EP3615650B1 - Composition for cleaning surfaces - Google Patents

Composition for cleaning surfaces Download PDF

Info

Publication number
EP3615650B1
EP3615650B1 EP18723670.8A EP18723670A EP3615650B1 EP 3615650 B1 EP3615650 B1 EP 3615650B1 EP 18723670 A EP18723670 A EP 18723670A EP 3615650 B1 EP3615650 B1 EP 3615650B1
Authority
EP
European Patent Office
Prior art keywords
weight
acid
composition
composition according
salt
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.)
Active
Application number
EP18723670.8A
Other languages
German (de)
French (fr)
Other versions
EP3615650C0 (en
EP3615650A1 (en
Inventor
Daniel Herzog
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.)
Thonhauser GmbH
Original Assignee
Thonhauser GmbH
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 Thonhauser GmbH filed Critical Thonhauser GmbH
Publication of EP3615650A1 publication Critical patent/EP3615650A1/en
Application granted granted Critical
Publication of EP3615650C0 publication Critical patent/EP3615650C0/en
Publication of EP3615650B1 publication Critical patent/EP3615650B1/en
Active legal-status Critical Current
Anticipated expiration legal-status Critical

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
    • C11D3/16—Organic compounds
    • C11D3/36—Organic compounds containing phosphorus
    • C11D3/361—Phosphonates, phosphinates or phosphonites
    • 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
    • C11D3/046—Salts
    • 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
    • C11D1/02—Anionic compounds
    • C11D1/34—Derivatives of acids of phosphorus
    • C11D1/342—Phosphonates; Phosphinates or phosphonites
    • 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
    • C11D17/0008—Detergent materials or soaps characterised by their shape or physical properties aqueous liquid non soap compositions
    • 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
    • C11D17/04—Detergent materials or soaps characterised by their shape or physical properties combined with or containing other objects
    • C11D17/041—Compositions releasably affixed on a substrate or incorporated into a dispensing means
    • 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
    • C11D3/044—Hydroxides or bases
    • 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
    • C11D3/36—Organic compounds containing phosphorus
    • C11D3/364—Organic compounds containing phosphorus containing nitrogen
    • 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
    • C11D3/36—Organic compounds containing phosphorus
    • C11D3/365—Organic compounds containing phosphorus containing carboxyl groups
    • 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
    • C11D3/3937—Stabilising agents
    • 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
    • C11D3/3942—Inorganic per-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
    • C11D2111/00—Cleaning compositions characterised by the objects to be cleaned; Cleaning compositions characterised by non-standard cleaning or washing processes
    • C11D2111/10—Objects to be cleaned
    • C11D2111/14—Hard surfaces

Definitions

  • the present invention relates to compositions for cleaning surfaces and/or for detecting organic substances in a solution or on a surface.
  • salts of permanganic acid and in particular potassium permanganate are often used as oxidizing agents (see WO 03/035812 and WO 2014/122277 ).
  • compositions comprising persulfate, potassium permanganate and phosphate are disclosed.
  • EP 2 450 114 discloses compositions which may include, inter alia, potassium permanganate and persulfates. Phosphonates can be added to these compositions as stabilizers, which can serve to stabilize hydrogen peroxide and persulfate.
  • phosphate-free bleaching agents are described which, in addition to peroxides, can include, inter alia, nitrogen-containing polyphosphonates.
  • organic phosphonates as defined above can be used in detergents instead of phosphates.
  • the organic phosphonates used according to the invention are also distinguished above all by the fact that they are able to significantly increase the stability and thus the shelf life of the salts of permanganic acid, iron acid and chromic acid present therein. This is surprising, inter alia, since salts of the aforementioned acids--as strong oxidizing agents--are able on the one hand to oxidize organic compounds.
  • organic phosphonates whose organic radicals comprise heteroalkyl, heterocycloalkyl or heteroaryl radicals do not result in a stable composition with regard to the salts of permanganic acid, iron acid and/or chromic acid present in the composition.
  • organic phosphonates comprising heteroalkyl, heterocycloalkyl and / or heteroaryl radicals are not suitable to be used in a composition according to the invention, since this surprisingly destabilizes the salts of permanganic acid, iron acid and chromic acid, so that they are no longer used as a color indicator for the detection of organic compounds can be used.
  • organic phosphonates of the type defined at the outset have a stabilizing and not a destabilizing effect on salts of permanganic acid, iron acid and chromic acid.
  • the organic phosphonates according to the invention therefore comprise exclusively homoalkyl, homocycloalkyl and homoaryl radicals, ie these radicals have neither an O, S nor N atom in the chain or in the ring instead of C atoms.
  • organic phosphonates such as amino-tris(methylenephosphonic acid) (ATMP), diethylenetriaminepenta(methylenephosphonic acid) (DTPMP) and ethylenediaminetetra(methylenephosphonic acid) (EDTMP) including heteroalkyls lead to a rapid reduction of the salts of permanganic acid, iron acid and chromic acid whereas HEDP and PBTC, both lacking heteroalkyls, do not show these properties.
  • ATMP amino-tris(methylenephosphonic acid)
  • DTPMP diethylenetriaminepenta(methylenephosphonic acid)
  • ETMP ethylenediaminetetra(methylenephosphonic acid)
  • An organic phosphonate is then suitable for the purpose of the invention if this within 30 minutes at room temperature (40 ° C) at most 30%, preferably at most 25%, even more preferably at most 20%, Mn (VII) (in permanganate) to Mn (VI) is implemented. This conversion can be measured, for example, at an absorption of 425 nm (absorption maximum of Mn(VI)). If the salts of permanganic acid, iron acid and chromic acid are reduced more quickly, the corresponding compositions can only be used to a limited extent for the determination of organic compounds in a sample, since it is not possible to determine whether the reduction of the salts actually comes from the sample to be examined.
  • the composition according to the invention can comprise several different salts of permanganic acid, ferric acid and chromic acid, where the composition can comprise salts with the same anion and different cations and/or salts with different anions and the same cation.
  • Salts of permanganic acid, iron acid and chromic acid preferably include the anions MnO 4 - , FeO 4 2- or CrO 4 2- , the cations preferably being metal ions, in particular alkali metal ions.
  • the composition according to the invention thus preferably comprises at least two, even more preferably at least three, even more preferably at least five salts of permanganic acid, ferric acid and/or chromic acid.
  • Salts of permanganic acid, ferric acid and chromic acid are known oxidizing agents.
  • the composition according to the invention can comprise at least, preferably at least two, even more preferably at least three, even more preferably at least four, further oxidizing agents. I.e. these other oxidizing agents are not salts of permanganic acid, iron acid and chromic acid.
  • composition according to the invention comprises at least one, preferably at least two, even more preferably at least three, even more preferably at least four, organic phosphonates.
  • “Phosphonates” are organic compounds ("organic phosphonates") of phosphonic acid (H 3 PO 3 ).
  • An "organic phosphonate” has the general formula on, where R 1 is an organic radical, X 1 is OH or OM 1 and X 2 is OH or OM 2 , where M 1 and M 2 can represent an alkali metal ion or ammonium ion.
  • the organic radical R 1 can be a substituted or unsubstituted C 1 -C 12 alkyl radical, C 3 -C 10 cycloalkyl radical or C 6 -C 14 aryl radical, the organic radical being attached to 1 to 3 further phosphonate groups of the general formula (I) may be bound.
  • Organic phosphonate compounds can have the general structure R-PO(OH) 2 where R can be an alkyl or aryl radical or other organic radical. If a phosphonate comprises more than one of these organic phosphonates, it is referred to as bisphosphonates or polyphosphonates.
  • Organic phosphonates can be acids or exist as salts, preferably as alkali metal salts.
  • the composition according to the invention which can be in solid form or as an aqueous solution, is suitable for cleaning and disinfecting surfaces, in particular metallic, ceramic or glass surfaces, which are resistant to oxidizing agents because of the oxidizing agents present therein are essentially resistant.
  • the metallic surfaces to be cleaned comprise or consist of stainless steel and/or inert metals (such as platinum, gold) or metal alloys, with surfaces consisting of or comprising stainless steel being particularly preferred since these are usually used in the production plants in the pharmaceutical industry and in food production (including beverage production such as wine and beer production). Pipes and containers of any kind are particularly preferably cleaned or disinfected with the composition according to the invention. Accordingly, a surface can be any shape and part of any object.
  • composition according to the invention contaminants of any kind can be removed from a surface.
  • the usual contaminants in the food industry (e.g. fat and protein deposits, burnt-on food residues) and the pharmaceutical industry (e.g. residues from the manufacture of medicines) are preferably cleaned.
  • the composition according to the invention can also be used for disinfecting surfaces.
  • Cells of all kinds, in particular microorganisms such as bacteria, archaea, fungi, algae and protozoa, but also animal, human and plant cells are destroyed or at least damaged to such an extent that they are no longer viable.
  • viruses can also be rendered harmless with the composition according to the invention.
  • the composition according to the invention can be used either batchwise (ie discontinuously) or continuously (eg by passing the aqueous cleaning solution according to the invention through pipes or containers to be cleaned).
  • the composition according to the invention is particularly preferably used as part of a CIP process (“Cleaning in Place” process, site-specific cleaning process).
  • CIP processes typically involve several process steps such as (1) pre-rinsing to remove gross contamination, (2) cleaning with an alkaline agent (usually an alkali hydroxide), (3) removal of the cleaning agent by rinsing with water, (4) optional Acid treatment to remove limescale, (5) optional acid removal with water; and (6) disinfection.
  • At least step (2) of a CIP process is always carried out at temperatures of at least 70°C in order to enable efficient cleaning of the alkaline agent.
  • the salt of the at least one organic phosphonate is an alkali metal salt (sodium, potassium or lithium salt)
  • the at least one salt of permanganic acid, iron acid and/or chromic acid is an alkali metal salt, preferably selected from the group consisting of potassium permanganate, potassium ferrate and potassium dichromate, the composition according to the invention particularly preferably comprising potassium permanganate.
  • Persulfates are salts of peroxodisulfuric acid H 2 S 2 O 8 or peroxomonosulfuric acid H 2 SO 5 and have a high oxidation potential. Persulfates are therefore well suited for cleaning and/or disinfecting surfaces.
  • the at least one persulfate is a salt of peroxodisulfuric acid or of peroxomonosulfuric acid.
  • the at least one persulfate is a peroxodisulfate selected from the group consisting of sodium peroxodisulfate, potassium peroxodisulfate and ammonium peroxodisulfate and/or a peroxomonosulfate selected from the group consisting of potassium peroxomonosulfate.
  • the composition comprises at least one calcium salt, which is preferably selected from the group consisting of calcium nitrate.
  • composition according to the invention comprises the at least one salt of permanganic acid, ferric acid and/or chromic acid in a weight ratio to the at least one organic phosphonate of preferably 1:50 to 1:500, preferably 1:75 to 1:300, even more preferably 1 :100 to 1:200.
  • composition according to the invention can be provided both essentially anhydrous and in aqueous form.
  • the composition is an aqueous composition.
  • the composition comprises added water, the aqueous composition preferably being prepared by initially introducing water and adding the individual components.
  • the aqueous composition comprises more than 30% by weight, preferably more than 40% by weight, even more preferably more than 50% by weight, even more preferably more than 60% by weight, even more preferably more than 70% by weight %, even more preferably more than 75% by weight, even more preferably more than 80% by weight, even more preferably more than 85% by weight, even more preferably more than 90% by weight, water.
  • composition according to the invention as an aqueous composition has the advantage that it can be used directly and immediately for cleaning/disinfecting surfaces or for detecting organic/biological contamination.
  • composition according to the invention has a lower water content (e.g. less than 60%, preferably less than 50%, even more preferably less than 40%, even more preferably less than 30%), it can be used as a concentrate which, before use, water or other cleaning solutions comprising, for example, alkali hydroxides (e.g. NaOH, KOH).
  • alkali hydroxides e.g. NaOH, KOH
  • the aqueous composition comprises from 0.1% to 2% by weight, preferably from 0.2% to 1.5% by weight, even more preferably from 0.3% to 1% by weight, even more preferably 0.4% by weight to 0.8% by weight, even more preferably 0.4% by weight to 0.6% by weight, even more preferably 0.5% by weight, of the at least one further oxidizing agent.
  • the aqueous composition preferably comprises 0.01% to 1% by weight, preferably 0.02% to 0.9% by weight, more preferably 0.05% to 0.8% by weight, even more preferably 0.075% by weight to 0.7% by weight, even more preferably 0.1% to 0.6% by weight, even more preferably 0.2% to 0.6% by weight, even more preferably 0.3% to 0.6% by weight %, of the at least one organic phosphonate.
  • the aqueous composition comprises 0.1% to 3% by weight, preferably 0.2% to 2% by weight, even more preferably 0.3 to 1% by weight, of the at least one calcium salt.
  • the composition is essentially anhydrous.
  • composition of the invention comprises no more than 10%, preferably no more than 5% by weight water of hydration and/or water of constitution.
  • the composition comprises less than 20% by weight, preferably less than 10% by weight, even more preferably less than 5% by weight, even more preferably less than 1% by weight, water.
  • the composition comprises at least one alkali metal hydroxide.
  • the composition according to the invention comprises at least one alkali metal hydroxide.
  • Alkaline hydroxides are often used for cleaning surfaces because, on the one hand, the negatively charged hydroxide ions attach themselves both to the dirt and to the surface to be cleaned, which leads to electrostatic repulsion of the dirt, and, on the other hand, oils and fats in the presence of hydroxides in a saponification reaction be converted into water-soluble soaps.
  • Alkali hydroxides also referred to as “alkali metal hydroxides” are hydroxides of the alkali metals and have the general formula MeOH (Me - alkali metal). "Alkali hydroxides” easily dissolve in water with strong heating to form strongly alkaline solutions.
  • the at least one alkali metal hydroxide comprises NaOH, KOH or LiOH, NaOH or KOH being particularly preferably used.
  • the aqueous composition preferably comprises from 0.1% to 5%, preferably from 0.2% to 3%, more preferably from 0.3% to 1.5%, even more preferably from 0.4% to 5% by weight 1% by weight, even more preferably 0.4% by weight to 0.8% by weight, even more preferably 0.5% by weight, of the at least one alkali metal hydroxide.
  • the composition according to the invention can also be part of a kit that can be used to clean surfaces and/or to detect organic substances in a solution or on a surface.
  • the kit comprises a container containing at least one alkali metal hydroxide, either in an aqueous solution or essentially anhydrous, as defined herein.
  • the content or corresponding proportions of the content of the two containers can be blended, mixed and/or provided with water before they are used.
  • the at least one alkali metal hydroxide is NaOH, KOH or LiOH.
  • Yet another aspect of the present invention relates to a method for cleaning surfaces and/or for detecting organic substances in a solution or on a surface, comprising the step of bringing a composition into contact according to the present invention or a composition obtainable by mixing the components in the containers a1 and b1 or a2, b2 and b3 of the kit according to the invention with the surface to be cleaned or the surface or solution on or in which organic substances are determined.
  • composition according to the invention can be used in methods for cleaning surfaces and/or for detecting organic substances in a solution or on a surface.
  • Corresponding methods are sufficiently known to the person skilled in the art and comprise at least the steps of applying the composition according to the invention to a surface to be cleaned and removing it after a customary exposure time.
  • the surface is then usually rinsed with water in order to remove residues of the composition according to the invention and any dirt residues that may still be present.
  • Example 1 Stability of compositions containing potassium permanganate
  • compositions and test plan are Compositions and test plan:
  • compositions A to O and Comparative Compositions 1 to 5 were mixed and dissolved in water. Subsequently, the compositions were incubated at 40°C for a total of 60 minutes in a closed vessel. In the first 30 minutes, after 5 minutes of incubation, the absorption of the aqueous compositions was measured at 425 nm and at 580 nm (absorption maximum of permanganate). The decrease in absorbance of the measured compositions at 580 nm shows the reduction of potassium permanganate in the solution. After 30 minutes, the measurement interval was extended to 10 minutes.
  • compositions A to E Absorption of compositions A to E at 580 nm, with the absorption values at minute 0 being set at 100% and the further measurement results of the investigation being correlated accordingly (mean value of three independent measurements).
  • Composition/ time of measurement [min] A B C D E 0 100% 100% 100% 100% 100% 100% 5 98.7% 99.1% 91.9% 93.5% 92.2% 10 95.3% 97.2% 82.2% 87.0% 85.1% 15 93.1% 94.7% 70.7% 72.2% 69.3% 20 91.9% 92.8% 63.1% 62.8% 63.6% 25 87.1% 87.9% 55.8% 53.7% 56.8% 30 85.0% 84.3% 50.2% 48.3% 47.9% 40 82.6% 82.1% 41.0% 42.4% 41.5% 50 81.1% 80.3% 35.9% 36.8% 37.1% 60 79.9% 78.1% 31.2% 30.9% 29.3%
  • Cleaning solutions or compositions can also include other oxidizing agents with inorganic peroxidases and persulfates.
  • oxidizing agents with inorganic peroxidases and persulfates.
  • the influence of such oxidizing agents on the stability of potassium permanganate was also analyzed.
  • Table C: ⁇ /b> Absorption of the compositions K to O at 580 nm, whereby the absorption values at minute 0 were set at 100% and the further measurement results of the investigation were correlated accordingly (mean value of three independent measurements).

