EP1966363B1 - Inhibiting the corrosive properties of liquid cleaning agents containing hypochlorite - Google Patents

Inhibiting the corrosive properties of liquid cleaning agents containing hypochlorite Download PDF

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EP1966363B1
EP1966363B1 EP06819024A EP06819024A EP1966363B1 EP 1966363 B1 EP1966363 B1 EP 1966363B1 EP 06819024 A EP06819024 A EP 06819024A EP 06819024 A EP06819024 A EP 06819024A EP 1966363 B1 EP1966363 B1 EP 1966363B1
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Prior art keywords
alkali metal
cleaning agent
use according
hypochlorite
alkyl
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German (de)
French (fr)
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EP1966363A1 (en
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Carlos Malet
Xavier Closa Cruxens
Miguel Osset
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Henkel AG and Co KGaA
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Henkel AG and Co KGaA
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    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
    • C11D3/395—Bleaching agents
    • C11D3/3956—Liquid 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
    • C11D1/00—Detergent compositions based essentially on surface-active compounds; Use of these compounds as a detergent
    • C11D1/02—Anionic compounds
    • C11D1/12—Sulfonic acids or sulfuric acid esters; Salts thereof
    • C11D1/29—Sulfates of polyoxyalkylene ethers
    • 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
    • C11D3/0005—Other compounding ingredients characterised by their effect
    • C11D3/0073—Anticorrosion 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
    • C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
    • C11D3/0005—Other compounding ingredients characterised by their effect
    • C11D3/0084—Antioxidants; Free-radical scavengers
    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
    • C11D3/02—Inorganic compounds ; Elemental compounds
    • C11D3/04—Water-soluble compounds
    • C11D3/08—Silicates
    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • 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
    • C11D2111/16—Metals

