EP0994178A1 - Cleaning compositions and their use - Google Patents

Cleaning compositions and their use Download PDF

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Publication number
EP0994178A1
EP0994178A1 EP99120336A EP99120336A EP0994178A1 EP 0994178 A1 EP0994178 A1 EP 0994178A1 EP 99120336 A EP99120336 A EP 99120336A EP 99120336 A EP99120336 A EP 99120336A EP 0994178 A1 EP0994178 A1 EP 0994178A1
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EP
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Prior art keywords
cleaning
weight
agent according
cleaning agent
carbon atoms
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EP99120336A
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German (de)
French (fr)
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EP0994178B1 (en
Inventor
Andreas c/o B. Braun Medical AG Arndt
Nadeshda c/o B. Braun Medical AG Arndt
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B Braun Medical AG
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B Braun Medical AG
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Classifications

    • CCHEMISTRY; METALLURGY
    • C11ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11DDETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D3/00Other compounding ingredients of detergent compositions covered in group C11D1/00
    • C11D3/16Organic compounds
    • C11D3/26Organic compounds containing nitrogen
    • C11D3/28Heterocyclic compounds containing nitrogen in the ring
    • CCHEMISTRY; METALLURGY
    • C11ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11DDETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D1/00Detergent compositions based essentially on surface-active compounds; Use of these compounds as a detergent
    • C11D1/66Non-ionic compounds
    • C11D1/83Mixtures of non-ionic with anionic compounds
    • CCHEMISTRY; METALLURGY
    • C11ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11DDETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D1/00Detergent compositions based essentially on surface-active compounds; Use of these compounds as a detergent
    • C11D1/02Anionic compounds
    • C11D1/04Carboxylic acids or salts thereof
    • C11D1/06Ether- or thioether carboxylic acids
    • CCHEMISTRY; METALLURGY
    • C11ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11DDETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D1/00Detergent compositions based essentially on surface-active compounds; Use of these compounds as a detergent
    • C11D1/66Non-ionic compounds
    • C11D1/72Ethers of polyoxyalkylene glycols
    • C11D1/721End blocked ethers
    • CCHEMISTRY; METALLURGY
    • C11ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11DDETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D1/00Detergent compositions based essentially on surface-active compounds; Use of these compounds as a detergent
    • C11D1/66Non-ionic compounds
    • C11D1/722Ethers of polyoxyalkylene glycols having mixed oxyalkylene groups; Polyalkoxylated fatty alcohols or polyalkoxylated alkylaryl alcohols with mixed oxyalkylele groups
    • CCHEMISTRY; METALLURGY
    • C11ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11DDETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D1/00Detergent compositions based essentially on surface-active compounds; Use of these compounds as a detergent
    • C11D1/66Non-ionic compounds
    • C11D1/75Amino oxides

Definitions

  • the invention relates to compositions comprising ether carboxylates, nonionic Surfactants and N-alkylpyrrolidones as well as other auxiliary substances.
  • the compositions are characterized by a particular low foam level and at the same time lower Surface tension and high cleaning activity.
  • the compositions do not contain cumene sulfonate as a solubilizer and can if necessary can also be formulated without solvents.
  • the agents according to the invention become mechanical and manual cleaning of hard surfaces, especially of medical devices, surgical instruments, rigid and flexible Endoscopes, inventory and other inanimate surfaces are used.
  • Surgical instruments are increasingly being machined today prepared special cleaning and disinfection machines.
  • the cleaning step is particularly sensitive because it is residue-free Cleaning blood, secretion and protein contaminants prevents incrustations of residual contamination from the subsequent thermal or thermo-chemical Disinfection step. How difficult a mechanical residue-free Cleaning is actually done mostly on microsurgical Instruments and flexible endoscopes clearly, which is a complicated system of sometimes extremely narrow channels, branches and spindly cavities form.
  • sensitive materials e.g. complicated optics, special adhesives, light guides, more sensitive to corrosion Metals and highly elastic plastics a particularly gentle treatment, the functionality of the sometimes very expensive devices even after many Processing cycles not to be affected.
  • Alkaline cleaners attempt this task by adding active chlorine or to meet active oxygen compounds, which also without the addition of surfactants are able to solve protein contamination from surfaces.
  • the disadvantage here is the high pH and the associated poor quality Material compatibility, especially compared to anodized aluminum, but also Nonferrous metals or special alloys. Therefore, in recent times, have increased mildly alkaline and pH neutral cleaners are suggested based on low-foam non-ionic and / or anionic surfactants are built up and Supporting the cleaning effect may contain proteolytic enzymes can.
  • EP-A-0 268 227 describes a cleaning agent which contains at least one non-ionic low-foaming surfactant, complexing agents, proteolytic enzymes as well contains other detergent ingredients.
  • nonionic surfactants Investment products of ethylene oxide and optionally propylene oxide saturated fatty alcohols claimed in which the terminal hydroxyl groups can be etherified, esterified or acetalized with an aliphatic alcohol.
  • Comparable cleaning agents on this basis make themselves low Use the cloud point of the surfactants used.
  • Such a detergent solution is usually clear at lower temperatures to become warm tarnish.
  • This partial separation from the aqueous phase means that Surfactants mostly at temperatures above 25-30 ° C as foam inhibitors, see above that even mechanical cleaning processes with high turbulence without problems can be carried out.
  • the aqueous phase becomes surface-active in this way Withdrawn substance, so that especially at higher temperatures 45 ° C increased wetting problems occur on the surfaces to be cleaned can and the cleaning effect of such a solution on the mechanical
  • the strength of the solution remains limited. Provided the temperature of the cleaning solution but is still below the cloud point, can be in washing machines and disinfectors increased foaming occur, which in the case of cleaning from flexible endoscopes to automatic system shutdown and thus an interruption of the cleaning process due to pressure loss Can cause foaming.
  • DE-A-196 07 530 describes a cleaner which, in addition to enzymes, complexing agents and other customary constituents, contains an anionic surfactant of the type of a short-chain C 5 -C 10 alkyl sulfate salt as the surfactant base. It is known that anionic surfactants have a good cleaning-supporting effect, surfactants with hydrophobic residues from 10 carbon atoms tend to form a lot of foam. If, as described in DE-A-196 07 530, surfactants with short-chain branched hydrophobic radicals are used, it is possible to produce formulations whose dilute solutions are characterized by a constant low foam formation over the entire temperature range, but strong in their wetting ability and cleaning activity to be desired.
  • the surfactant base should have good biodegradability and for improvement no biologically hard fluorosurfactants are used come.
  • the agent and its working solutions should preferably pH be neutral to slightly acidic to ensure optimal tolerance of the product and its solution compared to the usual flexible ones used in medicine Ensure plastic materials and metallic materials.
  • alkyl polyglycol ether carboxylates The class of alkyl polyglycol ether carboxylates is known for its good cleaning properties with a relatively low to moderate tendency to foam. These products are commercially available from KAO Corporation under the collective name Akypo R LF.
  • Akypo R LF The collective name of alkyl polyglycol ether carboxylates.
  • initial attempts at formulation with octyl ether carboxylates showed that the cleaning solutions made from them tended to foam excessively.
  • Attempts to contain the foam by using a blend with the particularly short-chain butyl ether carboxylate did not bring the hoped-for success, since the foam now disintegrated faster, but the initial foam height at time 0 remained almost unchanged.
  • low-foam, storage-stable formulations that meet the requirements mentioned above if the mixtures contain at least one ether carboxylate, at least one contain nonionic surfactant and at least one N-alkylpyrrolidone.
  • This composition can be present as a concentrate, which is in aqueous or aqueous-alcoholic Solution can be used (application solution).
  • composition according to the invention is in a special embodiment free of difficult or non-degradable foam dampers, such as EO-PO block polymers in particular, Silicone derivatives and / or paraffin oil and solubilizers, such as in particular cumene or xylene sulfonates.
  • difficult or non-degradable foam dampers such as EO-PO block polymers in particular, Silicone derivatives and / or paraffin oil and solubilizers, such as in particular cumene or xylene sulfonates.
  • the ether carboxylates of the formula I are in the cleaning agent according to the invention preferably in a total concentration of 0.1-10% by weight, particularly preferably in a concentration of 0.1-7% by weight, based on the total amount of the concentrate included.
  • the mono-, di- and trivalent metal ions can be, for example Act alkali and / or alkaline earth metal ions.
  • the alkyl radical R 1 preferably contains 4-13, particularly preferably 4-10 carbon atoms.
  • K preferably takes an integer between 0 and 9, particularly preferably between 5 and 9.
  • a preferred ether carboxylate is sodium C 8 alkyl ether carboxylate (6 EO) (sodium capryleth (6) carboxylate).
  • the nonionic surfactants of formula II are in the agent according to the invention preferably in a concentration of 0.1-30% by weight, particularly preferably in a concentration of 0.1-15 wt .-%, based on the total amount of Concentrate.
  • M preferably takes an integer between 3 and 20 on.
  • the particularly preferred nonionic surfactants are one Octyl ethoxylate with 6-10 EO, terminally sealed with an octylglyceryl ether, as it e.g. by HACOBA AG (Basel) under the trade name TN 55 ether surfactant is offered.
  • N-alkylpyrrolidones in the agent according to the invention are preferably in a concentration of 0.01-15 wt .-%, particularly preferably in a concentration of 0.01-5 wt .-%, based on the total amount of the concentrate.
  • the aqueous solution comprises at least a total 1.0% by weight of components (a), (b) and (c), based on the Total amount of solution.
  • the 100% by weight missing part can be replaced by the optional mentioned below Components and water are added.
  • the cleaning agent can additionally 0.1-30 wt .-%, preferably 0.5-20 Wt .-% contain complexing agents and water hardness stabilizers, with salts organic acids, e.g. Salts of citric acid, gluconic acid, nitrilotriacetic acid, EDTA, aminotrismethylenephosphonic acid, hydroxyethane diphosphonic acid, Phosphonobutane tricarboxylic acid, but also polymers, e.g. Polyacrylates, polycarboxylates, Maleic acid / acrylic acid copolymers or mixtures thereof for Can come into play.
  • salts organic acids e.g. Salts of citric acid, gluconic acid, nitrilotriacetic acid, EDTA, aminotrismethylenephosphonic acid, hydroxyethane diphosphonic acid, Phosphonobutane tricarboxylic acid
  • polymers e.g. Polyacrylates, polycarboxylates, Maleic acid / acrylic acid copoly
  • the agent can contain up to 20% by weight, preferably 1 to 20% by weight.
  • Prefers are polyhydric alcohols, especially propylene glycol, glycerin, sorbitol as well as mixtures of these alcohols.
  • the agent according to the invention can contain up to 5% by weight of corrosion inhibitors, Preservatives, dyes and odor correctors included.
  • the agent according to the invention can still contain up to 20% by weight, preferably 0.1 to 5 wt .-% of other nonionic surfactants that do not fall under the Formula II fall and which are selected from the group of alkyl alkoxylates, Alkylphenol alkoxylates, alkyl polyglucosides, alkyldimethylamine oxides, alkyl fatty acid amides and amide ether carboxylates, the terminal hydroxyl groups the alkyl alkoxylates and alkylphenol alkoxylates can also be etherified.
  • the alkyl group has the usual range of 6 for such surfactants up to 18 carbon atoms.
  • the agent according to the invention can additionally contain up to 20% by weight, preferably 0.01 to 7% by weight, of further anionic and / or amphoteric surfactants which are selected from the group consisting of alkyl sulfates, alkyl sulfonates, alkyl ether sulfates, alkyl C 6 -C 18 aryl sulfonates, alkylbetaines, alkyliminodipropionates, alkylamidopropylbetaines, the essential prerequisite being that the foam behavior of the agent according to the invention and of the application solution is not impaired by the additives.
  • the alkyl group in each case has the range from 6 to 18, preferably 6 to 12, carbon atoms customary for such surfactants.
  • the agent according to the invention up to 10 wt .-%, preferably up to 6% by weight of ethylene glycol monoalkyl ether, diethylene glycol monoalkyl ether, Propylene glycol monoalkyl ether, dipropylene glycol monoalkyl ether or their Add mixtures, the saturated linear or branched alkyl radical 1-6 Has carbon atoms.
  • the pH of the agent is preferably between 4.0 and 13.0 between 4.0 and 9.0 and preferred in the case of an enzyme-containing version Values set between 4.0 and 8.5.
  • the pH is regulated expediently with sodium hydroxide, potassium hydroxide and / or organic alkanolamines, e.g. Triethanolamine or triisopropanolamine or with the organic acids described above.
  • the cleaning agent can be used as the concentrate or used as an aqueous or aqueous / alcoholic solution (application solution) become.
  • An alcohol is preferred in the aqueous / alcoholic application solution used with two or three carbon atoms.
  • the application solutions contain the cleaning agent (concentrate) in one Proportion from 0.1 to 10% by volume, preferably from 0.1 to 2% by volume.
  • the cleaning agents and application solutions according to the invention can be used for Cleaning inanimate surfaces, especially medical ones Equipment, surgical instruments, anesthetic materials, rigid and flexible endoscopes are used. They are particularly suitable Cleaning agents according to the invention and application solutions for cleaning of surgical instruments, rigid and flexible endoscopes in cleaning and disinfection machines. After the cleaning process, a thermal or chemical-thermal disinfection with the usual for this Disinfectants can be used.
  • the invention Cleaning agents and the application solutions can also be used without any problems Cleaning of other inanimate surfaces can be used, such as especially for cleaning bed frames, floors and inventory as well as for Bedpan cleaning.
  • the surface tension was determined in a process known to the person skilled in the art using a commercially available tensiometer from Krüss determined a platinum-iridium ring, the sample vessel was thermostated.
  • the foam values were determined in a swivel foam test. This was done in 50 ml of solution are placed in a 100 ml measuring cylinder, thermostated, 30 times Rotated 180 ° C and then immediately read the foam volume in ml.
  • Recipe 1 was formulated without enzymes, while recipe 2 contains enzymes.
  • Recipe component Recipe 1 Recipe 2 C 8 alkyl ether carboxylic acid 6 EO 4.0 3.5 TN55 ether surfactant 3.0 3.0 N-dodecylpyrrolidone 0.5 1.0 Citric acid 7 2nd Polyacrylate (e.g. Sokalan R types ex. BASF) 4th 10th Triethanolamine - 3rd Enzyme solution (e.g. Savinase R 16.0 L ex.Novo Northern Ireland) - 5 Propylene glycol - 20th Purified water ad 100 ad 100
  • the pH of the formulations according to the invention was in each case with sodium hydroxide solution and citric acid set to 6.0.
  • the recipes Preserved each with 0.1% methyl paraben to protect them against microbial To protect spoilage.
  • the cleaning activity of the formulations according to the invention was determined using a plausible experimental model.
  • stainless steel screws with coagulable Sheep blood contaminated dried at 30 ° C for 1 hour and then always 3 contaminated screws in one each with 200 ml of the concerned Beaker filled with 0.5% detergent solution.
  • inventive Recipes through a constant low temperature independent Foam formation with a particularly low surface tension, a high cloud point and have a particularly good cleaning ability.
  • good material compatibility with instrument steel, anodized aluminum, copper, brass and flexible materials such as Neoprene, soft PVC, polyethylene, rubber, silicone elastomers and latex determined.
  • Tests for the mechanical processing of commercially available Gastroscopes in various cleaning and disinfection machines confirm the advantageous suitability of the agents according to the invention for the described application.