Landscapes

  • Chemical & Material Sciences (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Oil, Petroleum & Natural Gas (AREA)
  • Wood Science & Technology (AREA)
  • Organic Chemistry (AREA)
  • Inorganic Chemistry (AREA)
  • Detergent Compositions (AREA)

Description

Die vorliegende Erfindung betrifft Zusammensetzung zur Reinigung von Oberflächen und/oder zur Detektion von organischen Substanzen in einer Lösung oder auf einer Oberfläche.The present invention relates to compositions for cleaning surfaces and/or for detecting organic substances in a solution or on a surface.

Die Reinigung und die Desinfektion von Oberflächen ist u.a. im Bereich der Lebensmittelerzeugung und der Arzneimttelherstellung von großer Bedeutung. Vor allem Vorrichtungen, die im Produktionsprozess mit Lebensmitteln und Arzneimitteln bzw. deren Ausgangsprodukte in Kontakt kommen, müssen regelmäßig einer gründlichen Reinigung und Desinfektion unterzogen werden. In vielen Reinigungsverfahren werden Reinigungslösungen auf Basis von Alkalihydroxiden oder stark oxidierenden Substanzen eingesetzt. Um die Effizienz einer Reinigung zu überprüfen werden häufig wässrige Reinigungs- oder Detektionslösungen eingesetzt, die ein Oxidationsmittel umfassen, das bei dessen Reduktion mit, beispielsweise, organischen Verbindungen in der Lage ist, die Farbe der entsprechenden Lösungen zu verändern. Durch die durch die Reduktion des Oxidationsmittels bedingte Farbänderung ist es somit möglich festzustellen, ob in einer Lösung oder auf einer Oberfläche organische Verbindungen vorhanden sind. Erfolgt keine Farbänderung ist davon auszugehen, dass keine das Oxidationsmittel reduzierenden Verbindungen vorhanden sind. Als Oxidationsmittel werden häufig Salze der Permangansäure und insbesondere Kaliumpermanganat eingesetzt (siehe WO 03/035812 und WO 2014/122277 ).The cleaning and disinfection of surfaces is of great importance, among other things, in the field of food production and the manufacture of medicines. Above all, devices that come into contact with food and medicines or their starting products during the production process must be thoroughly cleaned and disinfected on a regular basis. Cleaning solutions based on alkali hydroxides or strongly oxidizing substances are used in many cleaning processes. In order to check the efficiency of a cleaning, aqueous cleaning or detection solutions are often used which comprise an oxidizing agent which, when it is reduced with, for example, organic compounds, is able to change the color of the corresponding solutions. The color change caused by the reduction of the oxidizing agent makes it possible to determine whether organic compounds are present in a solution or on a surface. If there is no color change, it can be assumed that no compounds reducing the oxidizing agent are present. Salts of permanganic acid and in particular potassium permanganate are often used as oxidizing agents (see WO 03/035812 and WO 2014/122277 ).

In der WO 2005/044968 und der WO 02/31098 werden Zusammensetzungen umfassend Persulfat, Kaliumpermanganat und Phosphat offenbart. In der EP 2 450 114 werden Zusammensetzungen offenbart, welche unter anderem Kaliumpermanganat und Persulfate umfassen können. Diesen Zusammensetzungen können Phosphonate als Stabilisatoren zugesetzt werden, die zur Stabilisierung von Wasserstoffperoxid und Persulfat dienen können. In der EP 0 313 145 werden phosphatsfreie Bleichmittel beschrieben, welche neben Peroxiden u.a. stickstoffhaltig Polyphosphonate umfassen können.In the WO 2005/044968 and the WO 02/31098 compositions comprising persulfate, potassium permanganate and phosphate are disclosed. In the EP 2 450 114 discloses compositions which may include, inter alia, potassium permanganate and persulfates. Phosphonates can be added to these compositions as stabilizers, which can serve to stabilize hydrogen peroxide and persulfate. In the EP 0 313 145 phosphate-free bleaching agents are described which, in addition to peroxides, can include, inter alia, nitrogen-containing polyphosphonates.

Viele Reinigungsmittel beinhalten Phosphate, um die Härte des bei der Reinigung eingesetzten Wassers zu reduzieren und die Reinigung zu verbessern. Da Phosphate jedoch zu ökologischen Problemen führen können, ist es erstrebenswert anstelle von Phosphaten andere Stoffe einzusetzen.Many detergents contain phosphates to reduce the hardness of the water used in cleaning and improve cleaning. However, since phosphates are too ecological can lead to problems, it is desirable to use other substances instead of phosphates.

Es ist somit eine Aufgabe der vorliegenden Erfindung eine Zusammensetzung zur Verfügung zu stellen, die u.a. geeignet ist Oberflächen zu reinigen und die keine Phosphate umfasst.It is therefore an object of the present invention to provide a composition which is suitable, inter alia, for cleaning surfaces and which does not comprise any phosphates.

Die vorliegende Erfindung betrifft daher eine Zusammensetzung zur Reinigung von Oberflächen und/oder zur Detektion von organischen Substanzen in einer Lösung oder auf einer Oberfläche umfassend

  1. a) mindestens ein Salz der Permangansäure, Eisensäure und/oder Chromsäure,
  2. b) mindestens ein organisches Phosphonat und
  3. c) mindestens ein Persulfat
wobei das mindestens eine organische Phosphonat ausgewählt ist aus der Gruppe bestehend aus 1-Hydroxyethan-(1,1-diphosphonsäure), 2-Phosphonobutan-1,2,4-Tricarbonsäure und einem Salz davon.The present invention therefore relates to a composition for cleaning surfaces and/or for detecting organic substances in a solution or on a surface
  1. a) at least one salt of permanganic acid, iron acid and/or chromic acid,
  2. b) at least one organic phosphonate and
  3. c) at least one persulfate
wherein the at least one organic phosphonate is selected from the group consisting of 1-hydroxyethane-(1,1-diphosphonic acid), 2-phosphonobutane-1,2,4-tricarboxylic acid and a salt thereof.

