasserfreie Natriumcarbonat aufstäubt und anschließend nacheinander Natriumhydrogencarbonat, der Bleichaktivator und ab¬ schließend mit geringem Energieeintrag die Aktivsauerstoff abspaltende Verbindung zugibt und das so erhaltene Gesamtgemisch zu Tabletten ver¬ preßt.7. The method according to claim 4, characterized in that first all liquid components of the composition are applied to the sodium citrate, then the anhydrous sodium carbonate is dusted on and then, in succession, sodium bicarbonate, the bleach activator and, finally, the active oxygen-releasing compound are added with little energy input and the total mixture thus obtained is compressed into tablets.
8. Verwendung der Tabletten nach Anspruch 1 bis 7, dadurch gekennzeich¬ net, daß man sie einem strömungstechnisch günstigen Teil der Geschirr¬ spülmaschine zufügt und sie bereits dem Vorspülgang aussetzt. 8. Use of the tablets according to claim 1 to 7, characterized gekennzeich¬ net that they are added to a fluidically favorable part of the dishwasher and they are already exposed to the pre-wash.
EP94912526A 1993-04-01 1994-03-23 Stable, bifunctional, phosphate-, metasilicate- and polymer-free low alkaline detergent tablets for dishwashing machines, and process for producing the same Expired - Lifetime EP0692020B1 (en)

Applications Claiming Priority (3)

Application Number Priority Date Filing Date Title
DE4315048 1993-04-01
DE4315048A DE4315048A1 (en) 1993-04-01 1993-04-01 Process for the production of stable, bifunctional, phosphate, metasilicate and polymer-free, low-alkaline detergent tablets for automatic dishwashing
PCT/EP1994/000932 WO1994023011A1 (en) 1993-04-01 1994-03-23 Stable, bifunctional, phosphate-, metasilicate- and polymer-free low alkaline detergent tablets for dishwashing machines, and process for producing the same

Publications (2)

Publication Number Publication Date
EP0692020A1 true EP0692020A1 (en) 1996-01-17
EP0692020B1 EP0692020B1 (en) 1997-11-12

Family

ID=6487366

Family Applications (1)

Application Number Title Priority Date Filing Date
EP94912526A Expired - Lifetime EP0692020B1 (en) 1993-04-01 1994-03-23 Stable, bifunctional, phosphate-, metasilicate- and polymer-free low alkaline detergent tablets for dishwashing machines, and process for producing the same

Country Status (10)

Country Link
US (1) US5691293A (en)
EP (1) EP0692020B1 (en)
AT (1) ATE160169T1 (en)
CZ (1) CZ286894B6 (en)
DE (2) DE4315048A1 (en)
DK (1) DK0692020T3 (en)
ES (1) ES2110742T3 (en)
HU (1) HUT72020A (en)
PL (1) PL177250B1 (en)
WO (1) WO1994023011A1 (en)

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP3567094A1 (en) 2007-02-06 2019-11-13 Henkel AG & Co. KGaA Cleaning product