Abstract

Detergent comprises (a) 0.1-30 wt.% ether-carboxylate(s) (I), (b) 0.1-40 wt.% alk(en)yl- or phenyl-ethoxylate terminated with alk(en)yl or phenyl glyceryl ether (II) and (c) 0.01-20 wt.% N-alkylpyrrolidone(s) (III), with an (un)saturated, linear or branched 6-18 C alkyl group, in aqueous solution. Detergent comprises (a) 0.1-30 wt.% ether-carboxylate(s) of formula (I), (b) 0.1-40 wt.% alk(en)yl- or phenyl-ethoxylate terminated with alk(en)yl or phenyl glyceryl ether of formula (II) and (c) 0.01-20 wt.% N-alkylpyrrolidone(s) (III), with an (un)saturated, linear or branched 6-18 carbon (C) alkyl group, in aqueous solution; R<1)<O-CH2-CH2-)k-OCH2COOM (I) R<2)<O-CH2-CH2-)m-CH2-CH(OH)-CH2-RO<3> (II) k = 0-12; m = 1-40; R<1> = (un)saturated, linear or branched 4-18 C alkyl or 10-18 C phenylalkyl; M = a mono-, di- or trivalent metal cation and/or a proton (H<+>); R<2>, R<3> = (un)saturated, linear or branched 3-18 C alkyl or 10-18 C phenylalkyl. An Independent claim is also included for application solutions of the detergent in aqueous or aqueous-alcoholic solution.

Description

Die Erfindung betrifft Zusammensetzungen umfassend Ethercarboxylate, nichtionischen Tenside und N-Alkylpyrrolidone sowie weitere Hilfsstoffe. Die Zusammensetzungen zeichnen sich durch besondere Schaumarmut bei gleichzeitig niedriger Oberflächenspannung und hoher Reinigungsaktivität aus. Die Zusammensetzungen enthalten kein Cumolsulfonat als Lösungsvermittler und können bei Bedarf auch lösemittelfrei formuliert werden. Die erfindungsgemäßen Mittel werden zur maschinellen und manuellen Reinigung von harten Oberflächen, inbesondere von medizinischen Geräten, chirurgischem Instrumentarium, starren und flexiblen Endoskopen, Inventar und weiteren unbelebten Oberflächen eingesetzt.The invention relates to compositions comprising ether carboxylates, nonionic Surfactants and N-alkylpyrrolidones as well as other auxiliary substances. The compositions are characterized by a particular low foam level and at the same time lower Surface tension and high cleaning activity. The compositions do not contain cumene sulfonate as a solubilizer and can if necessary can also be formulated without solvents. The agents according to the invention become mechanical and manual cleaning of hard surfaces, especially of medical devices, surgical instruments, rigid and flexible Endoscopes, inventory and other inanimate surfaces are used.

Stand der TechnikState of the art

Chirurgisches Instrumentarium wird heute in zunehmendem Masse maschinell in speziellen Reinigungs- und Desinfektionsautomaten aufbereitet. Eine Schlüsselrolle kommt dabei den verwendeten Reinigungs- und Desinfektionsmitteln zu, die, den Verfahren Rechnung tragend, spezifischen Anforderungen gerecht werden müssen. Besonders sensibel ist der Reinigungsschritt, denn eine rückstandfreie Reinigung von Blut-, Sekret- und Proteinkontaminationen verhindert Inkrustrationen von Restverschmutzungen durch den nachfolgenden thermischen bzw. thermisch-chemischen Desinfektionsschritt. Wie schwierig eine maschinelle rückstandsfreie Reinigung tatsächlich ist, wird vor allem an mikrochirurgischen Instrumenten und flexiblen Endoskopen deutlich, die ein kompliziertes System von teilweise extrem engen Kanälen, Verzweigungen und spenigen Hohlräumen bilden. Andererseits erfordert der Einsatz empfindlicher Materialien, z.B. komplizierter Optiken, spezieller Klebstoffe, Lichtleiter, korrosionsempfindlicher Metalle und hochelastischer Kunststoffe eine besonders schonende Behandlung, um die Funktionsfähigkeit der teilweise sehr teuren Geräte auch nach vielen Aufbereitungszyklen nicht zu beeinträchtigen. Surgical instruments are increasingly being machined today prepared special cleaning and disinfection machines. A key role the cleaning agents and disinfectants used, which, taking into account the procedure, meeting specific requirements have to. The cleaning step is particularly sensitive because it is residue-free Cleaning blood, secretion and protein contaminants prevents incrustations of residual contamination from the subsequent thermal or thermo-chemical Disinfection step. How difficult a mechanical residue-free Cleaning is actually done mostly on microsurgical Instruments and flexible endoscopes clearly, which is a complicated system of sometimes extremely narrow channels, branches and spindly cavities form. On the other hand, the use of sensitive materials, e.g. complicated optics, special adhesives, light guides, more sensitive to corrosion Metals and highly elastic plastics a particularly gentle treatment, the functionality of the sometimes very expensive devices even after many Processing cycles not to be affected.