Definitions

  • the present invention relates to the reduction of corrosivity of hypochlorite on metal surfaces when using hypochlorite-containing liquid detergents for cleaning metal surfaces.
  • Hard surface cleaners such as kitchen and bathroom cleaners, have historically been highly abrasive powders, optionally containing low levels of surfactants and properly referred to as scouring powders. They were aggressive not only to the user's hand, but also to the surface with which they were brought into contact for cleaning purposes. In some cases, a bleaching agent has been incorporated into such scrubbing powders to oxidatively break up soils and thereby facilitate their removability. Although modern abrasive cleaners are now much more skin-friendly in their composition, these cleaners still rely essentially on the action of Abrasivstoffs to remove stains, which in particular soap deposits, which are usually derived mainly from personal hygiene, from hard Remove surfaces such as bathroom tiles or sinks.
  • hypochlorite is known to be a highly effective bleaching agent and has been used for a long time, optionally with soaps and / or synthetic surfactants, to remove stains and all sorts of soils from laundry to textiles as well as hard surface cleaning. It is normally sold in concentrations of about 2 to 10% by weight in water for household use. While the use of hypochlorite agents an excellent disinfecting performance and very good Cleaning results achieved on hard surfaces, observed in sensitive cleaning in some cases, a change in the surface. This can range from a slight impairment of the visual impression to the appearance of pits in the surface or even pitting, with severe cases usually occurring only with improper use of the agent.
  • the sensitive surfaces mentioned here include, in particular, those made of metal, for example steel surfaces, such as those found in kitchen sinks, as housing surfaces of domestic appliances or linings of kitchen or bathroom cabinets.
  • metal for example steel surfaces, such as those found in kitchen sinks, as housing surfaces of domestic appliances or linings of kitchen or bathroom cabinets.
  • Hypochlorite-containing detergents are biespielweise EP 311 175 . DE 19700799 unnd EP903403 known.
  • hypochlorite detergent positively influences the corrosion behavior.
  • the metal surface is a steel surface, since then the improvement effect of the combination used in the invention is particularly pronounced.
  • the combination used according to the invention is preferably a constituent of the hypochlorite-containing cleaning agent.
  • the cleaning agent contains 0.5 wt .-% to 10 wt .-%, in particular 2 wt .-% to 5.5 wt .-% alkali metal hypochlorite.
  • alkali metal hypochlorites such as potassium hypochlorite
  • sodium hypochlorite it is still preferable to use sodium hypochlorite in the present invention.
  • aqueous sodium hypochlorite solutions often contain considerable amounts of chloride salts. These can readily be used for the production of corrosion-enhanced agents according to the invention, so that it is not necessarily dependent on the use of high-purity NaOCl.
  • hypochlorite-containing agents are alkaline, it being preferred according to the invention, when the cleaning agent contains more than 0 wt .-% up to 5 wt .-%, in particular 0.1 wt .-% to 2 wt .-% alkali metal hydroxide.
  • more than 0 wt .-% up to 5 wt .-%, in particular 0.1 wt .-% to 2.5 wt .-% alkali metal silicate in the agent is preferably, more than 0 wt .-% up to 5 wt .-%, in particular 0.1 wt .-% to 2.5 wt .-% alkali metal silicate in the agent. This not only improves the corrosion behavior but also increases the storage stability of the hypochlorite.
  • alkyl (alkoxy) n- sulfate which may also be referred to as alkyl ether sulfate and by reacting alcohols (preferably having 6 to 22 carbon atoms) with alkylene oxides, in particular ethylene oxide, and subsequent Sulfation and neutralization, especially with alkaline alkali metal salts such as alkali metal hydroxides, is available.
  • alcohols preferably having 6 to 22 carbon atoms
  • alkylene oxides in particular ethylene oxide
  • alkaline alkali metal salts such as alkali metal hydroxides
  • the alkyl (alkoxy) n- sulphate preferably has a C 8-18 , in particular C 12-16 -alkyl group, -OCH 2 CH 2 - and / or -OCHCH 3 CH 2 -alkoxy group (s), where n is preferably is a number from 1 to 6, especially 2 to 5.
  • the preferred alkali hydroxide is sodium hydroxide, and also the alkali salts mentioned in connection with the other ingredients of the compositions are preferably the sodium salts.
  • the alkali metal silicate sodium silicate and / or the alkali metal counterion of the ether sulfate is the sodium ion.
  • the cleaning agent may contain up to 5% by weight of additional bleach-stable surfactant.
  • betaines in particular those of the general formula I, wherein R 1 is an alkyl or alkenyl group having 6 to 22 carbon atoms or a group R 4 is CO-NH- (CH 2 ) n -, R 2 is hydrogen or an alkyl group having 1 to 4 carbon atoms, R 3 is hydrogen or an alkyl group with 1 to 4 carbon atoms, R 4 is an alkyl or alkenyl group having 6 to 22 carbon atoms, m is a number from 1 to 6 and n is a number from 1 to 3.
  • particularly suitable members of this class of surfactants include C 12-18 alkyl dimethyl betaine, commercially available as coconut betaine, and C 10-16 alkyl dimethyl betaine, commercially available as lauryl betaine.
  • the preparations may additionally contain sequestering agents, preferably phosphates, alkyl phosphates, alkylphosphonic acids and among these in particular those having at least one amine oxide substituent on the alkyl group, referred to herein as Aminoxidphosphonklaren, polyacrylic acids and / or phosphono-containing polyacrylic acids, which are also present in the form of their alkali metal salts can.
  • sequestering agents preferably phosphates, alkyl phosphates, alkylphosphonic acids and among these in particular those having at least one amine oxide substituent on the alkyl group
  • Aminoxidphosphonklaren phosphates, alkyl phosphates, alkylphosphonic acids and among these in particular those having at least one amine oxide substituent on the alkyl group
  • Aminoxidphosphonklaren phosphates, alkyl phosphates, alkylphosphonic acids and among these in particular those having at least one amine oxide substituent on the alkyl group
  • Amine oxide phosphonic acids are the amine oxide based on aminotrimethylene phosphonic acid. Preferably, from 0.01% to 2% by weight of such sequestering agents are present.
  • the agents contain 0.1% by weight to 2% by weight of carbonate, in particular alkali carbonate.
  • the corrosion-improved preparations according to the invention may contain small amounts of one or more pale-stable dyes or fragrances.
  • the optional perfume component is preferably of higher relative volatility than the ingredients optionally responsible for a bleaching odor.
  • the stabilized compositions according to the invention can be prepared in a simple manner by mixing the above-mentioned ingredients in the indicated amounts. They are applied after dilution with water or, if desired, also undiluted.

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Description

Die vorliegende Erfindung betrifft die Verminderung der KorrosivitƤt von Hypochlorit an MetalloberflƤchen beim Einsatz hypochlorit-haltiger flĆ¼ssiger Reinigungsmittel zur Reinigung von MetalloberflƤchen.The present invention relates to the reduction of corrosivity of hypochlorite on metal surfaces when using hypochlorite-containing liquid detergents for cleaning metal surfaces.