Families Citing this family (43)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US5898025A (en) * 1992-09-25 1999-04-27 Henkel Kommanditgesellschaft Auf Aktien Mildly alkaline dishwashing detergents
DE4408718A1 (en) * 1994-03-15 1995-09-21 Henkel Kgaa Breakage and storage stable, polyfunctional cleaning tablets, process for their preparation and their use
GB2303635A (en) * 1995-07-25 1997-02-26 Procter & Gamble Detergent compositions in compacted solid form
DE19606765A1 (en) * 1996-02-23 1997-08-28 Henkel Kgaa Process for the production of dishwasher tablets
US5900395A (en) * 1996-12-23 1999-05-04 Lever Brothers Company Machine dishwashing tablets containing an oxygen bleach system
EP1184450B1 (en) * 1997-11-26 2006-02-01 The Procter & Gamble Company Detergent tablet
US6399564B1 (en) * 1997-11-26 2002-06-04 The Procter & Gamble Company Detergent tablet
PT1184450E (en) * 1997-11-26 2006-06-30 Procter & Gamble TECHNICAL FIELD DETERGENT PILLS.
DE19752601C1 (en) * 1997-11-28 1998-12-10 Henkel Kgaa Production of dishwasher detergent tablet with good breaking strength
DE19758180A1 (en) * 1997-12-30 1999-07-01 Henkel Kgaa Detergent tablets with bleach activators
DE19919443A1 (en) * 1999-04-29 2000-11-02 Henkel Kgaa Effervescent tablets with tableting aids and process for their preparation
EP1065265B1 (en) * 1999-06-30 2008-09-24 Kao Corporation Germicidal detergent composition
GB2367830A (en) * 2000-10-12 2002-04-17 Procter & Gamble Process for preparing tablets
US7153820B2 (en) 2001-08-13 2006-12-26 Ecolab Inc. Solid detergent composition and method for solidifying a detergent composition
GB2390853A (en) * 2002-07-16 2004-01-21 Reckitt Benckiser Nv Cleaning composition containing hydrophobic component
US7368418B2 (en) * 2002-12-02 2008-05-06 Diamond Chemical Company, Inc. Laundry compositions
US20080188392A1 (en) * 2002-12-02 2008-08-07 Diamond Chemical Company, Inc. Laundry Compositions
US6896567B1 (en) 2003-02-18 2005-05-24 Philip T. Esposito Marine motor cooling system flushing apparatus and method
US20060234900A1 (en) * 2005-04-13 2006-10-19 Ecolab Inc. Composition and process for preparing a phosphonate and phosphate-free automatic dishwashing powder
US20100120651A1 (en) * 2005-07-11 2010-05-13 Genencor International, Inc. Enzyme fabric care tablets for consumers and methods
DE102007006628A1 (en) 2007-02-06 2008-08-07 Henkel Ag & Co. Kgaa cleaning supplies
DE102007044417A1 (en) 2007-09-17 2009-03-19 Henkel Ag & Co. Kgaa cleaning supplies
DE102007044418A1 (en) 2007-09-17 2009-03-19 Henkel Ag & Co. Kgaa cleaning supplies
WO2008095554A2 (en) * 2007-02-06 2008-08-14 Henkel Ag & Co. Kgaa Detergents
DE102007006629A1 (en) 2007-02-06 2008-08-07 Henkel Ag & Co. Kgaa cleaning supplies
DE102007006627A1 (en) * 2007-02-06 2008-08-07 Henkel Ag & Co. Kgaa cleaning supplies
US20080274931A1 (en) * 2007-05-02 2008-11-06 Veripak, Inc. Bio-friendly automatic dish washing tablets processes and all natural products thereby
US7759300B2 (en) * 2007-07-02 2010-07-20 Ecolab Inc. Solidification matrix including a salt of a straight chain saturated mono-, di-, or tri- carboxylic acid
DE102007059677A1 (en) * 2007-12-10 2009-06-25 Henkel Ag & Co. Kgaa cleaning supplies
DE102008060470A1 (en) 2008-12-05 2010-06-10 Henkel Ag & Co. Kgaa cleaning supplies
DE102008063801A1 (en) 2008-12-19 2010-06-24 Henkel Ag & Co. Kgaa Machine dishwashing detergent
DE102009029637A1 (en) 2009-09-21 2011-03-24 Henkel Ag & Co. Kgaa Machine dishwashing detergent
DE102009029635A1 (en) 2009-09-21 2011-03-24 Henkel Ag & Co. Kgaa Machine dishwashing detergent
DE102009029636A1 (en) 2009-09-21 2011-03-24 Henkel Ag & Co. Kgaa Machine dishwashing detergent
DE102009046216A1 (en) 2009-10-30 2011-05-12 Henkel Ag & Co. Kgaa Machine dishwashing detergent
DE102011007695A1 (en) 2011-04-19 2012-10-25 Henkel Ag & Co. Kgaa Phosphate-free dishwashing detergent
DE102013100195A1 (en) * 2013-01-10 2014-07-24 Budich International Gmbh Cleaner tablet with integrated pre-cleaner
DE102016212248A1 (en) 2016-07-05 2018-01-11 Henkel Ag & Co. Kgaa Dishwashing detergent containing sugar acid and aminocarboxylic acid
DE102017212561A1 (en) 2017-07-21 2019-01-24 Henkel Ag & Co. Kgaa Dishwashing detergent containing citrate dihydrate and anhydrate
CN108816005A (en) * 2018-06-29 2018-11-16 上海衡元高分子材料有限公司 composition for regulating environmental humidity
US11753607B2 (en) * 2019-04-19 2023-09-12 One Home Brands, Inc. Stable anhydrous dish soap and method of making same
US11261409B2 (en) * 2019-04-19 2022-03-01 One Home Brands, Inc. Tablet production
WO2024129938A1 (en) * 2022-12-14 2024-06-20 Colgate-Palmolive Company Home care compositions