Da in automatischen Reinigungsprozessen hohe Turbulenzen auftreten, werden an die eingesetzten Reinigungsmittel besondere Anforderungen in Bezug auf das Schaumverhalten gestellt.Since high turbulence occurs in automatic cleaning processes the cleaning agents used have special requirements with regard to the Foam behavior posed.

Alkalische Reiniger versuchen dieser Aufgabe durch den Zusatz von Aktivchlor oder Aktivsauerstoffverbindungen gerecht zu werden, welche auch ohne den Zusatz von Tensiden Proteinverschmutzungen von Oberflächen zu lösen vermögen. Nachteilig ist dabei der hohe pH-Wert und die damit einhergehende mangelhafte Materialverträglichkeit, insbesondere gegenüber eloxiertem Aluminium, aber auch Buntmetallen bzw. Speziallegierungen. In neuerer Zeit wurden deshalb vermehrt mildalkalische und pH-neutrale Reiniger vorgeschlagen, die auf der Basis schaumarmer nichtionischer und/oder anionischer Tenside aufgebaut sind und zur Unterstützung der Reinigungswirkung gegebenenfalls proteolytische Enzyme enthalten können.Alkaline cleaners attempt this task by adding active chlorine or to meet active oxygen compounds, which also without the addition of surfactants are able to solve protein contamination from surfaces. The disadvantage here is the high pH and the associated poor quality Material compatibility, especially compared to anodized aluminum, but also Nonferrous metals or special alloys. Therefore, in recent times, have increased mildly alkaline and pH neutral cleaners are suggested based on low-foam non-ionic and / or anionic surfactants are built up and Supporting the cleaning effect may contain proteolytic enzymes can.

Damit die Enzyme auch an schwer zugänglichen Stellen ihre Wirkung entfalten können, ist die Tensioaktivität solcher Reinigungsmittel ein besonders wichtiges Kriterium.So that the enzymes work even in hard-to-reach places the tensioactivity of such cleaning agents is particularly important Criteria.

Die EP-A-0 268 227 beschreibt ein Reinigungsmittel, welches mindestens ein nichtionisches schaumarmes Tensid, Komplexbildner, proteolytische Enzyme sowie weitere Reinigungsmittelbestandteile enthält. Als nichtionische Tenside werden Anlagemngsprodukte von Ethylenoxid und gegebenenfalls Propylenoxid an gesättigte Fettalkohole beansprucht, in denen die endständigen Hydroxylgruppen mit einem aliphatischen Alkohol verethert, verestert oder acetalisiert sein können.EP-A-0 268 227 describes a cleaning agent which contains at least one non-ionic low-foaming surfactant, complexing agents, proteolytic enzymes as well contains other detergent ingredients. As nonionic surfactants Investment products of ethylene oxide and optionally propylene oxide saturated fatty alcohols claimed in which the terminal hydroxyl groups can be etherified, esterified or acetalized with an aliphatic alcohol.

Vergleichbare Reinigungsmittel auf dieser Basis machen sich dabei den niedrigen Trübungspunkt der eingesetzten Tenside zunutze. Eine solche Reinigungsmittellösung ist bei tieferen Temperaturen in der Regel klar, um sich bei Erwärmung einzutrüben. Durch diese partielle Trennung von der wässrigen Phase wirken die Tenside meist bei Temperaturen oberhalb von 25-30°C als Schauminhibitoren, so daß auch maschinelle Reinigungsvorgänge mit hohen Turbulenzen problemlos durchgeführt werden können. Gleichzeitig treten dabei aber auch mehrere Probleme zu Tage. Einerseits wird der wässrigen Phase auf diese Weise oberflächenaktive Substanz entzogen, so daß vor allem bei höheren Temperaturen ab 45°C verstärkt Benetzungsprobleme an den zu reinigenden Oberflächen auftreten können und die Reinigungswirkung einer solchen Lösung auf die mechanische Kraft der Lösung beschränkt bleibt. Sofern die Temperatur der Reinigungslösung aber noch unterhalb des Trübungspunktes liegt, kann in Wasch- und Desinfektionsautomaten verstärktes Schäumen auftreten, welches im Falle einer Reinigung von flexiblen Endoskopen bis zum automatischen Abschalten des Systems und damit einer Unterbrechung des Reinigungsprozesses infolge Druckverlustes durch Schaumbildung führen kann.Comparable cleaning agents on this basis make themselves low Use the cloud point of the surfactants used. Such a detergent solution is usually clear at lower temperatures to become warm tarnish. This partial separation from the aqueous phase means that Surfactants mostly at temperatures above 25-30 ° C as foam inhibitors, see above that even mechanical cleaning processes with high turbulence without problems can be carried out. At the same time, however, several problems arise to day. On the one hand, the aqueous phase becomes surface-active in this way Withdrawn substance, so that especially at higher temperatures 45 ° C increased wetting problems occur on the surfaces to be cleaned can and the cleaning effect of such a solution on the mechanical The strength of the solution remains limited. Provided the temperature of the cleaning solution but is still below the cloud point, can be in washing machines and disinfectors increased foaming occur, which in the case of cleaning from flexible endoscopes to automatic system shutdown and thus an interruption of the cleaning process due to pressure loss Can cause foaming.

Ein solches Problem kann immer dann auftreten, wenn der Wasserzulauf des Reinigungsautomaten über kaltes enthärtetes Leitungswasser erfolgt, das Reinigungsmittel direkt nach der Enthärtungsphase zudosiert wird und anschließend das Reinigungsprogramm beginnt. Aus diesem Grund verfügen die marktgängigen Reinigungs- und Desinfektionsautomaten über eine Programmoption, bei der das Zulaufwasser zunächst auf Temperaturen von bis zu 35°C vorgewärmt und erst anschließend das Reinigungsmittel zudosiert wird. Gleichzeitig ist bekannt, daß insbesondere Blutkontaminationen bevorzugt mit Reinigungslösungen von niedrigerer Temperatur zu beseitigen sind, während bei höheren Temperaturen die einsetzende Denaturierung bzw. die weiter fortschreitende Blutgerinnung eine effektive Reinigung eher erschweren kann.Such a problem can always occur when the water supply to the Automatic cleaning machines take place over cold softened tap water, the cleaning agent is added immediately after the softening phase and then the cleaning program begins. For this reason, the marketable Automatic cleaning and disinfection via a program option in which the inlet water is preheated to temperatures of up to 35 ° C and only then the detergent is added. At the same time it is known that in particular blood contamination preferably with cleaning solutions from lower temperatures are to be eliminated while at higher temperatures the onset of denaturation or the progressive blood coagulation effective cleaning can complicate.

Eine Lösung des Problems bestünde darin, nichtionische schaumarme Tenside mit besonders niedrigem Trübungspunkt einzusetzen, so daß im Extremfall bei einer Wasserzulaufstemperatur von 10°C noch eine schaumfreie Arbeit der Reinigungslösung ermöglicht wird. Eine ganze Reihe im Markt befindlicher Reinigungsmittel für die maschinelle Instrumentenaufbereitung sind auf diesen Parameter optimiert. Allerdings treten auch hier teilweise gravierende Nachteile zu Tage. So läßt die Wärmestabilität solcher Mischungen oft zu wünschen übrig, teilweise tritt schon bei Temperaturen ab 35°C eine schleichende Entmischung der Formulierung ein. One solution to the problem would be to use non-ionic low-foam surfactants use with a particularly low cloud point, so that in extreme cases a water inlet temperature of 10 ° C still a foam-free work of the cleaning solution is made possible. A whole range of cleaning agents on the market for machine instrument preparation are based on this parameter optimized. However, here too there are serious disadvantages Days. The thermal stability of such mixtures often leaves something to be desired, sometimes a gradual segregation occurs even at temperatures from 35 ° C the wording.

Um die Lagerstabitität der Reinigungsmittel auch bei höheren Temperaturen sicherzustellen, bzw. ihre Homogenität in der Formulierung überhaupt erst zu gewährleisten, müssen für die Herstellung solcher Produkte teilweise hohe Einsatzmengen spezieller Lösungsvermittler bzw. Konfektionierhilfsmittel, beispielsweise Cumolsulfonat oder Xylolsulfonat eingesetzt werden. Da dem Lösungsvermittler außer der Klarstellung der Formulierung keine weiteren Aufgaben zukommen, ist der Nutzen des Einsatzes solcher Lösungsvermittler eher gering, wenn man bedenkt, daß das Abwasser dadurch zusätzlich belastet wird.The storage stability of the cleaning agents, even at higher temperatures ensure, or to ensure their homogeneity in the formulation in the first place, sometimes have to use large amounts for the production of such products special solubilizer or assembly aids, for example Cumene sulfonate or xylene sulfonate can be used. Because the solution broker apart from clarifying the wording, there are no other tasks the benefits of using such solution brokers are rather small, considering that the wastewater is additionally polluted.