Es hat sich in überraschender Weise gezeigt, dass organische Phosphonate wie oben definiert anstelle von Phosphaten in Reinigungsmittel eingesetzt werden können. Die erfindungsgemäß eingesetzten organischen Phosphonate zeichnen sich vor allem auch dadurch aus, dass sie in der Lage sind, die Stabilität und damit die Lagerfähigkeit der darin befindlichen Salze der Permangansäure, Eisensäure und Chromsäure signifikant zu erhöhen. Dies ist u.a. dahingehend überraschend, da Salze der zuvor genannten Säuren - als starke Oxidationsmittel - in der Lage sind, einerseits organische Verbindungen zu oxidieren. Zudem hat sich gezeigt, dass organische Phosphonate, deren organische Reste Heteroalkyl-, Heterocycloalkyl- oder Heteroaryl-Reste umfassen keine stabile Zusammensetzung in Hinblick auf die in der Zusammensetzung befindlichen Salze der Permangansäure, Eisensäure und/oder Chromsäure ergeben. D.h. organische Phosphonate umfassend Heteroalkyl-, Heterocycloalkyl- und/oder Heteroaryl-Reste sind nicht geeignet in einer erfindungsgemäßen Zusammensetzung eingesetzt zu werden, da dadurch die Salze der Permangansäure, Eisensäure und Chromsäure überraschenderweise destabilisiert werden, so dass diese nicht mehr als Farbindikator zur Detektion von organischen Verbindungen eingesetzt werden können. Bei derartigen nicht erfindungsgemäßen organischen Phosphonaten käme es zu einer unerwünschten Farbänderung der Zusammensetzung, wodurch diese nicht mehr geeignet ist, organische Substanzen durch Farbänderung, wie z.B. in der WO 03/035812 beschrieben, nachzuweisen. Überraschenderweise zeigen organische Phosphonate der eingangs definierten Art einen stabilisierenden und keinen destabilisierenden Effekt auf Salze der Permangansäure, Eisensäure und Chromsäure. Die erfindungsgemäßen organischen Phosphonate umfassen daher ausschließlich Homoalkyl-, Homocycloalkyl- und Homoaryl-Reste, d.h. diese Reste weisen in der Kette bzw. im Ring anstelle von C-Atomen weder ein O-, S- noch N-Atom auf.Surprisingly, it has been found that organic phosphonates as defined above can be used in detergents instead of phosphates. The organic phosphonates used according to the invention are also distinguished above all by the fact that they are able to significantly increase the stability and thus the shelf life of the salts of permanganic acid, iron acid and chromic acid present therein. This is surprising, inter alia, since salts of the aforementioned acids--as strong oxidizing agents--are able on the one hand to oxidize organic compounds. In addition, it has been shown that organic phosphonates whose organic radicals comprise heteroalkyl, heterocycloalkyl or heteroaryl radicals do not result in a stable composition with regard to the salts of permanganic acid, iron acid and/or chromic acid present in the composition. Ie organic phosphonates comprising heteroalkyl, heterocycloalkyl and / or heteroaryl radicals are not suitable to be used in a composition according to the invention, since this surprisingly destabilizes the salts of permanganic acid, iron acid and chromic acid, so that they are no longer used as a color indicator for the detection of organic compounds can be used. In such non-inventive organic phosphonates, there would be an undesirable color change in the composition, which this is no longer suitable, organic substances by color change, such as in the WO 03/035812 described to be proven. Surprisingly, organic phosphonates of the type defined at the outset have a stabilizing and not a destabilizing effect on salts of permanganic acid, iron acid and chromic acid. The organic phosphonates according to the invention therefore comprise exclusively homoalkyl, homocycloalkyl and homoaryl radicals, ie these radicals have neither an O, S nor N atom in the chain or in the ring instead of C atoms.

Es wurde überraschenderweise experimentell festgestellt, dass organische Phosphonate wie Amino-tris(methylenphosphonsäure) (ATMP), Diethylentriaminpenta(methylenphosphonsäure) (DTPMP) und Ethylendiamintetra(methylenphosphonsäure) (EDTMP) umfassend Heteroalkyle zu einer raschen Reduktion der Salze der Permangansäure, Eisensäure und Chromsäure führen wohingegen HEDP und PBTC, beide weisen keine Heteroalkyle auf, diese Eigenschaften nicht zeigen. Ein organisches Phosphonat ist für den erfindungsgemäßen Zweck dann geeignet, wenn dieses innerhalb von 30 Minuten bei Raumtemperatur (40°C) maximal 30%, vorzugsweise maximal 25%, noch mehr bevorzugt maximal 20%, Mn(VII) (in Permanganat) zu Mn(VI) umgesetzt wird. Diese Umsetzung kann beispielsweise bei einer Absorption von 425nm (Absorptionsmaximum von Mn(VI)) gemessen werden. Erfolgt eine raschere Reduktion der Salze der Permangansäure, Eisensäure und Chromsäure können entsprechende Zusammensetzungen nur bedingt zur Bestimmung von organischen Verbindungen in einer Probe herangezogen werden, da es dadurch nicht möglich ist festzustellen, ob die Reduktion der Salze tatsächlich von der zu untersuchenden Probe stammt.It was surprisingly found experimentally that organic phosphonates such as amino-tris(methylenephosphonic acid) (ATMP), diethylenetriaminepenta(methylenephosphonic acid) (DTPMP) and ethylenediaminetetra(methylenephosphonic acid) (EDTMP) including heteroalkyls lead to a rapid reduction of the salts of permanganic acid, iron acid and chromic acid whereas HEDP and PBTC, both lacking heteroalkyls, do not show these properties. An organic phosphonate is then suitable for the purpose of the invention if this within 30 minutes at room temperature (40 ° C) at most 30%, preferably at most 25%, even more preferably at most 20%, Mn (VII) (in permanganate) to Mn (VI) is implemented. This conversion can be measured, for example, at an absorption of 425 nm (absorption maximum of Mn(VI)). If the salts of permanganic acid, iron acid and chromic acid are reduced more quickly, the corresponding compositions can only be used to a limited extent for the determination of organic compounds in a sample, since it is not possible to determine whether the reduction of the salts actually comes from the sample to be examined.

Die erfindungsgemäße Zusammensetzung kann mehrere verschiedene Salze der Permangansäure, Eisensäure und Chromsäure umfassen, wobei die Zusammensetzung Salze mit demselben Anion und unterschiedlichen Kationen und/oder Salze mit unterschiedlichen Anionen und demselben Kation umfassen kann. Salze der Permangansäure, Eisensäure und Chromsäure umfassen vorzugsweise die Anionen MnO4 -, FeO4 2- bzw. CrO4 2-, wobei die Kationen vorzugsweise Metallionen, insbesondere Alkalimetallionen, sind. Vorzugsweise umfasst die erfindungsgemäße Zusammensetzung somit mindestens zwei, noch mehr bevorzugt mindestens drei, noch mehr bevorzugt mindestens fünf Salze der Permangansäure, Eisensäure und/oder Chromsäure.The composition according to the invention can comprise several different salts of permanganic acid, ferric acid and chromic acid, where the composition can comprise salts with the same anion and different cations and/or salts with different anions and the same cation. Salts of permanganic acid, iron acid and chromic acid preferably include the anions MnO 4 - , FeO 4 2- or CrO 4 2- , the cations preferably being metal ions, in particular alkali metal ions. The composition according to the invention thus preferably comprises at least two, even more preferably at least three, even more preferably at least five salts of permanganic acid, ferric acid and/or chromic acid.

Salze der Permangansäure, Eisensäure und Chromsäure sind bekannte Oxidationsmittel. Die erfindungsgemäße Zusammensetzung kann neben diesen Oxidationsmittel mindestens, vorzugsweise mindestens zwei, noch mehr bevorzugt mindestens drei, noch mehr bevorzugt mindestens vier, weitere Oxidationsmittel umfassen. D.h. diese weiteren Oxidationsmittel sind keine Salze der Permangansäure, Eisensäure und Chromsäure.Salts of permanganic acid, ferric acid and chromic acid are known oxidizing agents. In addition to these oxidizing agents, the composition according to the invention can comprise at least, preferably at least two, even more preferably at least three, even more preferably at least four, further oxidizing agents. I.e. these other oxidizing agents are not salts of permanganic acid, iron acid and chromic acid.

Die erfindungsgemäße Zusammensetzung umfasst mindestens ein, vorzugsweise mindestens zwei, noch mehr bevorzugt mindestens drei, noch mehr bevorzugt mindestens vier, organische Phosphonate. "Phosphonate" sind organische Verbindungen ("organische Phosphonate") der Phosphonsäure (H3PO3). Ein "organisches Phosphonat" weist die allgemeine Formel

Figure imgb0001
auf, wobei R1 ein organischer Rest, X1 OH oder OM1 und X2 OH oder OM2 ist, wobei M1 und M2 für ein Alkalimetallion oder Ammoniumion stehen kann. Der organische Rest R1 kann ein substituierter oder unsubstituierter C1-C12 Alkyl-Rest, C3-C10-Cycloalkyl-Rest oder C6-C14-Aryl-Rest sein, wobei der organische Rest an 1 bis 3 weiteren Phosphonatgruppen der allgemeinen Formel (I) gebunden sein kann.The composition according to the invention comprises at least one, preferably at least two, even more preferably at least three, even more preferably at least four, organic phosphonates. "Phosphonates" are organic compounds ("organic phosphonates") of phosphonic acid (H 3 PO 3 ). An "organic phosphonate" has the general formula
Figure imgb0001
 on, where R 1 is an organic radical, X 1 is OH or OM 1 and X 2 is OH or OM 2 , where M 1 and M 2 can represent an alkali metal ion or ammonium ion. The organic radical R 1 can be a substituted or unsubstituted C 1 -C 12 alkyl radical, C 3 -C 10 cycloalkyl radical or C 6 -C 14 aryl radical, the organic radical being attached to 1 to 3 further phosphonate groups of the general formula (I) may be bound.

Organische Phosphonat-Verbindungen können die allgemeine Struktur R-PO(OH)2 aufweisen, wobei R ein Alkyl- oder Aryl-Rest oder ein sonstiger organischer Rest sein kann. Umfasst ein Phosphonat mehr als eine dieser organischen Phosphonate so spricht man von Bisphosphonaten oder Polyphosphonaten. Organische Phosphonate können Säuren sein oder als Salze, vorzugsweise als Alkalimetallsalze, vorliegen.Organic phosphonate compounds can have the general structure R-PO(OH) 2 where R can be an alkyl or aryl radical or other organic radical. If a phosphonate comprises more than one of these organic phosphonates, it is referred to as bisphosphonates or polyphosphonates. Organic phosphonates can be acids or exist as salts, preferably as alkali metal salts.