Reinigungsmittel fĆ¼r harte OberflƤchen, beispielsweise KĆ¼chen- und Badezimmerreiniger, sind in der Vergangenheit hoch abrasive Pulver gewesen, die gegebenenfalls geringe Mengen an Tensiden enthielten und zutreffend als Scheuerpulver bezeichnet wurden. Sie waren aggressiv nicht nur zur Hand des Benutzers, sondern auch zu der OberflƤche, mit der sie zu Reinigungszwecken in Kontakt gebracht wurden. In einigen FƤllen wurde ein Bleichmittel in derartige Scheuerpulver eingearbeitet, um Anschmutzungen oxidativ aufzubrechen und dadurch ihre Entfernbarkeit zu erleichtern. Auch wenn moderne Abrasivreiniger inzwischen deutlich hautfreundlicher in ihrer Zusammensetzung sind, verlassen sich diese Reiniger dennoch im wesentlichen auf die Wirkung des Abrasivstoffs, um Anschmutzungen zu entfernen, zu denen insbesondere auch Seifenablagerungen, die in der Regel im Wesentlichen aus der persƶnlichen Hygiene stammen, von harten OberflƤchen, wie beispielsweise von Badezimmerkacheln oder Waschbecken, zu entfernen.Hard surface cleaners, such as kitchen and bathroom cleaners, have historically been highly abrasive powders, optionally containing low levels of surfactants and properly referred to as scouring powders. They were aggressive not only to the user's hand, but also to the surface with which they were brought into contact for cleaning purposes. In some cases, a bleaching agent has been incorporated into such scrubbing powders to oxidatively break up soils and thereby facilitate their removability. Although modern abrasive cleaners are now much more skin-friendly in their composition, these cleaners still rely essentially on the action of Abrasivstoffs to remove stains, which in particular soap deposits, which are usually derived mainly from personal hygiene, from hard Remove surfaces such as bathroom tiles or sinks.

Zur Entfernung der Anschmutzungen wird Ć¼blicherweise nach der Anwendung des Reinigungsmittels ein Nachwischen mit einem feuchten oder auch trockenen Tuch erforderlich. Erstrebenswert ist auƟerdem, daƟ das Reinigungsmittel die auf der harten OberflƤche befindliche Anschmutzung durchdringt und so das Abheben der Anschmutzung von der OberflƤche erleichtert. Natriumhypochlorit ist bekannt als hoch effektives Bleichmittel und wird seit langem, gegebenenfalls zusammen mit Seifen und/oder synthetischen Tensiden, zur Entfernung von Flecken und allen Arten von Anschmutzungen bei der WƤsche von Textilien wie auch beim Reinigen harter OberflƤchen benutzt. Es wird normalerweise in Konzentrationen von etwa 2 bis 10 Gew.-% in Wasser fĆ¼r die Verwendung in Haushalten vertrieben. WƤhrend man beim Einsatz von hypochlorithaltigen Mitteln eine ausgezeichnete Desinfektionsleistung und sehr gute Reinigungsergebnisse an harten OberflƤchen erzielt, beobachtet man an empfindlichem Reinigungsgut in einigen FƤllen eine VerƤnderung der OberflƤche. Diese kann von einer leichten BeeintrƤchtigung des optischen Eindrucks bis hin zum Auftreten von Vertiefungen in der OberflƤche oder sogar LochfraƟ bestehen, wobei schwere FƤlle normalerweise nur bei unsachgemƤƟer Anwendung des Mittels auftreten.To remove stains, it is usually necessary to wipe with a damp or dry cloth after using the cleaner. It is also desirable that the cleaning agent penetrate the soil on the hard surface so as to facilitate the lifting of the soil from the surface. Sodium hypochlorite is known to be a highly effective bleaching agent and has been used for a long time, optionally with soaps and / or synthetic surfactants, to remove stains and all sorts of soils from laundry to textiles as well as hard surface cleaning. It is normally sold in concentrations of about 2 to 10% by weight in water for household use. While the use of hypochlorite agents an excellent disinfecting performance and very good Cleaning results achieved on hard surfaces, observed in sensitive cleaning in some cases, a change in the surface. This can range from a slight impairment of the visual impression to the appearance of pits in the surface or even pitting, with severe cases usually occurring only with improper use of the agent.