In der DE-A-196 07 530 wird ein Reiniger beschrieben, der neben Enzymen, Komplexbildnern und weiteren üblichen Bestandteilen als Tensidbasis ein anionisches Tensid vom Typ eines kurzkettigen C5-C10 Alkylsulfatsalzes enthält. Es ist bekannt, daß anionische Tenside eine gute reinigungsunterstützende Wirkung aufweisen, wobei Tenside mit hydrophoben Resten ab 10 Kohlenstoffatomen zu starker Schaumbildung neigen. Sofern, wie in DE-A-196 07 530 beschrieben, Tenside mit kurzkettigen verzweigten hydrophobem Rest eingesetzt werden, ist es möglich, Formulierungen herzustellen, deren verdünnte Lösungen sich im gesamten Temperaturbereich durch eine gleichbleibende niedrige Schaumbildung auszeichnen, in ihrer Netzfähigkeit und Reinigungsaktivität aber stark zu wünschen lassen.DE-A-196 07 530 describes a cleaner which, in addition to enzymes, complexing agents and other customary constituents, contains an anionic surfactant of the type of a short-chain C 5 -C 10 alkyl sulfate salt as the surfactant base. It is known that anionic surfactants have a good cleaning-supporting effect, surfactants with hydrophobic residues from 10 carbon atoms tend to form a lot of foam. If, as described in DE-A-196 07 530, surfactants with short-chain branched hydrophobic radicals are used, it is possible to produce formulations whose dilute solutions are characterized by a constant low foam formation over the entire temperature range, but strong in their wetting ability and cleaning activity to be desired.

Es wurde deshalb versucht, ein Reinigungsmittel zu entwickeln, welches in allen Temperaturbereichen nur eine gleichbleibende geringe oder überhaupt keine Schaumbildung entwickeln sollte. Das Schaumverhalten sollte auch in Gegenwart von Eiweiß konstant niedrig bleiben. Auf den Einsatz biologisch schwer oder nicht abbaubarer Schaumdämpfer, wie z.B. EO-PO Blockpolymere, Silikonderivate und Paraffinöl sollte dabei nach Möglichkeit verzichtet werden, ebenso auf den Zusatz von Lösungsvermittlern vom Typ des Cumolsulfonates oder Xylolsulfonates. Gleichzeitig sollte das Mittel aber auch noch bei Temperaturen oberhalb von 40°C seine Lagerstabilität bewahren. Wesentlich für das Mittel sollte ein ausgeprägt gutes Netz- und Reinigungsvermögen insbesondere gegenüber Blut und Proteinverschmutzungen, auch an besonders schwer zugänglichen Stellen sein. Dabei sollte die Tensidbasis eine gute biologische Abbaubarkeit aufweisen und zur Verbesserung der Netzfähigkeit keine biologisch harten Fluortenside zum Einsatz kommen. Zudem sollte das Mittel und seine Gebrauchslösungen bevorzugt pH neutral bis schwach sauer sein, um eine optimale Verträglichkeit des Mittels und seiner Lösung gegenüber den üblichen in der Medizin eingesetzten flexiblen Kunststoff-Materialien und metallischen Werkstoffen zu gewährleisten.An attempt was therefore made to develop a cleaning agent which can be found in all Temperature ranges only a constant little or none at all Should develop foam. The foam behavior should also be in the presence of protein remain consistently low. On the use of biologically difficult or not degradable foam damper, such as EO-PO block polymers, silicone derivatives and Paraffin oil should be avoided if possible, as well as the addition of solubilizers of the cumene sulfonate or xylene sulfonate type. At the same time, the agent should also be used at temperatures above 40 ° C maintain its storage stability. Essential for the agent should be a pronounced good wetting and cleaning ability, especially against blood and protein contamination, even in places that are particularly difficult to access. Here the surfactant base should have good biodegradability and for improvement no biologically hard fluorosurfactants are used come. In addition, the agent and its working solutions should preferably pH be neutral to slightly acidic to ensure optimal tolerance of the product and its solution compared to the usual flexible ones used in medicine Ensure plastic materials and metallic materials.

Bei der Lösung der Aufgabe wurde davon ausgegangen, daß das Mittel neben dem möglichen Einsatz von Enzymen bevorzugt auf der Basis anionischer tensioaktiver Wirkstoffe aufgebaut sein sollte, um eine optimale Reinigungswirkung zu erzielen.When solving the problem, it was assumed that the means in addition to the possible use of enzymes preferably based on anionic tensioactive Active ingredients should be built up to achieve an optimal cleaning effect achieve.

Die Substanzklasse der Alkylpolygtykolethercarboxylate ist bekannt für ihr gutes Reinigungsvermögen bei relativ geringer bis moderater Schäumneigung. Kommerziell erhältlich sind diese Produkte bei der KAO-Corporation unter der Sammelbezeichnung AkypoR LF. Erste Formulierungsversuche mit Octylethercarboxylaten zeigten jedoch, daß die daraus hergestellten Reinigungslösungen zu starkem Schäumen neigten. Versuche, den Schaum durch Einsatz eines Blends mit dem besonders kurzkettigen Butylethercarboxylat einzudämmen, brachten nicht den erhofften Erfolg, da der Schaum nun zwar schneller zerfiel, die Initialschaumhöhe zum Zeitpunkt 0 aber nahezu unverändert blieb. Deshalb wurde im weiteren versucht, das Schäumverhalten durch Zusätze von Alkylpolyalkylenglycolethern bzw. von mit Alkylresten endständig verschlossenen Fettalkohol EO/PO-Addukten zu minimieren. Im Ergebnis zeigte sich, daß entweder bei Raumtemperatur klare Formulierungen erhalten wurden, deren Anwendungslösungen stark schäumten oder schwach schäumende Anwendungslösungen auf bei Raumtemperatur instabile Formulierungen zurückgeführt werden konnten, die nur durch erhebliche Zusätze an Cumolsulfonat oder Lösemittel, z.B. Ethylenglycolmonomethylether hinsichtlich ihres Lagerverhaltens zu stabilisieren waren.The class of alkyl polyglycol ether carboxylates is known for its good cleaning properties with a relatively low to moderate tendency to foam. These products are commercially available from KAO Corporation under the collective name Akypo R LF. However, initial attempts at formulation with octyl ether carboxylates showed that the cleaning solutions made from them tended to foam excessively. Attempts to contain the foam by using a blend with the particularly short-chain butyl ether carboxylate did not bring the hoped-for success, since the foam now disintegrated faster, but the initial foam height at time 0 remained almost unchanged. For this reason, attempts were subsequently made to minimize the foaming behavior by adding alkyl polyalkylene glycol ethers or fatty alcohol EO / PO adducts which are terminated with alkyl radicals. The result showed that either clear formulations were obtained at room temperature, the use solutions of which foamed strongly or low-foaming use solutions could be attributed to formulations which were unstable at room temperature and which could only be stabilized with regard to their storage behavior by substantial additions of cumene sulfonate or solvents, for example ethylene glycol monomethyl ether.

Überraschend wurde nun gefunden, daß sich schaumarme lagerstabile Formulierungen, die den eingangs erwähnten Anforderungen entsprechen, herstellen lassen, wenn die Mischungen wenigstens ein Ethercarboxylat, wenigstens ein nichtionisches Tensid und wenigstens ein N-Alkylpyrrolidon enthalten. Diese Zusammensetzung kann als Konzentrat vorliegen, welches in wässriger oder wässrig-alkoholischer Lösung zur Anwendung kommen kann (Anwendungslösung).Surprisingly, it has now been found that low-foam, storage-stable formulations, that meet the requirements mentioned above if the mixtures contain at least one ether carboxylate, at least one contain nonionic surfactant and at least one N-alkylpyrrolidone. This composition can be present as a concentrate, which is in aqueous or aqueous-alcoholic Solution can be used (application solution).

Dementsprechend betrifft die vorliegende Erfindung ein Reinigungsmittel umfassend in wässriger Lösung als Konzentrat

  • (a) 0,1 - 30 Gew.-% wenigstens eines Ethercarboxylates der Formel I R1(O-CH2-CH2-)k-OCH2COOM     k = 0-12
  • (b) 0,1 - 40 Gew.-% wenigstens eines nichtionischen Tensids der Formel II
    Figure 00060001
  • (c) 0,01 - 20 Gew.-% wenigstens eines N-Alkylpyrrolidons worin
  • R1 - einen gesättigten oder ungesättigten, linearen oder verzweigten Alkylrest mit 4-18 Kohlenstoffatomen oder einen Phenylalkylrest mit 10-18 Kohlenstoffatomen,
  • M - ein einwertiges, zweiwertiges, dreiwertiges Metallkation und/oder ein Proton (H+),
  • R2 und R3 jeweils einen gesättigten oder ungesättigten, linearen oder verzweigten Alkyrest mit 3-18 Kohlenstoffatomen oder einen Phenylalkylrest mit 10-18 Kohlenstoffatomen bedeuten,
    das N-Alkylpyrrolidon einen gesättigten oder ungesättigten, linearen oder verzweigten Alkylrest mit 6 bis 18 Kohlenstoffatomen aufweist,
  • und die Gewichts%-Anteile auf die Gesamtmenge der wässrigen Lösung bezogen sind. Accordingly, the present invention relates to a cleaning agent comprising in aqueous solution as a concentrate
  • (a) 0.1-30% by weight of at least one ether carboxylate of the formula I. R 1 (O-CH 2 -CH 2 -) k -OCH 2 COOM k = 0-12
  • (b) 0.1-40% by weight of at least one nonionic surfactant of the formula II
    Figure 00060001
  • (c) 0.01-20% by weight of at least one N-alkylpyrrolidone wherein
  • R 1 - a saturated or unsaturated, linear or branched alkyl radical with 4-18 carbon atoms or a phenylalkyl radical with 10-18 carbon atoms,
  • M - a monovalent, divalent, trivalent metal cation and / or a proton (H + ),
  • R 2 and R 3 each represent a saturated or unsaturated, linear or branched alkyl radical having 3-18 carbon atoms or a phenylalkyl radical having 10-18 carbon atoms,
    the N-alkylpyrrolidone has a saturated or unsaturated, linear or branched alkyl radical having 6 to 18 carbon atoms,
  • and the weight percentages are based on the total amount of the aqueous solution.