Family Cites Families (19)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CA1125620A (en) * 1978-03-21 1982-06-15 Eric D. Barford Lavatory cleansing blocks
GB8310080D0 (en) * 1983-04-14 1983-05-18 Interox Chemicals Ltd Bleach composition
GB8328075D0 (en) * 1983-10-20 1983-11-23 Unilever Plc Dishwashing compositions
DE3541145A1 (en) * 1985-11-21 1987-05-27 Henkel Kgaa UNIFORMED DETERGENT TABLETS FOR MACHINE DISHWASHER
JPH01210121A (en) * 1988-02-16 1989-08-23 Kawasaki Steel Corp Operating method for tension leveler
US4911858A (en) * 1988-09-15 1990-03-27 Kiwi Brands, Inc. Toilet bowl cleaner
US5055305A (en) * 1988-12-02 1991-10-08 Richardson-Vicks, Inc. Cleansing compositions
DE3937469A1 (en) * 1989-11-10 1991-05-16 Henkel Kgaa GRANULAR, ALKALINE, PHOSPHATE-FREE CLEANING ADDITIVE
GB9003741D0 (en) * 1990-02-19 1990-04-18 Unilever Plc Bleach activation
DE4010524A1 (en) * 1990-04-02 1991-10-10 Henkel Kgaa STABLE, BIFUNCTIONAL, PHOSPHATE-FREE DETERGENT TABLETS FOR THE MACHINE DISHWASHER
SE468092B (en) * 1990-11-14 1992-11-02 Eka Nobel Ab ALKALIMETAL SILICATE IN SOLID FORM CONTAINING SODIUM AND POTASSIUM, PREPARED FOR ITS PREPARATION AND ITS USE IN CLEANING COMPOSITIONS
JPH06505286A (en) * 1990-11-14 1994-06-16 ザ、プロクター、エンド、ギャンブル、カンパニー Non-phosphate dishwashing compositions containing oxygen bleach systems
DK166548B1 (en) * 1991-03-15 1993-06-07 Cleantabs As PHOSPHATE-FREE MACHINE DISHWASH
DE4112075A1 (en) * 1991-04-12 1992-10-15 Henkel Kgaa METHOD FOR PRODUCING STABLE, BIFUNCTIONAL, PHOSPATE AND METASILICATE-FREE LOW-ALKALINE DETERGENT TABLETS FOR THE MACHINE DISHWASHER
US5468411A (en) * 1991-05-31 1995-11-21 Colgate Palmolive Co. Powdered automatic dishwashing composition containing enzymes
US5173207A (en) * 1991-05-31 1992-12-22 Colgate-Palmolive Company Powered automatic dishwashing composition containing enzymes
DE4121307A1 (en) * 1991-06-27 1993-01-07 Henkel Kgaa METHOD FOR THE PRODUCTION OF STABLE, BIFUNCTIONAL, PHOSPHATE AND METASILICATE-FREE LOW-ALKALINE DETERGENT TABLETS FOR THE MACHINE DISHWASHER
GB9114184D0 (en) * 1991-07-01 1991-08-21 Unilever Plc Detergent composition
WO1993002510A1 (en) * 1991-07-17 1993-02-04 Tutankhamon Electronics Network monitor and test apparatus

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
See references of WO9423011A1 *

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP3567094A1 (en) 2007-02-06 2019-11-13 Henkel AG & Co. KGaA Cleaning product