Die erfindungsgemäße Zusammensetzung, die in fester Form oder als wässrige Lösung vorliegen kann, eignet sich aufgrund der darin vorhandenen Oxidationsmittel zur Reinigung und Desinfektion von Oberflächen, insbesondere von metallischen, keramischen oder Glas-Oberflächen, die gegenüber Oxidatidationsmitteln im Wesentlichen resistent sind. Gemäß einer bevorzugten Ausführungsform der vorliegenden Erfindung umfassen bzw. bestehen die zu reinigenden metallischen Oberflächen aus Edelstahl und/oder inerten Metallen (wie z.B. Platin, Gold) oder Metalllegierungen, wobei Oberflächen bestehend aus oder umfassend Edelstahl besonders bevorzugt sind, da diese üblicherweise in den Produktionsanlagen der pharmazeutischen Industrie und bei der Lebensmittelherstellung (inkludiert auch die Getränkeherstellung wie die Wein- und Biererzeugung) zum Einsatz kommen. Besonders bevorzugt werden mit der erfindungsgemäßen Zusammensetzung Rohre und Behältnisse jeglicher Art gereinigt bzw. desinfiziert. Demgemäß kann eine Oberfläche jegliche Form und Teil von einem beliebigen Objekt sein.The composition according to the invention, which can be in solid form or as an aqueous solution, is suitable for cleaning and disinfecting surfaces, in particular metallic, ceramic or glass surfaces, which are resistant to oxidizing agents because of the oxidizing agents present therein are essentially resistant. According to a preferred embodiment of the present invention, the metallic surfaces to be cleaned comprise or consist of stainless steel and/or inert metals (such as platinum, gold) or metal alloys, with surfaces consisting of or comprising stainless steel being particularly preferred since these are usually used in the production plants in the pharmaceutical industry and in food production (including beverage production such as wine and beer production). Pipes and containers of any kind are particularly preferably cleaned or disinfected with the composition according to the invention. Accordingly, a surface can be any shape and part of any object.

Mit der erfindungsgemäßen Zusammensetzung können Verunreinigungen jeglicher Art von einer Oberfläche entfernt werden. Vorzugsweise werden übliche Verunreinigungen der Lebensmittelindustrie (z.B. Fett- und Eiweißablagerungen, eingebrannte Lebensmittelreste) und der pharmazeutischen Industrie (z.B. Rückstände der Herstellung von Arzneimitteln) gereinigt. Neben dem Einsatz zum Reinigen von Oberflächen kann die erfindungsgemäße Zusammensetzung auch zur Desinfektion von Oberflächen herangezogen werden. Dabei werden Zellen jeglicher Art, insbesondere Mikroorganismen wie Bakterien, Archaea, Pilze, Algen und Protozoen, aber auch tierische, menschliche und pflanzliche Zellen zerstört oder zumindest so weit geschädigt, dass diese nicht mehr lebensfähig sind. Zudem können mit der erfindungsgemäßen Zusammensetzung auch Viren unschädlich gemacht werden.With the composition according to the invention, contaminants of any kind can be removed from a surface. The usual contaminants in the food industry (e.g. fat and protein deposits, burnt-on food residues) and the pharmaceutical industry (e.g. residues from the manufacture of medicines) are preferably cleaned. In addition to being used for cleaning surfaces, the composition according to the invention can also be used for disinfecting surfaces. Cells of all kinds, in particular microorganisms such as bacteria, archaea, fungi, algae and protozoa, but also animal, human and plant cells are destroyed or at least damaged to such an extent that they are no longer viable. In addition, viruses can also be rendered harmless with the composition according to the invention.

Die erfindungsgemäße Zusammensetzung kann entweder batchweise (d.h. diskontinuierlich) oder kontinuierlich (z.B. durch Durchleiten der erfindungsgemäßen wässrigen Reinigungslösung durch zu reinigende Rohre oder Behältnisse) eingesetzt werden. Die erfindungsgemäße Zusammensetzung wird besonders bevorzugt im Rahmen eines CIP-Verfahrens ("Cleaning in Place"-Verfahren, ortsgebundenes Reinigungsverfahren) eingesetzt. CIP-Verfahren umfassen in der Regel mehrere Verfahrensschritte wie (1) Vorspülen, um grobe Verschmutzungen zu entfernen, (2) Reinigen mit einem alkalischen Mittel (meist einem Alkalihydroxid), (3) Entfernung des Reinigungsmittels durch Spülen mit Wasser, (4) optionale Säurebehandlung zur Entfernung von Kalkablagerungen, (5) optionale Entfernung der Säure mit Wasser und (6) Desinfektion. Zumindest Schritt (2) eines CIP-Verfahrens wird stets mit Temperaturen von mindestens 70°C durchgeführt, um eine effiziente Reinigung des alkalischen Mittels zu ermöglichen.The composition according to the invention can be used either batchwise (ie discontinuously) or continuously (eg by passing the aqueous cleaning solution according to the invention through pipes or containers to be cleaned). The composition according to the invention is particularly preferably used as part of a CIP process (“Cleaning in Place” process, site-specific cleaning process). CIP processes typically involve several process steps such as (1) pre-rinsing to remove gross contamination, (2) cleaning with an alkaline agent (usually an alkali hydroxide), (3) removal of the cleaning agent by rinsing with water, (4) optional Acid treatment to remove limescale, (5) optional acid removal with water; and (6) disinfection. At least step (2) of a CIP process is always carried out at temperatures of at least 70°C in order to enable efficient cleaning of the alkaline agent.

Gemäß einer weiteren bevorzugten Ausführungsform der vorliegenden Erfindung ist das Salz des mindestens einen organischen Phosphonats ein Alkalisalz (Natrium-, Kalium- oder Lithiumsalz)According to a further preferred embodiment of the present invention, the salt of the at least one organic phosphonate is an alkali metal salt (sodium, potassium or lithium salt)

Gemäß einer bevorzugten Ausführungsform der vorliegenden Erfindung ist das mindestens eine Salz der Permangansäure, Eisensäure und/oder Chromsäure ein Alkalisalz, vorzugsweise ausgewählt aus der Gruppe bestehend aus Kaliumpermanganat, Kaliumferrat und Kaliumdichromat, wobei besonders bevorzugt die erfindungsgemäße Zusammensetzung Kaliumpermanganat umfasst.According to a preferred embodiment of the present invention, the at least one salt of permanganic acid, iron acid and/or chromic acid is an alkali metal salt, preferably selected from the group consisting of potassium permanganate, potassium ferrate and potassium dichromate, the composition according to the invention particularly preferably comprising potassium permanganate.

"Persulfate" sind Salze der Peroxodischwefelsäure H2S2O8 oder der Peroxomonoschwefelsäure H2SO5 und weisen ein hohes Oxidationspotential auf. Persulfate eignen sich daher gut zur Reinigung und/oder Desinfektion von Oberflächen."Persulfates" are salts of peroxodisulfuric acid H 2 S 2 O 8 or peroxomonosulfuric acid H 2 SO 5 and have a high oxidation potential. Persulfates are therefore well suited for cleaning and/or disinfecting surfaces.

Gemäß einer besonders bevorzugten Ausführungsform der vorliegenden Erfindung ist das mindestens eine Persulfat ein Salz der Peroxodischwefelsäure oder der Peroxomonoschwefelsäure.According to a particularly preferred embodiment of the present invention, the at least one persulfate is a salt of peroxodisulfuric acid or of peroxomonosulfuric acid.

Gemäß einer weiteren bevorzugten Ausführungsform der vorliegenden Erfindung ist das mindestens eine Persulfat ein Peroxodisulfat ausgewählt aus der Gruppe bestehend aus Natriumperoxodisulfat, Kaliumperoxodisulfat und, Ammoniumperoxodisulfat und/oder ein Peroxomonosulfat ausgewählt aus der Gruppe bestehend aus Kaliumperoxomonosulfat.According to a further preferred embodiment of the present invention, the at least one persulfate is a peroxodisulfate selected from the group consisting of sodium peroxodisulfate, potassium peroxodisulfate and ammonium peroxodisulfate and/or a peroxomonosulfate selected from the group consisting of potassium peroxomonosulfate.

Gemäß einer besonders bevorzugten Ausführungsform der vorliegenden Erfindung umfasst die Zusammensetzung mindestens ein Calciumsalz, welches vorzugsweise ausgewählt ist aus der Gruppe bestehend aus Calciumnitrat.According to a particularly preferred embodiment of the present invention, the composition comprises at least one calcium salt, which is preferably selected from the group consisting of calcium nitrate.

Die erfindungsgemäße Zusammensetzung umfasst das mindestens eine Salz der Permangansäure, Eisensäure und/oder Chromsäure in einem Gewichtsverhältnis zu dem mindestens einen organischen Phosphonats von vorzugsweise 1:50 bis 1:500, vorzugsweise von 1:75 bis 1:300, noch mehr bevorzugt von 1:100 bis 1:200.The composition according to the invention comprises the at least one salt of permanganic acid, ferric acid and/or chromic acid in a weight ratio to the at least one organic phosphonate of preferably 1:50 to 1:500, preferably 1:75 to 1:300, even more preferably 1 :100 to 1:200.

Die erfindungsgemäße Zusammensetzung kann sowohl im Wesentlichen wasserfrei als auch in wässriger Form bereitgestellt werden.The composition according to the invention can be provided both essentially anhydrous and in aqueous form.

Gemäß einer bevorzugten Ausführungsform der vorliegenden Erfindung ist die Zusammensetzung eine wässrige Zusammensetzung. Dabei umfasst die Zusammensetzung zugesetztes Wasser, wobei die wässrige Zusammensetzung vorzugsweise dadurch hergestellt wird, dass Wasser vorgelegt und die einzelnen Komponenten hinzugegeben werden.According to a preferred embodiment of the present invention, the composition is an aqueous composition. The composition comprises added water, the aqueous composition preferably being prepared by initially introducing water and adding the individual components.

Gemäß einer weiteren bevorzugten Ausführungsform der vorliegenden Erfindung umfasst die wässrige Zusammensetzung mehr als 30 Gew%, vorzugsweise mehr als 40 Gew%, noch mehr bevorzugt mehr als 50 Gew%, noch mehr bevorzugt mehr als 60 Gew%, noch mehr bevorzugt mehr als 70 Gew%, noch mehr bevorzugt mehr als 75 Gew%, noch mehr bevorzugt mehr als 80 Gew%, noch mehr bevorzugt mehr als 85 Gew%, noch mehr bevorzugt mehr als 90 Gew%, Wasser.According to a further preferred embodiment of the present invention, the aqueous composition comprises more than 30% by weight, preferably more than 40% by weight, even more preferably more than 50% by weight, even more preferably more than 60% by weight, even more preferably more than 70% by weight %, even more preferably more than 75% by weight, even more preferably more than 80% by weight, even more preferably more than 85% by weight, even more preferably more than 90% by weight, water.

"Gew%", wie hier verwendet, bedeutet "Gewichtsprozent"."Wt%" as used herein means "weight percent".

Das Bereitstellen der erfindungsgemäßen Zusammensetzung als wässrige Zusammensetzung hat den Vorteil, dass diese direkt und unmittelbar zum Reinigen/Desinfizieren von Oberflächen oder zum Detektieren von organischen/biologischen Verunreinigungen eingesetzt werden kann.Providing the composition according to the invention as an aqueous composition has the advantage that it can be used directly and immediately for cleaning/disinfecting surfaces or for detecting organic/biological contamination.

Umfasst die erfindungsgemäße Zusammensetzung einen geringeren Wasseranteil (z.B. weniger als 60%, vorzugsweise weniger als 50%, noch mehr bevorzugt weniger als 40%, noch mehr bevorzugt weniger als 30%), so kann diese als Konzentrat eingesetzt werden, welches vor dem Einsatz mit Wasser oder anderen Reinigungslösungen umfassend beispielsweise Alkalihydroxiden (z.B. NaOH, KOH) verdünnt wird.If the composition according to the invention has a lower water content (e.g. less than 60%, preferably less than 50%, even more preferably less than 40%, even more preferably less than 30%), it can be used as a concentrate which, before use, water or other cleaning solutions comprising, for example, alkali hydroxides (e.g. NaOH, KOH).