    In einer besonderen Ausgestaltung ist die erfindungsgemäße Zusammensetzung frei von schwer oder nicht abbaubaren Schaumdämpfern, wie insbesondere EO-PO-Blockpolymeren, Silikonderivaten und/oder Paraffinöl sowie Lösungsvermittlern, wie insbesondere Cumol- oder Xylolsulfonaten.The composition according to the invention is in a special embodiment free of difficult or non-degradable foam dampers, such as EO-PO block polymers in particular, Silicone derivatives and / or paraffin oil and solubilizers, such as in particular cumene or xylene sulfonates.

    Die Ethercarboxylate der Formel I sind in dem erfindungsgemässen Reinigungsmittel vorzugsweise in einer Gesamtkonzentration von 0,1-10 Gew.-%, besonders bevorzugt in einer Konzentration von 0,1-7 Gew.-%, bezogen auf die Gesamtmenge des Konzentrats enthalten.The ether carboxylates of the formula I are in the cleaning agent according to the invention preferably in a total concentration of 0.1-10% by weight, particularly preferably in a concentration of 0.1-7% by weight, based on the total amount of the concentrate included.

    Bei den ein-, zwei- und dreiwertigen Metallionen kann es sich beispielsweise um Alkali- und/oder Erdalkalimetallionen handeln.The mono-, di- and trivalent metal ions can be, for example Act alkali and / or alkaline earth metal ions.

    Vorzugsweise enthält der Alkylrest R1 4-13, insbesondere bevorzugt 4-10 Kohlenstoffatome. Bevorzugt nimmt k eine ganze Zahl zwischen 0 und 9 ein, besonders bevorzugt zwischen 5 und 9 ein.The alkyl radical R 1 preferably contains 4-13, particularly preferably 4-10 carbon atoms. K preferably takes an integer between 0 and 9, particularly preferably between 5 and 9.

    Ein bevorzugtes Ethercarboxylat ist Natrium C8-Alkylethercarboxylat (6 EO) (Natriumcapryleth(6)carboxylat).A preferred ether carboxylate is sodium C 8 alkyl ether carboxylate (6 EO) (sodium capryleth (6) carboxylate).

    Die nichtionischen Tenside der Formel II sind in dem erfindungsgemässen Mittel vorzugsweise in einer Konzentration von 0,1-30 Gew.-%, besonders bevorzugt in einer Konzentration von 0,1-15 Gew.-%, bezogen auf die Gesamtmenge des Konzentrats, enthalten. Bevorzugt nimmt m eine ganze Zahl zwischen 3 und 20 ein.The nonionic surfactants of formula II are in the agent according to the invention preferably in a concentration of 0.1-30% by weight, particularly preferably in a concentration of 0.1-15 wt .-%, based on the total amount of Concentrate. M preferably takes an integer between 3 and 20 on.

    Bei den besonders bevorzugten nichtionischen Tensiden handelt es sich um ein Octylethoxylat mit 6-10 EO, endständig verschlossen mit einem Octylglycerylether, wie es z.B. von der HACOBA AG (Basel) unter dem Handelsnamen Ethertensid TN 55 angeboten wird.The particularly preferred nonionic surfactants are one Octyl ethoxylate with 6-10 EO, terminally sealed with an octylglyceryl ether, as it e.g. by HACOBA AG (Basel) under the trade name TN 55 ether surfactant is offered.

    Die N-Alkylpyrrolidone sind in dem erfindungsgemässen Mittel vorzugsweise in einer Konzentration von 0,01-15 Gew.-%, besonders bevorzugt in einer Konzentration von 0,01-5 Gew.-%, bezogen auf die Gesamtmenge des Konzentrats, enthalten. Besonders bevorzugt sind dabei N-Octylpyrrolidon, N-Decylpyrrolidon und N-Laurylpyrrolidon.The N-alkylpyrrolidones in the agent according to the invention are preferably in a concentration of 0.01-15 wt .-%, particularly preferably in a concentration of 0.01-5 wt .-%, based on the total amount of the concentrate. N-Octylpyrrolidone, N-Decylpyrrolidone and are particularly preferred N-lauryl pyrrolidone.

    In einer bevorzugten Ausgestaltung umfaßt die wässrige Lösung insgesamt wenigstens 1,0 Gew.-% der Komponenten (a), (b) und (c), bezogen auf die Gesamtmenge der Lösung.In a preferred embodiment, the aqueous solution comprises at least a total 1.0% by weight of components (a), (b) and (c), based on the Total amount of solution.

    Der zu 100 Gew.-% fehlende Teil kann durch die nachfolgend erwähnten optionalen Komponenten und Wasser ergänzt werden.The 100% by weight missing part can be replaced by the optional mentioned below Components and water are added.

    So kann das Reinigungsmittel zusätzlich 0,1-30 Gew.-%, vorzugsweise 0,5-20 Gew.-% Komplexbildner und Wasserhärtestabilisatoren enthalten, wobei Salze organischer Säuren, z.B. Salze der Citronensäure, Glukonsäure, Nitrilotriessigsäure, EDTA, Aminotrismethylenphosphonsäure, Hydroxyethandiphosphonsäure, Phosphonobutantricarbonsäure, aber auch Polymere, z.B. Polyacrylate, Polycarboxylate, Maleinsäure-/Acrylsäuecopolymerisate bzw. deren Mischungen zum Einsatz kommen können.So the cleaning agent can additionally 0.1-30 wt .-%, preferably 0.5-20 Wt .-% contain complexing agents and water hardness stabilizers, with salts organic acids, e.g. Salts of citric acid, gluconic acid, nitrilotriacetic acid, EDTA, aminotrismethylenephosphonic acid, hydroxyethane diphosphonic acid, Phosphonobutane tricarboxylic acid, but also polymers, e.g. Polyacrylates, polycarboxylates, Maleic acid / acrylic acid copolymers or mixtures thereof for Can come into play.

    Weiterhin kann das Mittel bis 20 Gew.-%, vorzugsweise 1 bis 20 Gew.-% proteolytische Enzyme in Form ihrer handelsüblichen Lösungen enthalten, wobei dem erfindungsgemässen Mittel, sofern es Enzyme enthält, zur Enzymstabilisierung bis zu 50 Gew.-% einwertiger und/oder mehrwertiger Alkohole mit 2-6 Kohlenstoffatomen und 1-6 Hydroxylgruppen zugesetzt werden können. Bevorzugt sind dabei mehrwertige Alkohole, insbesondere Propylenglycol, Glycerin, Sorbitol sowie Mischungen dieser Alkohole.Furthermore, the agent can contain up to 20% by weight, preferably 1 to 20% by weight. contain proteolytic enzymes in the form of their commercially available solutions, wherein the agent according to the invention, if it contains enzymes, for enzyme stabilization up to 50% by weight of monohydric and / or polyhydric alcohols with 2-6 carbon atoms and 1-6 hydroxyl groups can be added. Prefers are polyhydric alcohols, especially propylene glycol, glycerin, sorbitol as well as mixtures of these alcohols.

    Außerdem kann das erfindungsgemässe Mittel bis zu 5 Gew.-% Korrosionsinhibitoren, Konservierungsmittel, Farbstoffe und Geruchskorrigenzien enthalten.In addition, the agent according to the invention can contain up to 5% by weight of corrosion inhibitors, Preservatives, dyes and odor correctors included.

    Ferner kann das erfindungsgemässe Mittel noch bis zu 20 Gew.-%, vorzugsweise 0,1 bis zu 5 Gew.-% weiterer nichtionischer Tenside enthalten, die nicht unter die Formel II fallen und die ausgewählt sind aus der Gruppe der Alkylalkoxylate, Alkylphenolalkoxylate, Alkylpolyglucoside, Alkyldimethylaminoxide, Alkylfettsäureamide und Amidethercarboxylate, wobei die endständigen Hydroxylgruppen der Alkylalkoxylate und Alkylphenolalkoxylate auch verethert sein können. Die Alkylgruppe weist dabei jeweils den für derartige Tenside üblichen Bereich von 6 bis 18 Kohlenstoffatome auf.Furthermore, the agent according to the invention can still contain up to 20% by weight, preferably 0.1 to 5 wt .-% of other nonionic surfactants that do not fall under the Formula II fall and which are selected from the group of alkyl alkoxylates, Alkylphenol alkoxylates, alkyl polyglucosides, alkyldimethylamine oxides, alkyl fatty acid amides and amide ether carboxylates, the terminal hydroxyl groups the alkyl alkoxylates and alkylphenol alkoxylates can also be etherified. The The alkyl group has the usual range of 6 for such surfactants up to 18 carbon atoms.

    Außerdem kann das erfindungsgemässe Mittel zusätzlich bis zu 20 Gew.-%, vorzugsweise 0,01 bis zu 7 Gew.-% weiterer anionischer und/oder amphoterer Tenside enthalten, die ausgewählt sind aus der Gruppe der Alkylsulfate, der Alkylsulfonate, Alkylethersulfate, Alkyl-C6-C18-arylsulfonate, Alkylbetaine, Alkyliminodipropionate, Alkylamidopropylbetaine, wobei als wesentliche Voraussetzung das Schaumverhalten des erfindungsgemässen Mittels sowie der Anwendungslösung durch die Zusätze nicht beeinträchtigt wird. Die Alkylgruppe weist dabei jeweils den für derartige Tenside üblichen Bereich von 6 bis 18, bevorzugt 6 bis 12 Kohlenstoffatome auf.In addition, the agent according to the invention can additionally contain up to 20% by weight, preferably 0.01 to 7% by weight, of further anionic and / or amphoteric surfactants which are selected from the group consisting of alkyl sulfates, alkyl sulfonates, alkyl ether sulfates, alkyl C 6 -C 18 aryl sulfonates, alkylbetaines, alkyliminodipropionates, alkylamidopropylbetaines, the essential prerequisite being that the foam behavior of the agent according to the invention and of the application solution is not impaired by the additives. The alkyl group in each case has the range from 6 to 18, preferably 6 to 12, carbon atoms customary for such surfactants.