Zu den hier angesprochenen empfindlichen OberflƤchen gehƶren insbesondere solche aus Metall, beispielsweise Stahl-OberflƤchen, wie sie etwa in KĆ¼chenspĆ¼len, als GehƤuseoberflƤchen von Haushaltsmaschinen oder Verkleidungen von KĆ¼chen- oder BadezimmerschrƤnken zu finden sind. Bei der Reinigung solcher OberflƤchen besteht die Gefahr, daƟ es durch die MetallkorrosivitƤt des Hypochlorits zu SchƤdigungen der OberflƤche kommen kann, insbesondere wenn man ein normalerweise nach VerdĆ¼nnen mit Wasser anzuwendendes Mittel unverdĆ¼nnt auf die MetalloberflƤche aufbringt und dort lƤngere Zeit belƤƟt. Hypochlorit enthaltende Reinigungsmittel sind biespielweise aus EP 311 175 , DE 19700799 unnd EP903403 bekannt.The sensitive surfaces mentioned here include, in particular, those made of metal, for example steel surfaces, such as those found in kitchen sinks, as housing surfaces of domestic appliances or linings of kitchen or bathroom cabinets. When cleaning such surfaces, there is a risk that the metal corrosivity of the hypochlorite can lead to damage to the surface, in particular if a solvent which is normally to be applied after dilution with water is applied undiluted to the metal surface and left there for a longer time. Hypochlorite-containing detergents are biespielweise EP 311 175 . DE 19700799 unnd EP903403 known.

Ɯberraschenderweise wurde nun gefunden, dass die Anpassung beziehungsweise die gezielte Auswahl der sonstigen Inhaltsstoffe hypochlorithaltiger Reinigungsmittel das Korrosionsverhalten positiv beeinfluƟt.Surprisingly, it has now been found that the adaptation or the targeted selection of the other ingredients hypochlorite detergent positively influences the corrosion behavior.

Gegenstand der vorliegenden Erfindung ist die Verwendung einer Kombination aus Alkalihydroxid, Alkalisilikat, Alkyl-(Alkoxy)n-sulfat mit n = 0,5 bis 10 und Alkylphoshat in einem Hypochlorit-enthaltenden wƤƟrigen flĆ¼ssigen Reinigungsmittel zur Verminderung der KorrosivitƤt von Hypochlorit an MetalloberflƤchen. Vorzugsweise ist dabei die MetalloberflƤche eine Stahl-OberflƤche, da dann der Verbesserungseffekt der erfindungsgemƤƟ verwendeten Kombination besonders ausgeprƤgt ist. Die erfindungsgemƤƟ verwendete Kombination ist vorzugsweise Bestandteil des hypochlorithaltigen Reinigungsmittels.The present invention is the use of a combination of alkali metal hydroxide, alkali silicate, alkyl (alkoxy) n -sulfate with n = 0.5 to 10 and Alkylphoshat in a hypochlorite-containing aqueous liquid detergent to reduce the corrosivity of hypochlorite to metal surfaces. Preferably, the metal surface is a steel surface, since then the improvement effect of the combination used in the invention is particularly pronounced. The combination used according to the invention is preferably a constituent of the hypochlorite-containing cleaning agent.

In einer bevorzugten AusfĆ¼hrungsform der Erfindung enthƤlt das Reinigungsmittel 0,5 Gew.-% bis 10 Gew.-%, insbesondere 2 Gew.-% bis 5,5 Gew.-% Alkalihypochlorit. Obzwar auch andere Alkalihypochlorite, wie beispielsweise Kaliumhypochlorit, brauchbar sind, ist es doch bevorzugt, erfindungsgemƤƟ Natriumhypochlorit einzusetzen. In handelsĆ¼blichen wƤƟrigen Natriumhypochlorit-Lƶsungen sind oft betrƤchtliche Mengen an Chlorid-Salzen enthalten. Diese kƶnnen ohne weiteres zur Herstellung erfindungsgemƤƟ korrosionsverbesserter Mittel.verwendet werden, so dass man auf den Einsatz von hochreinem NaOCl nicht notwendigerweise angewiesen ist.In a preferred embodiment of the invention, the cleaning agent contains 0.5 wt .-% to 10 wt .-%, in particular 2 wt .-% to 5.5 wt .-% alkali metal hypochlorite. Although other alkali metal hypochlorites, such as potassium hypochlorite, are useful, it is still preferable to use sodium hypochlorite in the present invention. In Commercially available aqueous sodium hypochlorite solutions often contain considerable amounts of chloride salts. These can readily be used for the production of corrosion-enhanced agents according to the invention, so that it is not necessarily dependent on the use of high-purity NaOCl.