Gemäß einer besonders bevorzugten Ausführungsform der vorliegenden Erfindung umfasst die wässrige Zusammensetzung 0,1 Gew% bis 2 Gew%, vorzugsweise 0,2 Gew% bis 1,5 Gew%, noch mehr bevorzugt 0,3 Gew% bis 1 Gew%, noch mehr bevorzugt 0,4 Gew% bis 0,8 Gew%, noch mehr bevorzugt 0,4 Gew% bis 0,6 Gew%, noch mehr bevorzugt 0,5 Gew%, des mindestens einen weiteren Oxidationsmittels umfasst.According to a particularly preferred embodiment of the present invention, the aqueous composition comprises from 0.1% to 2% by weight, preferably from 0.2% to 1.5% by weight, even more preferably from 0.3% to 1% by weight, even more preferably 0.4% by weight to 0.8% by weight, even more preferably 0.4% by weight to 0.6% by weight, even more preferably 0.5% by weight, of the at least one further oxidizing agent.

Die wässrige Zusammensetzung umfasst vorzugsweise 0,01 Gew% bis 1 Gew%, vorzugsweise 0,02 Gew% bis 0,9 Gew%, noch mehr bevorzugt 0,05 Gew% bis 0,8 Gew%, noch mehr bevorzugt 0,075 Gew% bis 0,7 Gew%, noch mehr bevorzugt 0,1 Gew% bis 0,6 Gew%, noch mehr bevorzugt 0,2 Gew% bis 0,6 Gew%, noch mehr bevorzugt 0,3 Gew% bis 0,6 Gew%, des mindestens einen organischen Phosphonats.The aqueous composition preferably comprises 0.01% to 1% by weight, preferably 0.02% to 0.9% by weight, more preferably 0.05% to 0.8% by weight, even more preferably 0.075% by weight to 0.7% by weight, even more preferably 0.1% to 0.6% by weight, even more preferably 0.2% to 0.6% by weight, even more preferably 0.3% to 0.6% by weight %, of the at least one organic phosphonate.

Gemäß einer weiteren bevorzugten Ausführungsform der vorliegenden Erfindung umfasst die wässrige Zusammensetzung 0,1 Gew% bis 3 Gew%, vorzugsweise 0,2 Gew% bis 2 Gew%, noch mehr bevorzugt 0,3 bis 1 Gew%, des mindestens einen Calciumsalzes umfasst.According to a further preferred embodiment of the present invention, the aqueous composition comprises 0.1% to 3% by weight, preferably 0.2% to 2% by weight, even more preferably 0.3 to 1% by weight, of the at least one calcium salt.

Gemäß einer bevorzugten Ausführungsform der vorliegenden Erfindung ist die Zusammensetzung im Wesentlichen wasserfrei.According to a preferred embodiment of the present invention, the composition is essentially anhydrous.

"Im Wesentlichen wasserfrei", wie hier verwendet, bedeutet, dass die erfindungsgemäße Zusammensetzung nicht mehr als 10 Gew%, vorzugsweise nicht mehr als 5 Gew% Hydratwasser und/oder Konstitutionswasser umfasst."Substantially anhydrous" as used herein means that the composition of the invention comprises no more than 10%, preferably no more than 5% by weight water of hydration and/or water of constitution.

Gemäß einer besonders bevorzugten Ausführungsform der vorliegenden Erfindung umfasst die Zusammensetzung weniger als 20 Gew%, vorzugsweise weniger als 10 Gew%, noch mehr bevorzugt weniger als 5 Gew%, noch mehr bevorzugt weniger als 1 Gew%, Wasser.According to a particularly preferred embodiment of the present invention, the composition comprises less than 20% by weight, preferably less than 10% by weight, even more preferably less than 5% by weight, even more preferably less than 1% by weight, water.

Gemäß einer weiteren bevorzugten Ausführungsform der vorliegenden Erfindung umfasst die Zusammensetzung mindestens ein Alkalihydroxid umfasst.According to a further preferred embodiment of the present invention, the composition comprises at least one alkali metal hydroxide.

Um die Reinigungswirkung der erfindungsgemäßen Zusammensetzung zu erhöhen, umfasst diese mindestens ein Alkalihydroxid. Alkalihydroxide werden häufig für die Reinigung von Oberflächen verwendet, da sich einerseits die negativ geladenen Hydroxidionen sowohl am Schmutz als auch an der zu reinigenden Oberfläche anlagern, was zu einer elektrostatischen Abstoßung des Schmutzes führt, und andererseits Öle und Fette bei Anwesenheit von Hydroxiden in einer Verseifungsreaktion in wasserlösliche Seifen umgewandelt werden.In order to increase the cleaning effect of the composition according to the invention, it comprises at least one alkali metal hydroxide. Alkaline hydroxides are often used for cleaning surfaces because, on the one hand, the negatively charged hydroxide ions attach themselves both to the dirt and to the surface to be cleaned, which leads to electrostatic repulsion of the dirt, and, on the other hand, oils and fats in the presence of hydroxides in a saponification reaction be converted into water-soluble soaps.

"Alkalihydroxide", auch als "Alkalimetallhydroxide" bezeichnet, sind Hydroxide der Alkalimetalle und weisen die allgemeine Formel MeOH (Me - Alkalimetall) auf. "Alkalihydroxide" lösen sich unter starker Erwärmung leicht in Wasser unter Bildung stark alkalischer Lösungen."Alkali hydroxides", also referred to as "alkali metal hydroxides", are hydroxides of the alkali metals and have the general formula MeOH (Me - alkali metal). "Alkali hydroxides" easily dissolve in water with strong heating to form strongly alkaline solutions.

Gemäß einer besonders bevorzugten Ausführungsform der vorliegenden Erfindung umfasst das mindestens eine Alkalihydroxid NaOH, KOH oder LiOH wobei besonders bevorzugt NaOH oder KOH eingesetzt wird.According to a particularly preferred embodiment of the present invention, the at least one alkali metal hydroxide comprises NaOH, KOH or LiOH, NaOH or KOH being particularly preferably used.

Die wässrige Zusammensetzung umfasst vorzugsweise 0,1 Gew% bis 5 Gew%, vorzugsweise 0,2 Gew% bis 3 Gew%, noch mehr bevorzugt 0,3 Gew% bis 1,5 Gew%, noch mehr bevorzugt 0,4 Gew% bis 1 Gew%, noch mehr bevorzugt 0,4 Gew% bis 0,8 Gew%, noch mehr bevorzugt 0,5 Gew%, des mindestens einen Alkalihydroxids.The aqueous composition preferably comprises from 0.1% to 5%, preferably from 0.2% to 3%, more preferably from 0.3% to 1.5%, even more preferably from 0.4% to 5% by weight 1% by weight, even more preferably 0.4% by weight to 0.8% by weight, even more preferably 0.5% by weight, of the at least one alkali metal hydroxide.

Ein weiterer Aspekt der vorliegenden Erfindung betrifft ein Kit zur Reinigung von Oberflächen und/oder zur Detektion von organischen Substanzen in einer Lösung oder auf einer Oberfläche umfassend

  • a1) ein Behältnis umfassend eine erfindungsgemäße Zusammensetzung und
  • b1) ein Behältnis umfassend mindestens ein Alkalihydroxid oder
  • a2) ein Behältnis umfassend mindestens ein erfindungsgemäßes Alkalisalz der Permangansäure, Eisensäure und/oder Chromsäure,
  • b2) ein Behältnis umfassend mindestens ein erfindungsgemäßes organisches Phosphonat und optional mindestens ein Persulfat und
  • c2) ein Behältnis umfassend mindestens ein Alkalihydroxid.
A further aspect of the present invention relates to a kit for cleaning surfaces and/or for detecting organic substances in a solution or on a surface
  • a1) a container comprising a composition according to the invention and
  • b1) a container comprising at least one alkali metal hydroxide or
  • a2) a container comprising at least one alkali metal salt of permanganic acid, iron acid and/or chromic acid according to the invention,
  • b2) a container comprising at least one organic phosphonate according to the invention and optionally at least one persulfate and
  • c2) a container comprising at least one alkali metal hydroxide.

Die erfindungsgemäße Zusammensetzung kann auch als Teil eines Kits sein, der zur Reinigung von Oberflächen und/oder zur Detektion von organischen Substanzen in einer Lösung oder auf einer Oberfläche eingesetzt werden kann. Neben der erfindungsgemäßen Zusammensetzung umfasst der Kit ein Behältnis, in dem sich mindestens ein Alkalihydroxid, entweder in einer wässrigen Lösung oder im Wesentlichen wasserfrei, wie hierin definiert, befindet. Der Inhalt oder entsprechende Anteile des Inhalts der beiden Behältnisse können vor deren Benutzung vermengt, vermischt und/oder mit Wasser versehen werden.The composition according to the invention can also be part of a kit that can be used to clean surfaces and/or to detect organic substances in a solution or on a surface. In addition to the composition according to the invention, the kit comprises a container containing at least one alkali metal hydroxide, either in an aqueous solution or essentially anhydrous, as defined herein. The content or corresponding proportions of the content of the two containers can be blended, mixed and/or provided with water before they are used.

Gemäß einer bevorzugten Ausführungsform der vorliegenden Erfindung ist das mindestens eine Alkalihydroxid NaOH, KOH oder LiOH.According to a preferred embodiment of the present invention, the at least one alkali metal hydroxide is NaOH, KOH or LiOH.

Ein noch weiterer Aspekt der vorliegenden Erfindung betrifft ein Verfahren zur Reinigung von Oberflächen und/oder zur Detektion von organischen Substanzen in einer Lösung oder auf einer Oberfläche umfassend den Schritt des Inkontaktbringens einer Zusammensetzung gemäß der vorliegenden Erfindung oder einer Zusammensetzung erhältlich durch Vermischen der Komponenten in den Behältnissen a1 und b1 oder a2, b2 und b3 des erfindungsgemäßen Kits mit der zu reinigenden Oberfläche oder der Oberfläche oder Lösung, auf oder in der organische Substanzen bestimmt werden.Yet another aspect of the present invention relates to a method for cleaning surfaces and/or for detecting organic substances in a solution or on a surface, comprising the step of bringing a composition into contact according to the present invention or a composition obtainable by mixing the components in the containers a1 and b1 or a2, b2 and b3 of the kit according to the invention with the surface to be cleaned or the surface or solution on or in which organic substances are determined.

Die erfindungsgemäße Zusammensetzung kann in Verfahren zur Reinigung von Oberflächen und/oder zur Detektion von organischen Substanzen in einer Lösung oder auf einer Oberfläche eingesetzt werden. Entsprechende Verfahren sind dem Fachmann hinreichend bekannt und umfassen zumindest die Schritte des Aufbringens der erfindungsgemäßen Zusammensetzung auf eine zu reinigende Oberfläche und dessen Entfernung nach einer üblichen Einwirkzeit. Üblicherweise wird die Oberfläche anschließend mit Wasser gespült, um Reste der erfindungsgemäßen Zusammensetzung und evtl. noch vorhandene Schmutzreste zu entfernen.The composition according to the invention can be used in methods for cleaning surfaces and/or for detecting organic substances in a solution or on a surface. Corresponding methods are sufficiently known to the person skilled in the art and comprise at least the steps of applying the composition according to the invention to a surface to be cleaned and removing it after a customary exposure time. The surface is then usually rinsed with water in order to remove residues of the composition according to the invention and any dirt residues that may still be present.