    Aus anwendungstechnischen Gründen kann es in bestimmten Fällen wünschenswert sein, dem erfindungsgemässen Mittel bis zu 10 Gew.-%, vorzugsweise bis zu 6 Gew.-% Ethylenglycolmonoalkylether, Diethylenglycolmonoalkylether, Propylenglycolmonoalkylether, Dipropylenglycolmonoalkylether bzw. deren Mischungen zuzusetzen, wobei der gesättigte lineare oder verzweigte Alkylrest 1-6 Kohlenstoffatome aufweist.It may be desirable in certain cases for technical reasons be, the agent according to the invention up to 10 wt .-%, preferably up to 6% by weight of ethylene glycol monoalkyl ether, diethylene glycol monoalkyl ether, Propylene glycol monoalkyl ether, dipropylene glycol monoalkyl ether or their Add mixtures, the saturated linear or branched alkyl radical 1-6 Has carbon atoms.

    Der pH-Wert des Mittels wird auf die Werte zwischen 4,0 und 13,0, vorzugsweise zwischen 4,0 und 9,0 und im Falle einer enzymhaltigen Ausführung bevorzugt auf Werte zwischen 4,0 und 8,5 eingestellt. Die Regulierung des pH-Wertes erfolgt dabei zweckmäßigerweise mit Natriumhydroxid, Kaliumhydroxid und/oder organischen Alkanolaminen, z.B. Triethanolamin oder Triisopropanolamin bzw. mit den oben beschriebenen organischen Säuren.The pH of the agent is preferably between 4.0 and 13.0 between 4.0 and 9.0 and preferred in the case of an enzyme-containing version Values set between 4.0 and 8.5. The pH is regulated expediently with sodium hydroxide, potassium hydroxide and / or organic alkanolamines, e.g. Triethanolamine or triisopropanolamine or with the organic acids described above.

    Das Reinigungsmittel kann als das vorangehend beschriebene Konzentrat oder als wässrige oder wässrig/alkoholische Lösung (Anwendungslösung) eingesetzt werden. In der wässrig/alkoholischen Anwendungslösung wird bevorzugt ein Alkohol mit zwei oder drei Kohlenstoffatomen eingesetzt.The cleaning agent can be used as the concentrate or used as an aqueous or aqueous / alcoholic solution (application solution) become. An alcohol is preferred in the aqueous / alcoholic application solution used with two or three carbon atoms.

    Die Anwendungslösungen enthalten das Reinigungsmittel (Konzentrat) in einem Anteil von 0,1 bis 10 Vol.-%, vorzugsweise von 0,1 bis 2 Vol.-%.The application solutions contain the cleaning agent (concentrate) in one Proportion from 0.1 to 10% by volume, preferably from 0.1 to 2% by volume.

    Die erfindungsgemäßen Reinigungsmittel und Anwendungslösungen können zur Reinigung von unbelebten Oberflächen, insbesondere von medizinischen Geräten, chirurgischem Instrumentarium, Anästhesiematerialien, starren und flexiblen Endoskopen eingesetzt werden. Besonders eignen sich die erfindungsgemäßen Reinigungsmittel und Anwendungslösungen zur Reinigung von chirurgischem Instrumentarium, starren und flexiblen Endoskopen in Reinigungs- und Desinfektionsautomaten. Dabei kann nach dem Reinigungssohritt eine thermische oder chemisch-thermische Desinfektion mit den üblichen für diese Zwecke einsetzbaren Desinfektionsmitteln erfolgen. Die erfindungsgemäßen Reinigungsmittel und die Anwendungslösungen können auch ohne weiteres zur Reinigung von anderen unbelebten Oberflächen verwendet werden, wie insbesondere zur Reinigung von Bettgestellen, Fußboden und Inventar sowie zur Steckbeckenreinigung.The cleaning agents and application solutions according to the invention can be used for Cleaning inanimate surfaces, especially medical ones Equipment, surgical instruments, anesthetic materials, rigid and flexible endoscopes are used. They are particularly suitable Cleaning agents according to the invention and application solutions for cleaning of surgical instruments, rigid and flexible endoscopes in cleaning and disinfection machines. After the cleaning process, a thermal or chemical-thermal disinfection with the usual for this Disinfectants can be used. The invention Cleaning agents and the application solutions can also be used without any problems Cleaning of other inanimate surfaces can be used, such as especially for cleaning bed frames, floors and inventory as well as for Bedpan cleaning.

    Die vorliegende Erfindung wird durch die nachfolgenden Beispiele näher beschrieben, ohne jedoch darauf beschränkt zu sein.The present invention is described in more detail by the following examples, without being limited to it.

    Beispiele: Examples :

    In den nachfolgenden Beispielen wurden, wenn nichts anderes angegeben, Gewichtsteile zur Beschreibung der Zusammensetzung angegeben, was Gew.-% entspricht.In the following examples, parts by weight, unless otherwise stated to describe the composition, what wt .-% corresponds.

    Die Oberflächenspannung wurde in einem dem Fachmann bekannten Verfahren unter Verwendung eines handelsüblichen Tensiometers der Firma Krüss mit einem Platin-Iridiumring bestimmt, wobei das Probegefäß thermostatiert wurde. The surface tension was determined in a process known to the person skilled in the art using a commercially available tensiometer from Krüss determined a platinum-iridium ring, the sample vessel was thermostated.

    Die Schaumwerte wurden in einem Schwenkschäumtest ermittelt. Dazu wurde in einem 100 ml Messzylinder 50 ml Lösung vorgelegt, thermostatiert, 30 mal um 180°C gedreht und anschließend sofort das Schaumvolumen in ml abgelesen.The foam values were determined in a swivel foam test. This was done in 50 ml of solution are placed in a 100 ml measuring cylinder, thermostated, 30 times Rotated 180 ° C and then immediately read the foam volume in ml.

    Es wurden 2 Rezepturen angesetzt. Dabei wurde Rezeptur 1 enzymfrei formuliert, während Rezeptur 2 enzymhaltig ist. Rezepturbestandteil Rezeptur 1 Rezeptur 2 C8 Alkylethercarbonsäure 6 EO 4,0 3,5 Ethertensid TN55 3,0 3,0 N-Dodecylpyrrolidon 0,5 1,0 Citronensäure 7 2 Polyacrylat (z.B. SokalanR Typen ex. BASF) 4 10 Triethanolamin - 3 Enzymlösung (z.B. SavinaseR 16.0 L ex. Novo Nordirsk) - 5 Propylenglycol - 20 Gereinigtes Wasser ad 100 ad 100 Two recipes were made. Recipe 1 was formulated without enzymes, while recipe 2 contains enzymes. Recipe component Recipe 1 Recipe 2 C 8 alkyl ether carboxylic acid 6 EO 4.0 3.5 TN55 ether surfactant 3.0 3.0 N-dodecylpyrrolidone 0.5 1.0 Citric acid 7 2nd Polyacrylate (e.g. Sokalan R types ex. BASF) 4th 10th Triethanolamine - 3rd Enzyme solution (e.g. Savinase R 16.0 L ex.Novo Northern Ireland) - 5 Propylene glycol - 20th Purified water ad 100 ad 100

    Der pH-Wert der erfindungsgemässen Rezepturen wurde jeweils mit Natronlauge und Citronensäure auf einen Wert von 6,0 eingestellt. Zusätzlich wurden die Rezepturen jeweils mit 0,1% Methylparaben konserviert, um sie gegen mikrobiellen Verderb zu schützen.The pH of the formulations according to the invention was in each case with sodium hydroxide solution and citric acid set to 6.0. In addition, the recipes Preserved each with 0.1% methyl paraben to protect them against microbial To protect spoilage.

    Um eine fundierte Aussage über die prinzipielle Eignung der erfindungsgemäßen Rezepturen für die beabsichtigten Einsatzgebiete zu treffen, wurde eine Reihe von physikochemischen Parametern ermittelt, wobei zu Vergleichszwecken folgende beispielhafte Auswahl der im Handel erhältlichen Reinigungsmittel herangezogen wurde: Produkt Zusammensetzung gemäß Herstellerangabe Handelsprodukt A Nichtionische Tenside, Enzyme Glycole, Lösungsvermittler (gemäß EP-A-0 268 227) Handelsprodukt B Nichtionische Tenside, Komplexbildner, Salze organischer Säuren, lösungsvermittelnder Alkohol Handelsprodukt C Anionische Tenside, Enzyme, Salze organischer Säuren, lösungsvermittelnder Alkohol, Konservierungsmittel (gemäß DE-A-196 07 530) In order to make a well-founded statement about the basic suitability of the formulations according to the invention for the intended areas of use, a number of physicochemical parameters were determined, the following exemplary selection of the commercially available cleaning agents being used for comparison purposes: product Composition according to the manufacturer's instructions Commercial product A Nonionic surfactants, enzymes glycols, solubilizers (according to EP-A-0 268 227) Commercial product B Nonionic surfactants, complexing agents, salts of organic acids, solvent alcohol Commercial product C Anionic surfactants, enzymes, salts of organic acids, solvent alcohol, preservatives (according to DE-A-196 07 530)

    Die Prüfungen wurden, sofern nicht anders beschrieben, mit den 0,5%igen Gebrauchslösungen durchgeführt.Unless otherwise stated, the tests were carried out with the 0.5% working solutions carried out.