Also Published As

Publication number Publication date
WO1994023011A1 (en) 1994-10-13
PL177250B1 (en) 1999-10-29
HUT72020A (en) 1996-03-28
DK0692020T3 (en) 1998-07-27
EP0692020B1 (en) 1997-11-12
DE59404581D1 (en) 1997-12-18
PL310951A1 (en) 1996-01-08
CZ253195A3 (en) 1996-05-15
ATE160169T1 (en) 1997-11-15
US5691293A (en) 1997-11-25
DE4315048A1 (en) 1994-10-06
HU9502850D0 (en) 1995-11-28
CZ286894B6 (en) 2000-07-12
ES2110742T3 (en) 1998-02-16

Similar Documents

Publication Publication Date Title
EP0692020B1 (en) Stable, bifunctional, phosphate-, metasilicate- and polymer-free low alkaline detergent tablets for dishwashing machines, and process for producing the same
DE4112075C2 (en)
US4828749A (en) Multilayer detergent tablets for dishwashing machines
EP0264701B1 (en) Cleaning agent tablets for the automatic dishwashing
EP0591282B1 (en) Method for the production of cleaning-agent tablets for machine dishwashing
EP0743978B1 (en) Bleaching tablet with builder substances
EP0224135A2 (en) Compact detergents
DE19710254A1 (en) Shaped or active cleaning moldings for household use
DE4408718A1 (en) Breakage and storage stable, polyfunctional cleaning tablets, process for their preparation and their use
EP0593952A1 (en) Product for releasing treatment agents into the wash liquid of an automatic washing or dishwashing machine
DE4429550A1 (en) Process for the production of detergent tablets
EP0523095B1 (en) Stable, bifunctional, phosphate-free detergent tablets for use in dishwashing machines
DE4403323A1 (en) Extruded washing or cleaning agents with improved dissolving properties
EP0871698B1 (en) Method of producing breakage-resistant detergent tablets
EP0888449B1 (en) Solid surfactant and builder-containing washing and cleaning agent with a high bulk density or compound for such an agent
EP0877791B1 (en) Process for the preparation of moulded bodies consisting of a washing or cleaning agent
DE19606765A1 (en) Process for the production of dishwasher tablets
EP0658190B1 (en) Process for producing detergent tablets
EP0846155B1 (en) Use of lipases in low-alkaline mechanical dishwashing agents
DE102015110425A1 (en) Pelletized cleaning agent, a process for its preparation and its use
DE19531197A1 (en) Use of lipases, opt. combined with org. acid, in low-alkaline dishwasher agents
WO1996022353A1 (en) Cleaning product containing an anti-corrosion agent for silver
DE102008008744A1 (en) Mechanical dishwashing composition, has high tetraacetyl ethylene diamine content to counteract adverse effect of glass corrosion inhibitor on bleaching agent

Legal Events

Date Code Title Description
PUAI Public reference made under article 153(3) epc to a published international application that has entered the european phase

Free format text: ORIGINAL CODE: 0009012

17P Request for examination filed

Effective date: 19950923

AK Designated contracting states

Kind code of ref document: A1

Designated state(s): AT BE CH DE DK ES FR GB IT LI NL PT SE

17Q First examination report despatched

Effective date: 19960425

GRAG Despatch of communication of intention to grant

Free format text: ORIGINAL CODE: EPIDOS AGRA

GRAH Despatch of communication of intention to grant a patent

Free format text: ORIGINAL CODE: EPIDOS IGRA

GRAH Despatch of communication of intention to grant a patent

Free format text: ORIGINAL CODE: EPIDOS IGRA

GRAA (expected) grant

Free format text: ORIGINAL CODE: 0009210

AK Designated contracting states

Kind code of ref document: B1

Designated state(s): AT BE CH DE DK ES FR GB IT LI NL PT SE

REF Corresponds to:

Ref document number: 160169

Country of ref document: AT

Date of ref document: 19971115

Kind code of ref document: T

REG Reference to a national code

Ref country code: CH

Ref legal event code: EP

ET Fr: translation filed
REF Corresponds to:

Ref document number: 59404581

Country of ref document: DE

Date of ref document: 19971218

ITF It: translation for a ep patent filed
REG Reference to a national code

Ref country code: ES

Ref legal event code: FG2A

Ref document number: 2110742

Country of ref document: ES

Kind code of ref document: T3

GBT Gb: translation of ep patent filed (gb section 77(6)(a)/1977)

Effective date: 19980130

REG Reference to a national code

Ref country code: PT

Ref legal event code: SC4A

Free format text: AVAILABILITY OF NATIONAL TRANSLATION

Effective date: 19971219

REG Reference to a national code

Ref country code: DK

Ref legal event code: T3

PLBE No opposition filed within time limit

Free format text: ORIGINAL CODE: 0009261

STAA Information on the status of an ep patent application or granted ep patent

Free format text: STATUS: NO OPPOSITION FILED WITHIN TIME LIMIT

26N No opposition filed
PGFP Annual fee paid to national office [announced via postgrant information from national office to epo]

Ref country code: SE

Payment date: 20010306

Year of fee payment: 8

PGFP Annual fee paid to national office [announced via postgrant information from national office to epo]

Ref country code: PT

Payment date: 20010308

Year of fee payment: 8

PGFP Annual fee paid to national office [announced via postgrant information from national office to epo]

Ref country code: DK

Payment date: 20010313

Year of fee payment: 8

PGFP Annual fee paid to national office [announced via postgrant information from national office to epo]

Ref country code: CH

Payment date: 20010327

Year of fee payment: 8

REG Reference to a national code

Ref country code: GB

Ref legal event code: IF02

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: SE

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 20020324

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: LI

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 20020331

Ref country code: CH

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 20020331

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: DK

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 20020402

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: PT

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 20020930

EUG Se: european patent has lapsed

Ref document number: 94912526.4

REG Reference to a national code

Ref country code: CH

Ref legal event code: PL

REG Reference to a national code

Ref country code: DK

Ref legal event code: EBP

REG Reference to a national code

Ref country code: PT

Ref legal event code: MM4A

Free format text: LAPSE DUE TO NON-PAYMENT OF FEES

Effective date: 20020930

PGFP Annual fee paid to national office [announced via postgrant information from national office to epo]

Ref country code: IT

Payment date: 20120317

Year of fee payment: 19

PGFP Annual fee paid to national office [announced via postgrant information from national office to epo]

Ref country code: DE

Payment date: 20130320

Year of fee payment: 20

Ref country code: FR

Payment date: 20130325

Year of fee payment: 20

Ref country code: GB

Payment date: 20130320

Year of fee payment: 20

Ref country code: ES

Payment date: 20130313

Year of fee payment: 20

PGFP Annual fee paid to national office [announced via postgrant information from national office to epo]

Ref country code: NL

Payment date: 20130309

Year of fee payment: 20

PGFP Annual fee paid to national office [announced via postgrant information from national office to epo]

Ref country code: AT

Payment date: 20130226

Year of fee payment: 20

PGFP Annual fee paid to national office [announced via postgrant information from national office to epo]

Ref country code: BE

Payment date: 20130312

Year of fee payment: 20

REG Reference to a national code

Ref country code: DE

Ref legal event code: R071

Ref document number: 59404581

Country of ref document: DE

REG Reference to a national code

Ref country code: NL

Ref legal event code: V4

Effective date: 20140323

BE20 Be: patent expired

Owner name: *HENKEL K.G.A.A.

Effective date: 20140323

REG Reference to a national code

Ref country code: GB

Ref legal event code: PE20

Expiry date: 20140322

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: DE

Free format text: LAPSE BECAUSE OF EXPIRATION OF PROTECTION

Effective date: 20140325

Ref country code: GB

Free format text: LAPSE BECAUSE OF EXPIRATION OF PROTECTION

Effective date: 20140322

REG Reference to a national code

Ref country code: AT

Ref legal event code: MK07

Ref document number: 160169

Country of ref document: AT

Kind code of ref document: T

Effective date: 20140323

REG Reference to a national code

Ref country code: ES

Ref legal event code: FD2A

Effective date: 20140926

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: ES

Free format text: LAPSE BECAUSE OF EXPIRATION OF PROTECTION

Effective date: 20140324