Die vorliegende Erfindung wird anhand der folgenden Beispiele eingehender erläutert, ohne jedoch auf diese beschränkt zu sein.The present invention is explained in more detail by the following examples without being limited to them.

BEISPIELE:EXAMPLES: Beispiel 1: Stabilität von Kaliumpermanganat-haltigen ZusammensetzungenExample 1: Stability of compositions containing potassium permanganate Zusammensetzungen und Versuchsplan:Compositions and test plan:

Um die Stabilität von Permanganat in Kaliumpermanganat-haltigen Zusammensetzungen zu untersuchen, wurden verschiedene Zusammensetzungen Hergestellt, wobei nur die Zusammensetzungen K und L erfindungsgemäße Zusammensetzungen ist.

  • Zusammensetzung A:
    • 0,04 g Kaliumpermanganat
    • 2 g 1-Hydroxyethan-(1,1-diphosphonsäure) (HEDP)
    • 996,4 g Wasser
  • Zusammensetzung B:
    • 0,04 g Kaliumpermanganat
    • 2 g 2-Phosphonobutan-1,2,4-tricarbonsäure (PBTC)
    • 996,4 g Wasser
  • Zusammensetzung C:
    • 0,04 g Kaliumpermanganat
    • 2 g Amino-tris(methylenphosphonsäure) (ATMP)
    • 996,4 g Wasser
  • Zusammensetzung D:
    • 0,04 g Kaliumpermanganat
    • 2 g Diethylentriaminpenta(methylenphosphonsäure) (DTPMP)
    • 996,4 g Wasser
  • Zusammensetzung E:
    • 0,04 g Kaliumpermanganat
    • 2 g Ethylendiamintetra(methylenphosphonsäure) (EDTMP) 996,4 g Wasser
  • Zusammensetzung F:
    • 0,04 g Kaliumpermanganat
    • 2 g 1-Hydroxyethan-(1,1-diphosphonsäure) (HEDP)
    • 5 g NaOH
    • 991,4 g Wasser
  • Zusammensetzung G:
    • 0,04 g Kaliumpermanganat
    • 2 g 2-Phosphonobutan-1,2,4-tricarbonsäure (PBTC)
    • 5 g NaOH
    • 991,4 g Wasser
  • Zusammensetzung H:
    • 0,04 g Kaliumpermanganat
    • 2 g Amino-tris(methylenphosphonsäure) (ATMP)
    • 5 g NaOH
    • 991,4 g Wasser
  • Zusammensetzung I:
    • 0,04 g Kaliumpermanganat
    • 2 g Diethylentriaminpenta(methylenphosphonsäure) (DTPMP)
    • 5 g NaOH
    • 991,4 g Wasser
  • Zusammensetzung J:
    • 0,04 g Kaliumpermanganat
    • 2 g Ethylendiamintetra(methylenphosphonsäure) (EDTMP)
    • 5 g NaOH
    • 991,4 g Wasser
  • Zusammensetzung K:
    • 0,04 g Kaliumpermanganat
    • 2 g 1-Hydroxyethan-(1,1-diphosphonsäure) (HEDP)
    • 5 g NaOH
    • 5 g Natriumperoxodisulfat
    • 986,4 g Wasser
  • Zusammensetzung L:
    • 0,04 g Kaliumpermanganat
    • 2 g 2-Phosphonobutan-1,2,4-tricarbonsäure (PBTC)
    • 5 g NaOH
    • 5 g Natriumperoxodisulfat
    • 986,4 g Wasser
  • Zusammensetzung M:
    • 0,04 g Kaliumpermanganat
    • 2 g Amino-tris(methylenphosphonsäure) (ATMP)
    • 5 g NaOH
    • 5 g Natriumperoxodisulfat
    • 986,4 g Wasser
  • Zusammensetzung N:
    • 0,04 g Kaliumpermanganat
    • 2 g Diethylentriaminpenta(methylenphosphonsäure) (DTPMP)
    • 5 g NaOH
    • 5 g Natriumperoxodisulfat
    • 986,4 g Wasser
  • Zusammensetzung O:
    • 0,04 g Kaliumpermanganat
    • 2 g Ethylendiamintetra(methylenphosphonsäure) (EDTMP)
    • 5 g NaOH
    • 5 g Natriumperoxodisulfat
    • 986,4 g Wasser
  • Vergleichszusammensetzung 1:
    • 0,04 g Kaliumpermanganat
    • 2 g 1-Hydroxyethan-(1,1-diphosphonsäure) (HEDP)
    • 5 g NaOH
    • 5 g Wasserstoffperoxid
    • 986,4 g Wasser
  • Vergleichszusammensetzung 2:
    • 0,04 g Kaliumpermanganat
    • 2 g 2-Phosphonobutan-1,2,4-tricarbonsäure (PBTC)
    • 5 g NaOH
    • 5 g Wasserstoffperoxid
    • 986,4 g Wasser
  • Vergleichszusammensetzung 3:
    • 0,04 g Kaliumpermanganat
    • 2 g Amino-tris(methylenphosphonsäure) (ATMP)
    • 5 g NaOH
    • 5 g Wasserstoffperoxid
    • 986,4 g Wasser
  • Vergleichszusammensetzung 4:
    • 0,04 g Kaliumpermanganat
    • 2 g Diethylentriaminpenta(methylenphosphonsäure) (DTPMP)
    • 5 g NaOH
    • 5 g Wasserstoffperoxid
    • 986,4 g Wasser
  • Vergleichszusammensetzung 5:
    • 0,04 g Kaliumpermanganat
    • 2 g Ethylendiamintetra(methylenphosphonsäure) (EDTMP)
    • 5 g NaOH
    • 5 g Wasserstoffperoxid
    • 986,4 g Wasser
In order to investigate the stability of permanganate in compositions containing potassium permanganate, various compositions were prepared, only compositions K and L being compositions according to the invention.
  • Composition A:
    • 0.04 g of potassium permanganate
    • 2 g 1-Hydroxyethane-(1,1-diphosphonic acid) (HEDP)
    • 996.4 grams of water
  • Composition B:
    • 0.04 g of potassium permanganate
    • 2 g 2-phosphonobutane-1,2,4-tricarboxylic acid (PBTC)
    • 996.4 grams of water
  • Composition C:
    • 0.04 g of potassium permanganate
    • 2 g amino-tris(methylenephosphonic acid) (ATMP)
    • 996.4 grams of water
  • Composition D:
    • 0.04 g of potassium permanganate
    • 2 g diethylene triamine penta (methylene phosphonic acid) (DTPMP)
    • 996.4 grams of water
  • Composition E:
    • 0.04 g of potassium permanganate
    • 2 g ethylenediaminetetra(methylenephosphonic acid) (EDTMP) 996.4 g water
  • Composition F:
    • 0.04 g of potassium permanganate
    • 2 g 1-Hydroxyethane-(1,1-diphosphonic acid) (HEDP)
    • 5g NaOH
    • 991.4 grams of water
  • Composition G:
    • 0.04 g of potassium permanganate
    • 2 g 2-phosphonobutane-1,2,4-tricarboxylic acid (PBTC)
    • 5g NaOH
    • 991.4 grams of water
  • Composition H:
    • 0.04 g of potassium permanganate
    • 2 g amino-tris(methylenephosphonic acid) (ATMP)
    • 5g NaOH
    • 991.4 grams of water
  • Composition I:
    • 0.04 g of potassium permanganate
    • 2 g diethylene triamine penta (methylene phosphonic acid) (DTPMP)
    • 5g NaOH
    • 991.4 grams of water
  • Composition J:
    • 0.04 g of potassium permanganate
    • 2 g ethylenediaminetetra(methylenephosphonic acid) (EDTMP)
    • 5g NaOH
    • 991.4 grams of water
  • Composition K:
    • 0.04 g of potassium permanganate
    • 2 g 1-Hydroxyethane-(1,1-diphosphonic acid) (HEDP)
    • 5g NaOH
    • 5 g sodium peroxodisulphate
    • 986.4 grams of water
  • Composition L:
    • 0.04 g of potassium permanganate
    • 2 g 2-phosphonobutane-1,2,4-tricarboxylic acid (PBTC)
    • 5g NaOH
    • 5 g sodium peroxodisulphate
    • 986.4 grams of water
  • Composition M:
    • 0.04 g of potassium permanganate
    • 2 g amino-tris(methylenephosphonic acid) (ATMP)
    • 5g NaOH
    • 5 g sodium peroxodisulphate
    • 986.4 grams of water
  • Composition N:
    • 0.04 g of potassium permanganate
    • 2 g diethylene triamine penta (methylene phosphonic acid) (DTPMP)
    • 5g NaOH
    • 5 g sodium peroxodisulphate
    • 986.4 grams of water
  • Composition O:
    • 0.04 g of potassium permanganate
    • 2 g ethylenediaminetetra(methylenephosphonic acid) (EDTMP)
    • 5g NaOH
    • 5 g sodium peroxodisulphate
    • 986.4 grams of water
  • Comparative composition 1:
    • 0.04 g of potassium permanganate
    • 2 g 1-Hydroxyethane-(1,1-diphosphonic acid) (HEDP)
    • 5g NaOH
    • 5 grams of hydrogen peroxide
    • 986.4 grams of water
  • Comparative composition 2:
    • 0.04 g of potassium permanganate
    • 2 g 2-phosphonobutane-1,2,4-tricarboxylic acid (PBTC)
    • 5g NaOH
    • 5 grams of hydrogen peroxide
    • 986.4 grams of water
  • Comparative composition 3:
    • 0.04 g of potassium permanganate
    • 2 g amino-tris(methylenephosphonic acid) (ATMP)
    • 5g NaOH
    • 5 grams of hydrogen peroxide
    • 986.4 grams of water
  • Comparative composition 4:
    • 0.04 g of potassium permanganate
    • 2 g diethylene triamine penta (methylene phosphonic acid) (DTPMP)
    • 5g NaOH
    • 5 grams of hydrogen peroxide
    • 986.4 grams of water
  • Comparative composition 5:
    • 0.04 g of potassium permanganate
    • 2 g ethylenediaminetetra(methylenephosphonic acid) (EDTMP)
    • 5g NaOH
    • 5 grams of hydrogen peroxide
    • 986.4 grams of water

Die Komponenten der Zusammensetzungen A bis O und der Vergleichszusammensetzungen 1 bis 5 wurden vermischt und in Wasser gelöst. Anschließend wurden die Zusammensetzungen bei 40°C für insgesamt 60 Minuten in einem geschlossenen Gefäß inkubiert. In den ersten 30 Minuten wurde nach jeweils nach 5 Minuten Inkubation die Absorption der wässrigen Zusammensetzungen bei 425 nm und bei 580 nm (Absorptionsmaximum von Permanganat) gemessen. Die Absorptionsabnahme der gemessenen Zusammensetzungen bei 580 nm zeigt die Reduktion von Kaliumpermanganat in der Lösung. Nach 30 Minuten wurde das Messinterval auf 10 Minuten verlängert. Je rascher die Abnahme der Absorption der Zusammensetzungen und somit die Reduktion des darin befindlichen Kaliumpermanganats erfolgt, desto ungeeigneter sind diese, um bei der Bestimmung des Vorhandenseins von organischen Verbindungen in Proben eingesetzt zu werden. Die Absorption bei Minute 0 jeder Zusammensetzung wurde mit 100% festgelegt, die Ergebnisse der Absorptionsmessungen zu den jeweiligen Zeitpunkten wurden zu jener bei Minute 0 korreliert.The components of Compositions A to O and Comparative Compositions 1 to 5 were mixed and dissolved in water. Subsequently, the compositions were incubated at 40°C for a total of 60 minutes in a closed vessel. In the first 30 minutes, after 5 minutes of incubation, the absorption of the aqueous compositions was measured at 425 nm and at 580 nm (absorption maximum of permanganate). The decrease in absorbance of the measured compositions at 580 nm shows the reduction of potassium permanganate in the solution. After 30 minutes, the measurement interval was extended to 10 minutes. je The quicker the decrease in the absorption of the compositions and thus the reduction of the potassium permanganate present therein occurs, the less suitable they are for use in determining the presence of organic compounds in samples. The absorbance at minute 0 of each composition was set at 100%, the results of the absorbance measurements at the respective time points were correlated to that at minute 0.