    Die ermittelten Resultate sind in der nachfolgenden Tabelle 1 aufgeführt: Handelsprodukt A Handelsprodukt B Handelsprodukt C Rezeptur 1 Rezeptur 2 Trübungspunkt (Konzentrat) 37°C 40°C keiner 64°C 50°C Oberflächenspannung (25°C) (Ringmethode) 32 mN/m 33 mN/m 50 mN/m 30 mN/m 31 mN/m Initialschaumwerte ohne Belastung (10 ± 2°C) 60 ml 20 ml 13 ml 5 ml 9 ml ohne Belastung (25 ± 2°C) 20 ml 5 ml 13 ml 6 ml 10 ml mit 0,3% Albumin (25 ± 2°C) 10 ml 2 ml 70 ml 0 ml 2 ml ohne Belastung (45 ± 2°C) 2 ml 2 ml 8 ml 2 ml 5 ml The results obtained are listed in Table 1 below: Commercial product A Commercial product B Commercial product C Recipe 1 Recipe 2 Cloud point (concentrate) 37 ° C 40 ° C none 64 ° C 50 ° C Surface tension (25 ° C) (ring method) 32 mN / m 33 mN / m 50 mN / m 30 mN / m 31 mN / m Initial foam values without load (10 ± 2 ° C) 60 ml 20 ml 13 ml 5 ml 9 ml without load (25 ± 2 ° C) 20 ml 5 ml 13 ml 6 ml 10 ml with 0.3% albumin (25 ± 2 ° C) 10 ml 2 ml 70 ml 0 ml 2 ml without load (45 ± 2 ° C) 2 ml 2 ml 8 ml 2 ml 5 ml

    Den Werten ist zu entnehmen, daß die erfindungsgemässen Rezepturen 1 und 2 einen signifikant höheren Trübungspunkt aufweisen als die Handelsprodukte A und B. Diese Aussage ist nicht unwesentlich, wenn man bedenkt, daß in den wärmeren Klimazonen durchaus Temperaturen von 40°C und höher erreicht werden können. Demgegenüber besitzt Handelsprodukt C aufgrund seiner Zusammensetzung erwartungsgemäß keinen Trübungspunkt. Sobald die Temperatur der Anwendungslösungen 10°C und niedriger beträgt, zeigt sich eine signifikante Zunahme der Initialsohaumhöhe im Fall der Handelsprodukte A und B, während im Fall der erfindungsgemäßen Rezepturen 1 und 2 sowie des Handelsprodukts C die Schaumhöhe jeweils unverändert bleibt.It can be seen from the values that recipes 1 and 2 according to the invention have a significantly higher cloud point than the commercial products A and B. This statement is not insignificant when you consider that in the warmer climates may reach temperatures of 40 ° C and higher can be. In contrast, commercial product C has due to its composition As expected, no cloud point. As soon as the temperature of the application solutions is 10 ° C and lower, a significant one is shown Increase in initial room height in the case of commercial products A and B while in the case of recipes 1 and 2 according to the invention and of the commercial product C the foam height remains unchanged.

    Unter Albuminbelastung treten die Nachteile des Handelsprodukts C zu Tage, es setzt eine ungewöhnlich starke Schaumbildung ein. Dieses Verhalten läßt darauf schließen, daß rein anionische Formulierungen nicht uneingeschränkt für die maschinelle Instrumentenaufbereitung, speziell für die automatische Reinigung von Kanälen flexibler Endoskope geeignet sind, da die abgelösten proteinhaltigen Verschmutzungen selbst als Schaumbooster fungieren würden. Demgegenüber zeigen die erfindungsgemäßen Rezepturen 1 und 2 eine ausgeglichen niedrige Schaumbildung.The disadvantages of the commercial product C come to light under albumin pollution uses an unusually strong foam formation. This behavior suggests conclude that purely anionic formulations are not unrestricted for machine Instrument reprocessing, especially for the automatic cleaning of Channels of flexible endoscopes are suitable because the detached protein-containing Soiling would itself act as a foam booster. In contrast formulations 1 and 2 according to the invention show a balanced low Foaming.

    Die Reinigungsaktivität der erfindungsgemäßen Rezepturen wurde anhand eines plausiblen Versuchsmodells ermittelt. Dazu wurden Edelstahlschrauben mit gerinnungsfähigem Schafblut kontaminiert, 1 Stunde bei 30°C getrocknet und anschließend immer 3 kontaminierte Schrauben in ein jeweils mit 200 ml der betreffenden 0,5%igen Reinigerlösung befülltes Becherglas gegeben.The cleaning activity of the formulations according to the invention was determined using a plausible experimental model. For this purpose, stainless steel screws with coagulable Sheep blood contaminated, dried at 30 ° C for 1 hour and then always 3 contaminated screws in one each with 200 ml of the concerned Beaker filled with 0.5% detergent solution.

    Während der Einwirkzeiten wurden die Reinigerlösungen jeweils mit gleicher Geschwindigkeit gerührt, um auf diese Weise eine definierte Turbulenz zu erreichen, ohne die Verschmutzung jedoch auf mechanischem Wege zu entfernen. Als Vergleichsmedium kam Wasser mit einer eingestellten Härte von 5° dH zum Einsatz, mit dieser Wasserqualität wurden auch die jeweiligen Reinigerlösungen hergestellt. Nach der Einwirkzeit wurden die gereinigten Schrauben entnommen. Der Reinigungseffekt wurde visuell anhand der an den Schrauben verbliebenen Restverschmutzung bestimmt und einem Bewertungssystem unterworfen. Die Note 1 steht für

    Figure 00130001
    vollständigen Reinigungserfolg" während die Note 5 keine Reinigungswirkung" bedeutet. Die Versuche wurden dreimal wiederholt. Die Ergebnisse (Mittelwerte) sind Tabelle 2 zu entnehmen. Reinigungserfolg Wasser Handelsprodukt A Handelsprodukt B Handelsprodukt C Rezeptur 1 Rezeptur 2 25°C 5 min 4,3 2,9 3,7 3,6 1,6 1,8 15 min 3,9 2,2 3,4 3,4 1,0 1,2 45°C 5 min 4,5 2,6 4,1 3,8 2,0 1,7 15 min 4,3 1,6 3,5 3,1 1,0 1,0 During the exposure times, the cleaning solutions were each stirred at the same speed in order to achieve a defined turbulence in this way, but without removing the contamination mechanically. Water with a set hardness of 5 ° dH was used as the reference medium; the respective cleaning solutions were also produced with this water quality. After the exposure time, the cleaned screws were removed. The cleaning effect was determined visually based on the residual contamination remaining on the screws and subjected to an evaluation system. The grade 1 stands for
    Figure 00130001
    complete cleaning success "while the grade 5 no cleaning effect "means. The tests were repeated three times. The results (mean values) are shown in Table 2. Cleaning success water Commercial product A Commercial product B Commercial product C Recipe 1 Recipe 2 25 ° C 5 min 4.3 2.9 3.7 3.6 1.6 1.8 15 minutes 3.9 2.2 3.4 3.4 1.0 1.2 45 ° C 5 min 4.5 2.6 4.1 3.8 2.0 1.7 15 minutes 4.3 1.6 3.5 3.1 1.0 1.0

    Zusammenfassend kann festgestellt werden, daß sich die erfindungsgemäßen Rezepturen durch eine von der Temperatur unabhängige gleichbleibend niedrige Schaumbildung bei besonders niedriger Oberflächenspannung, einen hohen Trübungspunkt und ein besonders gutes Reinigungsvermögen auszeichnen. In weiteren Versuchen wurde die gute Materialverträglichkeit gegenüber Instrumentenstahl, eloxiertem Aluminium, Kupfer, Messing sowie flexiblen Materialien wie Neopren, Weich-PVC, Polyethylen, Gummi, Silikonelastomeren und Latex ermittelt. Versuche zur maschinellen Aufbereitung von marktüblichen Gastroskopen in verschiedenen Reinigungs- und Desinfektionsautomaten bestätigen die vorteilhafte Eignung der erfindungsgemäßen Mittel für den beschriebenen Anwendungszweck.In summary, it can be stated that the inventive Recipes through a constant low temperature independent Foam formation with a particularly low surface tension, a high cloud point and have a particularly good cleaning ability. In further trials were the good material compatibility with instrument steel, anodized aluminum, copper, brass and flexible materials such as Neoprene, soft PVC, polyethylene, rubber, silicone elastomers and latex determined. Tests for the mechanical processing of commercially available Gastroscopes in various cleaning and disinfection machines confirm the advantageous suitability of the agents according to the invention for the described application.

    Als bemerkenswert stellte sich die gute Verträglichkeit einer Ausführungsform des erfindungsgemäßen Mittels gegenüber Acrylglas heraus, wobei das Acrylglas in mehreren Reinigungszyklen bei einer Temperatur von 60°C aufbereitet wurde.The good compatibility of an embodiment of the Agent according to the invention over acrylic glass, the acrylic glass in several cleaning cycles at a temperature of 60 ° C.

    Claims (17)

    Reinigungsmittel, umfassend in wässriger Lösung (a) 0,1 - 30 Gew.-% wenigstens eines Ethercarboxylates der Formel I R1(O-CH2-CH2-)k-OCH2COOM     k = 0-12 (b) 0,1 - 40 Gew.-% wenigstens eines nichtionischen Tensids der Formel II
    Figure 00150001
    (c) 0,01 - 20 Gew.-% wenigstens eines N-Alkylpyrrolidons worin R1 - einen gesättigten oder ungesättigten, linearen oder verzweigten Alkylrest mit 4-18 Kohlenstoffatomen oder einen Phenylalkylrest mit 10-18 Kohlenstoffatomen, M - ein einwertiges, zweiwertiges, dreiwertiges Metallkation und/oder ein Proton (H+), R2 und R3 jeweils einen gesättigten oder ungesättigten, linearen oder verzweigten Alkyrest mit 3-18 Kohlenstoffatomen oder einen Phenylalkylrest mit 10-18 Kohlenstoffatomen bedeuten,
    das N-Alkylpyrrolidon einen gesättigten oder ungesättigten, linearen oder verzweigten Alkylrest mit 6 bis 18 Kohlenstoffatomen aufweist,
    und die Gewichts%-Anteile auf die Gesamtmenge der wässrigen Lösung bezogen sind.
    Detergent, comprising in aqueous solution (a) 0.1-30% by weight of at least one ether carboxylate of the formula I. R 1 (O-CH 2 -CH 2 -) k -OCH 2 COOM k = 0-12 (b) 0.1-40% by weight of at least one nonionic surfactant of the formula II
    Figure 00150001
    (c) 0.01-20% by weight of at least one N-alkylpyrrolidone wherein R 1 - a saturated or unsaturated, linear or branched alkyl radical with 4-18 carbon atoms or a phenylalkyl radical with 10-18 carbon atoms, M - a monovalent, divalent, trivalent metal cation and / or a proton (H + ), R 2 and R 3 each represent a saturated or unsaturated, linear or branched alkyl radical having 3-18 carbon atoms or a phenylalkyl radical having 10-18 carbon atoms,
    the N-alkylpyrrolidone has a saturated or unsaturated, linear or branched alkyl radical having 6 to 18 carbon atoms,
    and the weight percentages are based on the total amount of the aqueous solution.
    Reinigungsmittel nach Anspruch 1, dadurch gekennzeichnet, daß die wässrige Lösung insgesamt wenigstens 1 Gew.-% der Komponenten (a), (b) und (c) umfaßt.Cleaning agent according to claim 1, characterized in that the aqueous solution in total at least 1% by weight of components (a), (b) and (c). Reinigungsmittel nach Anspruch 1 oder 2, dadurch gekennzeichnet, daß es zusätzlich 0,1-30 Gew.-% Komplexbildner und Wasserhärtestabilisatoren enthält.Cleaning agent according to claim 1 or 2, characterized in that it additionally 0.1-30% by weight of complexing agents and water hardness stabilizers contains. Reinigungsmittel nach einem oder mehreren der Ansprüche 1-3, dadurch gekennzeichnet, daß es zusätzlich bis zu 20 Gew.-% proteolytische Enzyme enthält.Cleaning agent according to one or more of claims 1-3, characterized characterized in that it is additionally up to 20 wt .-% proteolytic Contains enzymes. Reinigungsmittel nach einem oder mehreren der Ansprüche 1-4, dadurch gekennzeichnet, daß es in einer enzymhaltigen Ausführung zusätzlich bis zu 50 Gew.-% einwertiger und/oder mehrwertiger Alkohole mit 2-6 Kohlenstoffatomen und 1-6 Hydroxylgruppen enthält.Cleaning agent according to one or more of claims 1-4, characterized characterized in that it is additionally up to in an enzyme-containing version 50% by weight of monohydric and / or polyhydric alcohols with 2-6 carbon atoms and contains 1-6 hydroxyl groups. Reinigungsmittel nach einem oder mehreren der Ansprüche 1-5, dadurch gekennzeichnet, daß es zusätzlich bis zu 5 Gew.-% Korrosionsinhibitoren, Konservierungsmittel, Geruchskorrigenzien und Farbstoffe enthält.Cleaning agent according to one or more of claims 1-5, characterized characterized in that it additionally contains up to 5% by weight of corrosion inhibitors, Contains preservatives, odor correctors and dyes. Reinigungsmittel nach einem oder mehreren der Ansprüche 1-6, dadurch gekennzeichnet, daß es zusätzlich bis zu 30 Gew.-% nichtionischer Tenside enthält, die nicht aus der durch Formel II definierten Gruppe ausgewählt sind.Cleaning agent according to one or more of claims 1-6, characterized characterized in that it additionally contains up to 30% by weight of nonionic surfactants contains that is not selected from the group defined by Formula II are. Reinigungsmittel nach einem oder mehreren der Ansprüche 1-7, dadurch gekennzeichnet, daß es zusätzlich bis zu 20 Gew.-% anionischer, nicht unter die Formel I fallende und/oder amphoterer Tenside enthält.Cleaning agent according to one or more of claims 1-7, characterized characterized in that it is up to 20 wt .-% anionic, not contains formula I and / or amphoteric surfactants. Reinigungsmittel nach einem oder mehreren der Ansprüche 1-8, dadurch gekennzeichnet, daß es in einer enzymhaltigen Ausführung zusätzlich bis zu 10 Gew.-% Ethylenglycolmonoalkylether, Diethylenglycolmonoalkylether, Propylenglycolmonoalkylether, Dipropylenglycolmonoalkylether bzw. deren Mischungen enthält, wobei der gesättigte lineare oder verzweigte Alkylrest 1-6 kohlenstoffatome aufweist.Cleaning agent according to one or more of claims 1-8, characterized characterized in that it is additionally up to in an enzyme-containing version 10% by weight of ethylene glycol monoalkyl ether, diethylene glycol monoalkyl ether, Propylene glycol monoalkyl ether, dipropylene glycol monoalkyl ether or their Contains mixtures, the saturated linear or branched alkyl radical 1-6 carbon atoms. Reinigungsmittel nach einem oder mehreren der Ansprüche 1-9, dadurch gekennzeichnet, daß es einen pH-Wert von 4,0-13,0, im Falle einer enzymhaltigen Ausführung einen pH-Wert von 4,0-8,5 aufweist.Cleaning agent according to one or more of claims 1-9, characterized characterized in that it has a pH of 4.0-13.0, in the case of an enzyme-containing one Version has a pH of 4.0-8.5. Anwendungslösung umfassend das Reinigungsmittel wie in irgendeinem der Ansprüche 1-10 definiert in wässriger oder wässrig/alkoholischer Lösung.Application solution comprising the detergent as in any of claims 1-10 defined in aqueous or aqueous / alcoholic solution. Anwendungslösung gemäß Anspruch 11, dadurch gekennzeichnet, daß in der wässrig/alkoholischen Lösung ein einwertiger Alkohol mit zwei oder drei Kohlenstoffatomen eingesetzt wird.Application solution according to claim 11, characterized in that in the aqueous / alcoholic solution is a monohydric alcohol with two or three Carbon atoms is used. Verwendung des Reinigungsmittels gemäß irgendeinem der Ansprüche 1-10 und der Anwendungslösung gemäß irgendeinem der Ansprüche 11 oder 12 zur Reinigung von medizinischen Geräten, chirurgischem Instrumentarium, Anästhesiematerialien, starren und flexiblen Endoskopen.Use of the cleaning agent according to any one of claims 1-10 and the application solution according to any one of claims 11 or 12 for cleaning medical devices, surgical instruments, Anesthesia materials, rigid and flexible endoscopes. Verwendung gemäß Anspruch 13 zur Reinigung von chirurgischem Instrumentarium, starren und flexiblen Endoskopen in Reinigungs- und Desinfektionsautomaten.Use according to claim 13 for cleaning surgical instruments, rigid and flexible endoscopes in cleaning and disinfection machines. Verwendung gemäß Anspruch 14 zur Reinigung von chirurgischem Instrumentarium, starren und flexiblen Endoskopen in Reinigungs- und Desinfektionsautomaten, wobei nach dem Reinigungsschritt eine thermische oder chemisch-thermische Desinfektion mit den üblichen für diese Zwecke einsetzbaren Desinfektionsmitteln erfolgen kann. Use according to claim 14 for cleaning surgical instruments, rigid and flexible endoscopes in cleaning and disinfection machines, after the cleaning step a thermal or chemical-thermal disinfection with the usual usable for these purposes Disinfectants can be done. Verwendung gemäß irgendeinem der Ansprüche 13 bis 15 bei einer Anwendungstemperatur zwischen 5°C und 95°C.Use according to any one of claims 13 to 15 at an application temperature between 5 ° C and 95 ° C. Verwendung des Reinigungsmittels gemäß irgendeinem der Ansprüche 1-10 und seiner gebrauchsfertigen Anwendungslösung gemäß den Ansprüchen 11 oder 12 zur Reinigung von Bettgestellen, Fußböden, Inventar und weiteren unbelebten Oberflächen.Use of the cleaning agent according to any one of claims 1-10 and its ready-to-use application solution according to the claims 11 or 12 for cleaning bed frames, floors, inventory and other inanimate surfaces.
    EP99120336A 1998-10-15 1999-10-12 Cleaning compositions and their use Expired - Lifetime EP0994178B1 (en)

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    EP1139761B1 (en) * 1998-12-23 2003-06-11 Huntsman International Llc Herbicidal compositions and surfactant concentrates
    AU2003259326B2 (en) * 2002-08-22 2010-04-22 Reckitt Benckiser Llc Acidic hard surface cleaners
    WO2004018599A1 (en) 2002-08-22 2004-03-04 Reckitt Benckiser Inc Acidic hard surface cleaners
    US7696143B2 (en) 2002-08-22 2010-04-13 Reckitt Benckiser Inc. Acidic hard surface cleaners
    WO2004074417A1 (en) * 2003-02-24 2004-09-02 Unilever Plc Antimicrobial cleaning compositions
    US20090123449A1 (en) * 2006-04-21 2009-05-14 Kao Corporation Composition of Biofilm Control Agent
    WO2007141067A1 (en) * 2006-06-07 2007-12-13 Kao Corporation, S.A. Detergent composition
    RU2450047C2 (en) * 2006-06-07 2012-05-10 Као Корпорэйшн, С.А. Detergent composition
    US8343905B2 (en) 2006-06-07 2013-01-01 Kao Corporation, S.A. Detergent composition
    EP2438904A1 (en) * 2010-10-05 2012-04-11 Kao Corporation Cleansing composition
    WO2012045768A1 (en) * 2010-10-05 2012-04-12 Kao Corporation Cleansing composition
    US9271909B2 (en) 2010-10-05 2016-03-01 Kao Corporation Cleansing composition
    CN105154253A (en) * 2015-10-09 2015-12-16 湖北穆兰同大科技有限公司 Biological multienzyme cleaning agent and preparation method thereof

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    ES2192008T3 (en) 2003-09-16
    DE19847498C2 (en) 2002-05-08
    ATE232235T1 (en) 2003-02-15
    DE19847498A1 (en) 2000-04-20
    EP0994178B1 (en) 2003-02-05
    DE59904212D1 (en) 2003-03-13

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