Ergebnisse:Results:

Tabelle A: Absorption der Zusammensetzungen A bis E bei 580 nm, wobei die Absorptionswerte bei Minute 0 mit 100% festgelegt wurde und die weiteren Messergebnisse der Untersuchung entsprechend korreliert wurden (Mittelwert von drei unabhängigen Messungen). Table A: Absorption of compositions A to E at 580 nm, with the absorption values at minute 0 being set at 100% and the further measurement results of the investigation being correlated accordingly (mean value of three independent measurements). Zusammensetzung/ Messzeitpunkt [min]Composition/ time of measurement [min] AA BB CC DD EE 00 100%100% 100%100% 100%100% 100%100% 100%100% 55 98,7%98.7% 99,1%99.1% 91, 9%91.9% 93,5%93.5% 92,2%92.2% 1010 95,3%95.3% 97,2%97.2% 82,2%82.2% 87,0%87.0% 85,1%85.1% 1515 93,1%93.1% 94,7%94.7% 70,7%70.7% 72,2%72.2% 69,3%69.3% 2020 91, 9%91.9% 92,8%92.8% 63,1%63.1% 62,8%62.8% 63, 6%63.6% 2525 87,1%87.1% 87, 9%87.9% 55,8%55.8% 53,7%53.7% 56,8%56.8% 3030 85,0%85.0% 84,3%84.3% 50,2%50.2% 48,3%48.3% 47, 9%47.9% 4040 82, 6%82.6% 82,1%82.1% 41,0%41.0% 42,4%42.4% 41,5%41.5% 5050 81,1%81.1% 80,3%80.3% 35, 9%35.9% 36,8%36.8% 37,1%37.1% 6060 79, 9%79.9% 78,1%78.1% 31,2%31.2% 30, 9%30.9% 29,3%29.3%

Da in vielen Reinigungslösungen Alkalihydroxide vorhanden sind, die für eine effizientere Reinigung sorgen, wurde untersucht, ob das Vorhandensein von NaOH einen Einfluss auf die Reduktion von Kaliumpermanganat hat. Tabelle B: Absorption der Zusammensetzungen F bis J bei 580 nm, wobei die Absorptionswerte bei Minute 0 mit 100% festgelegt wurde und die weiteren Messergebnisse der Untersuchung entsprechend korreliert wurden (Mittelwert von drei unabhängigen Messungen). Zusammensetzung/ Messzeitpunkt [min] F G H I J 0 100% 100% 100% 100% 100% 5 99,1% 98,2% 93,2% 91,2% 94,4% 10 96,8% 97,1% 87,4% 86,3% 89,2% 15 94,1% 93,2% 80,1% 72,8% 71,3% 20 92,4% 91, 6% 72,8% 62, 9% 66,4% 25 89,3% 88, 9% 65,0% 53,4% 57, 6% 30 87,2% 86, 6% 59,7% 48, 6% 46,5% 40 85, 6% 85,4% 46,5% 42,5% 43,4% 50 83,7% 82,7% 38,4% 36,2% 35,7% 60 80,8% 79, 9% 31,3% 30,1% 30,8% Since alkali hydroxides are present in many cleaning solutions, which ensure more efficient cleaning, it was investigated whether the presence of NaOH has an influence on the reduction of potassium permanganate. <b>Table B:</b> Absorption of compositions F to J at 580 nm, whereby the absorption values at minute 0 were set at 100% and the further measurement results of the investigation were correlated accordingly (mean value of three independent measurements). Composition/ time of measurement [min] f G H I J 0 100% 100% 100% 100% 100% 5 99.1% 98.2% 93.2% 91.2% 94.4% 10 96.8% 97.1% 87.4% 86.3% 89.2% 15 94.1% 93.2% 80.1% 72.8% 71.3% 20 92.4% 91.6% 72.8% 62.9% 66.4% 25 89.3% 88.9% 65.0% 53.4% 57.6% 30 87.2% 86.6% 59.7% 48.6% 46.5% 40 85.6% 85.4% 46.5% 42.5% 43.4% 50 83.7% 82.7% 38.4% 36.2% 35.7% 60 80.8% 79.9% 31.3% 30.1% 30.8%

Reinigungslösungen bzw. -zusammensetzungen können ferner weitere Oxidationsmittel mit anorganische Peroxidasen und Persulfate umfassen. Auch der Einfluss solcher Oxidationsmittel auf die Stabilität von Kaliumpermanganat wurde analysiert. Tabelle C: Absorption der Zusammensetzungen K bis O bei 580 nm, wobei die Absorptionswerte bei Minute 0 mit 100% festgelegt wurde und die weiteren Messergebnisse der Untersuchung entsprechend korreliert wurden (Mittelwert von drei unabhängigen Messungen) . Zusammensetzung/ Messzeitpunkt [min] K L M N O 0 100% 100% 100% 100% 100% 5 97,2% 99, 7% 90,4% 91,7% 92, 6% 10 96,4% 96, 6% 79, 6% 86, 6% 89,3% 15 93, 9% 95,4% 71,3% 78, 9% 75, 9% 20 92,7% 94,3% 66,5% 67,0% 64,7% 25 89,0% 91, 9% 59,3% 56,3% 52, 6% 30 86,3% 87,8% 52,1% 49,4% 46,5% 40 85,1% 84,0% 43,1% 43, 9% 43,5% 50 84,3% 82,5% 36,7% 32,5% 31,1% 60 82,8% 79,2% 30, 6% 28, 6% 26,0% Cleaning solutions or compositions can also include other oxidizing agents with inorganic peroxidases and persulfates. The influence of such oxidizing agents on the stability of potassium permanganate was also analyzed. <b>Table C:</b> Absorption of the compositions K to O at 580 nm, whereby the absorption values at minute 0 were set at 100% and the further measurement results of the investigation were correlated accordingly (mean value of three independent measurements). Composition/ time of measurement [min] K L M N O 0 100% 100% 100% 100% 100% 5 97.2% 99.7% 90.4% 91.7% 92.6% 10 96.4% 96.6% 79.6% 86.6% 89.3% 15 93.9% 95.4% 71.3% 78.9% 75.9% 20 92.7% 94.3% 66.5% 67.0% 64.7% 25 89.0% 91.9% 59.3% 56.3% 52.6% 30 86.3% 87.8% 52.1% 49.4% 46.5% 40 85.1% 84.0% 43.1% 43.9% 43.5% 50 84.3% 82.5% 36.7% 32.5% 31.1% 60 82.8% 79.2% 30.6% 28.6% 26.0%

Die Ergebnisse der Absorptionsmessungen zeigen eindeutig und eindrucksvoll, dass eine bestimmte Gruppe von organischen Phosphonaten in der Lage ist, relativ stabile Kaliumpermanganatlösungen bereitzustellen. Der Einsatz von organischen Phosphonaten, die organische Gruppen mit Heteroatomen aufweisen, führte dazu, dass Kaliumpermanganat rascher reduziert wird. Tabelle D: Absorption der Vergleichszusammensetzungen 1 bis 5 bei 580 nm, wobei die Absorptionswerte bei Minute 0 mit 100% festgelegt wurde und die weiteren Messergebnisse der Untersuchung entsprechend korreliert wurden (Mittelwert von drei unabhängigen Messungen). Zusammensetzung/ Messzeitpunkt [min] 1 2 3 4 5 0 100% 100% 100% 100% 100% 5 90,1% 91,2% 70,4% 73,1% 72,8% 10 87,2% 89, 8% 67,5% 69,4% 69,1% 15 86,1% 88,2% 63,2% 65,7% 67,0% 20 84, 9% 85,7% 61,4% 62, 9% 61, 9% 25 81,7% 80,2% 58, 9% 56,4% 58,5% 30 77,1% 76,3% 54,2% 50,5% 53, 6% 40 74,2% 74,7% 49, 9% 46,3% 48,8% 50 71, 6% 70,5% 38,7% 39,2% 36,7% 60 65,8% 67,1% 32,1% 33,5% 31,1% The results of the absorption measurements clearly and impressively show that a certain group of organic phosphonates is able to provide relatively stable potassium permanganate solutions. The use of organic phosphonates, which have organic groups with heteroatoms, resulted in potassium permanganate being reduced more rapidly. <b>Table D:</b> Absorption of the comparative compositions 1 to 5 at 580 nm, whereby the absorption values at minute 0 were set at 100% and the further measurement results of the investigation were correlated accordingly (mean value of three independent measurements). Composition/ time of measurement [min] 1 2 3 4 5 0 100% 100% 100% 100% 100% 5 90.1% 91.2% 70.4% 73.1% 72.8% 10 87.2% 89.8% 67.5% 69.4% 69.1% 15 86.1% 88.2% 63.2% 65.7% 67.0% 20 84.9% 85.7% 61.4% 62.9% 61.9% 25 81.7% 80.2% 58.9% 56.4% 58.5% 30 77.1% 76.3% 54.2% 50.5% 53.6% 40 74.2% 74.7% 49.9% 46.3% 48.8% 50 71.6% 70.5% 38.7% 39.2% 36.7% 60 65.8% 67.1% 32.1% 33.5% 31.1%

Die Ergebnisse der Absorptionsmessungen belegen, dass die Verwendung eines alternativen Oxidationsmittels anstelle von Persulfat (d.h. Wasserstoffperoxid) zu einer verminderten Stabilität des Kaliumpermanganats führt. D.h. die Verwendung von Persulfaten führte im Vergleich zur Verwendung anderer Oxidationsmittel zu einer Stabilisierung des Permanganats.The results of the absorbance measurements show that the use of an alternative oxidizing agent instead of persulfate (i.e. hydrogen peroxide) leads to reduced stability of the potassium permanganate. This means that the use of persulfates leads to a stabilization of the permanganate compared to the use of other oxidizing agents.

Claims (13)

  1. A composition for cleaning surfaces and/or for detecting organic substances in a solution or on a surface, comprising
    a) at least one salt of the permanganic acid, ferric acid and/or chromic acid,
    b) at least one organic phosphonate and
    c) at least one persulphate,
    wherein at least one organic phosphonate is selected from the group consisting of 1-hydroxy ethane-(1,1-diphosphonic acid), 2-phosphono-butane-1,2,4-tricarboxylic acid and a salt thereof.
  2. The composition according to claim 1, wherein the salt of the at least one organic phosphonate is an alkali salt.
  3. The composition according to claim 1 or 2, wherein the at least one salt of the permanganic acid, ferric acid and/or chromic acid is an alkali salt, preferably selected from the group consisting of potassium permanganate, potassium ferrate and potassium dichromate.
  4. The composition according to any one of claims 1 to 3, wherein the at least one persulphate is a salt of the peroxo-disulphuric acid or of the peroxo-mono-sulphuric acid.
  5. The composition according to any one of claims 1 to4, wherein the at least one persulphate is a peroxo-disulphate selected from the group consisting of sodium peroxo-disulphate, potassium peroxo-disulphate and ammonium peroxo-disulphate and/or a peroxo-monosulphate selected from the group consisting of potassium peroxo-monosulphate.
  6. The composition according to any one of claims 1 to 5, wherein the composition comprises at least one calcium salt, which is preferably selected from the group consisting of calcium nitrate.
  7. The composition according to any one of claims 1 to 6, wherein the composition comprises the at least one salt of the permanganic acid, ferric acid and/or chromic acid at a weight ratio to the at least one organic phosphonate of 1:50 to 1:500, preferably 1:75 to 1:300, even more preferably 1: 100 to 1:200.
  8. The composition according to any one of claims 1 to 7, wherein the composition is an aqueous composition, wherein the composition comprises more than 50% by weight, preferably more than 70% by weight, even more preferably more than 90% by weight, water.
  9. The composition according to claims 7 or 8, wherein the aqueous composition comprises 0.01% by weight to 1% by weight, preferably 0.02% by weight to 0.9% by weight, even more preferably 0.05% by weight to 0.8% by weight, even more preferably 0.075% by weight to 0.7% by weight, even more preferably 0.1% by weight to 0.6% by weight, even more preferably 0.2% by weight to 0.6% by weight, even more preferably 0.3% by weight to 0.6% by weight, of the at least one organic phosphonate.
  10. The composition according to any one of claims 1 to 7, wherein the composition is substantially free of water.
  11. The composition according to any one of claims 1 to 10, wherein the composition includes at least one alkali hydroxide wherein the at least one alkali hydroxide is NaOH, KOH or LiOH.
  12. A kit for cleaning surfaces and/or for detecting organic substances in a solution or on a surface, comprising
    a1) a container comprising a composition according to any of claims 1 to 10 and
    b1) a container comprising at least one alkali hydroxide or
    a2) a container comprising at least one alkali salt of the permanganic acid, ferric acid and/or chromic acid as defined in claim 3,
    b2) a container comprising at least one organic phosphonate as defined in any one of claims 1 or2 and optionally at least one persulphate as defined in any one of claims 4 or 5 and
    c2) a container comprising at least one alkali hydroxide, wherein the at least one alkali hydroxide is NaOH, KOH or LiOH.
  13. A method for cleaning surfaces and/or for detecting organic substances in a solution or on a surface, comprising the step of contacting a composition according to any one of claims 1 to 11 or a composition obtainable by mixing the components in the containers a1 and b1 or a2, b2 and b3 with the surface to be cleaned or with the surface or solution, on or in which organic substances are to be detected.
EP18723670.8A 2017-04-29 2018-04-27 Composition for cleaning surfaces Active EP3615650B1 (en)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
ATA50350/2017A AT519943A1 (en) 2017-04-29 2017-04-29 COMPOSITION
PCT/AT2018/060086 WO2018195577A1 (en) 2017-04-29 2018-04-27 Composition for cleaning surfaces

Publications (3)

Publication Number Publication Date
EP3615650A1 EP3615650A1 (en) 2020-03-04
EP3615650C0 EP3615650C0 (en) 2023-08-02
EP3615650B1 true EP3615650B1 (en) 2023-08-02

Family

ID=62148057

Family Applications (1)

Application Number Title Priority Date Filing Date
EP18723670.8A Active EP3615650B1 (en) 2017-04-29 2018-04-27 Composition for cleaning surfaces

Country Status (6)

Country Link
US (1) US20200140783A1 (en)
EP (1) EP3615650B1 (en)
CN (1) CN110637079B (en)
AT (1) AT519943A1 (en)
CA (1) CA3060321A1 (en)
WO (1) WO2018195577A1 (en)

Family Cites Families (13)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3286475A (en) * 1963-03-27 1966-11-22 Nalco Chemical Co Method of agglomerating and stabilizing particulate matter by chemical treatment
GB8724901D0 (en) * 1987-10-23 1987-11-25 Unilever Plc Detergent bleach compositions
SE508954C2 (en) * 1997-03-21 1998-11-16 Eriksson Jan Olof Detergent, free from surfactants
AT408987B (en) * 2000-10-13 2002-04-25 Thonhauser Gmbh Dipl Ing Cleaner and disinfectant
AU2003238773A1 (en) * 2002-06-07 2003-12-22 Mallinckrodt Baker Inc. Microelectronic cleaning compositions containing oxidizers and organic solvents
TW200517406A (en) * 2003-10-29 2005-06-01 Nippon Catalytic Chem Ind Polymer, process for preparing the same, and use of the same
AT413032B (en) * 2003-11-11 2005-10-15 Thonhauser Gmbh Dipl Ing CLEANING, DISINFECTION AND INDICATORS
US8663607B2 (en) * 2007-03-09 2014-03-04 Battelle Memorial Institute Ferrate(VI)-containing compositions and methods of using ferrate(VI)
US8034759B2 (en) * 2008-10-31 2011-10-11 Ecolab Usa Inc. Enhanced stability peracid compositions
EP2450114A1 (en) * 2010-11-08 2012-05-09 Biorem Engineering SARL Gel comprising reactive oxidant release agent
CN102180540B (en) * 2011-03-24 2013-02-13 哈尔滨工业大学 Water treatment medicament for eliminating pollution through oxidation of high-activity intermediate state pentavalent manganese
US11127587B2 (en) * 2014-02-05 2021-09-21 Entegris, Inc. Non-amine post-CMP compositions and method of use
WO2016069576A1 (en) * 2014-10-31 2016-05-06 Entegris, Inc. Non-amine post-cmp compositions and method of use

Also Published As

Publication number Publication date
EP3615650C0 (en) 2023-08-02
CN110637079B (en) 2022-02-22
US20200140783A1 (en) 2020-05-07
AT519943A1 (en) 2018-11-15
EP3615650A1 (en) 2020-03-04
CN110637079A (en) 2019-12-31
WO2018195577A1 (en) 2018-11-01
CA3060321A1 (en) 2018-11-01

Similar Documents

Publication Publication Date Title
DE69412838T2 (en) POTENTIAL AQUEOUS OZONE DETERGENT COMPOSITION FOR REMOVING DIRT FROM A SURFACE
DE69819593T2 (en) Detergent formulations
EP0164514B1 (en) Use of lamellar crystalline sodium silicates in water-softening processes
DE69231686T2 (en) STABLE, ANTICORROSIVE PERESSIG- / PEROXID-STERILI-SATIONAL
DE3928747A1 (en) METHOD FOR DISINFECTING HARD SURFACES WITH CHLORDIOXIDE
DE19630615A1 (en) Process for cleaning and disinfecting surfaces and production facilities
DE2622458A1 (en) PROCESS FOR STABILIZATION OF SODIUM PERCARBONATE
AT408987B (en) Cleaner and disinfectant
DE69214517T2 (en) Simultaneous use of water-soluble polymers with ozone in cooling water circuits
DE69722353T2 (en) Cleaning, disinfecting and bleaching composition
EP3615650B1 (en) Composition for cleaning surfaces
AT413032B (en) CLEANING, DISINFECTION AND INDICATORS
EP3850072A1 (en) Silver protection agent
DE60105280T2 (en) sequestration
DE1617235A1 (en) Detergents
EP3615647B1 (en) Method for cleaning surfaces
DE1289815B (en) Stable aqueous bleach solution
EP1709978A1 (en) Cleaning and disinfection of surgical and medical instruments and devices
DE1469233A1 (en) A method and means for imparting complexing properties to an aqueous solution containing a chlorine developing agent
DE69808445T2 (en) CLEANING TOILET POOLS WITH LIQUID HYPOCHLORITE COMPOSITIONS
DE2106618A1 (en) Process for cleaning the surfaces of heat exchangers and other apparatus doors that come into contact with aqueous liquids containing mineral and / or organic substances
DE68907393T2 (en) Process for removing oxygen and preventing crust formation in boilers.
WO1998040107A2 (en) Use of a solution to deactivate endotoxins
EP3138401B1 (en) Disinfectant composition
DE135830C (en)

Legal Events

Date Code Title Description
STAA Information on the status of an ep patent application or granted ep patent

Free format text: STATUS: UNKNOWN

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

Free format text: STATUS: THE INTERNATIONAL PUBLICATION HAS BEEN MADE

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

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

Free format text: STATUS: REQUEST FOR EXAMINATION WAS MADE

17P Request for examination filed

Effective date: 20191119

AK Designated contracting states

Kind code of ref document: A1

Designated state(s): AL AT BE BG CH CY CZ DE DK EE ES FI FR GB GR HR HU IE IS IT LI LT LU LV MC MK MT NL NO PL PT RO RS SE SI SK SM TR

AX Request for extension of the european patent

Extension state: BA ME

DAV Request for validation of the european patent (deleted)
DAX Request for extension of the european patent (deleted)
STAA Information on the status of an ep patent application or granted ep patent

Free format text: STATUS: EXAMINATION IS IN PROGRESS

17Q First examination report despatched

Effective date: 20220627

GRAP Despatch of communication of intention to grant a patent

Free format text: ORIGINAL CODE: EPIDOSNIGR1

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

Free format text: STATUS: GRANT OF PATENT IS INTENDED

INTG Intention to grant announced

Effective date: 20230303

GRAS Grant fee paid

Free format text: ORIGINAL CODE: EPIDOSNIGR3

GRAA (expected) grant

Free format text: ORIGINAL CODE: 0009210

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

Free format text: STATUS: THE PATENT HAS BEEN GRANTED

AK Designated contracting states

Kind code of ref document: B1

Designated state(s): AL AT BE BG CH CY CZ DE DK EE ES FI FR GB GR HR HU IE IS IT LI LT LU LV MC MK MT NL NO PL PT RO RS SE SI SK SM TR

REG Reference to a national code

Ref country code: GB

Ref legal event code: FG4D

Free format text: NOT ENGLISH

REG Reference to a national code

Ref country code: CH

Ref legal event code: EP

REG Reference to a national code

Ref country code: DE

Ref legal event code: R096

Ref document number: 502018012857

Country of ref document: DE

REG Reference to a national code

Ref country code: IE

Ref legal event code: FG4D

Free format text: LANGUAGE OF EP DOCUMENT: GERMAN

U01 Request for unitary effect filed

Effective date: 20230808

U07 Unitary effect registered

Designated state(s): AT BE BG DE DK EE FI FR IT LT LU LV MT NL PT SE SI

Effective date: 20230811

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

Ref country code: GR

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20231103

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

Ref country code: IS

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20231202

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

Ref country code: RS

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20230802

Ref country code: NO

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20231102

Ref country code: IS

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20231202

Ref country code: HR

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20230802

Ref country code: GR

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20231103

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

Ref country code: PL

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20230802

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 FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20230802

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

Ref country code: SM

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20230802

Ref country code: RO

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20230802

Ref country code: ES

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20230802

Ref country code: CZ

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20230802

Ref country code: SK

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20230802

REG Reference to a national code

Ref country code: DE

Ref legal event code: R097

Ref document number: 502018012857

Country of ref document: DE

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

U21 Renewal fee paid with penalty [unitary effect]

Year of fee payment: 7

Effective date: 20240522

26N No opposition filed

Effective date: 20240503