Die hypochlorithaltigen Mittel sind alkalisch, wobei erfindungsgemƤƟ bevorzugt ist, wenn das Reinigungsmittel mehr als 0 Gew.-% bis zu 5 Gew.-%, insbesondere 0,1 Gew.-% bis 2 Gew.-% Alkalihydroxid enthƤlt.The hypochlorite-containing agents are alkaline, it being preferred according to the invention, when the cleaning agent contains more than 0 wt .-% up to 5 wt .-%, in particular 0.1 wt .-% to 2 wt .-% alkali metal hydroxide.

Vorzugsweise sind mehr als 0 Gew.-% bis zu 5 Gew.-%, insbesondere 0,1 Gew.-% bis 2,5 Gew.-% Alkalisilikat in dem Mittel enthalten. Dadurch wird nicht nur das Korrosionsverhalten verbessert, sondern auch die LagerstabilitƤt des Hypochlorits erhƶht.Preferably, more than 0 wt .-% up to 5 wt .-%, in particular 0.1 wt .-% to 2.5 wt .-% alkali metal silicate in the agent. This not only improves the corrosion behavior but also increases the storage stability of the hypochlorite.

Eine weitere Komponente der erfindungsgemƤƟ verwendeten Kombination ist ein Tensid in Form eines Alkyl-(Alkoxy)n-sulfats, das auch als Alkylethersulfat bezeichnet werden kann und durch Umsetzung von Alkoholen (vorzugsweise mit 6 bis 22 Kohlenstoffatomen) mit Alkylenoxiden, insbesondere Ethylenoxid, und anschlieƟende Sulfatierung und Neutralisation, insbesondere mit alkalischen Alkalisalzen wie Alkalihydroxiden, erhƤltlich ist. In Frage kommt insbesondere ein mit 2 Equivalenten Ethylenoxid alkoxyliertes C12-14-Fettalkoholethersulfat. Alkyl-(Alkoxy)n-sulfat ist vorzugsweise in dem Reinigungsmittel von mehr als 0 Gew.-% bis zu 5 Gew.-% enthalten. Das Alkyl-(Alkoxy)n-sulfat weist vorzugsweise eine C8-18-, insbesondere C12-16-Alkylgruppe, -OCH2CH2- und/oder -OCHCH3CH2- Alkoxygrupppe(n) auf, wobei n vorzugsweise eine Zahl von 1 bis 6, insbesondere 2 bis 5 ist.Another component of the combination used in the invention is a surfactant in the form of an alkyl (alkoxy) n- sulfate, which may also be referred to as alkyl ether sulfate and by reacting alcohols (preferably having 6 to 22 carbon atoms) with alkylene oxides, in particular ethylene oxide, and subsequent Sulfation and neutralization, especially with alkaline alkali metal salts such as alkali metal hydroxides, is available. In question is in particular a 2 equivalents of ethylene oxide alkoxylated C 12-14 fatty alcohol ether sulfate. Alkyl (alkoxy) n- sulfate is preferably included in the detergent from greater than 0% to 5% by weight. The alkyl (alkoxy) n- sulphate preferably has a C 8-18 , in particular C 12-16 -alkyl group, -OCH 2 CH 2 - and / or -OCHCH 3 CH 2 -alkoxy group (s), where n is preferably is a number from 1 to 6, especially 2 to 5.

Das bevorzugte Alkalihydroxid ist Natriumhydroxid, und auch die Alkalisalze, die im Zusammenhang mit den Ć¼brigen Inhaltsstoffen der Mittel genannt werden, sind vorzugsweise die Natriumsalze. So ist insbesondere das Alkalisilikat Natriumsilikat und/oder das Alkalimetall-Gegenion des Ethersulfats das Natriumion.The preferred alkali hydroxide is sodium hydroxide, and also the alkali salts mentioned in connection with the other ingredients of the compositions are preferably the sodium salts. Thus, in particular, the alkali metal silicate sodium silicate and / or the alkali metal counterion of the ether sulfate is the sodium ion.

Das Reinigungsmittel kann gewĆ¼nschtenfalls bis zu 5 Gew.-% zusƤtzlichen bleichstabilen Tensides enthalten. Bevorzugt sind Betaine, insbesondere solche der allgemeinen Formel I,

Figure imgb0001
in der R1 eine Alkyl- oder Alkenylgruppe mit 6 bis 22 Kohlenstoffatomen oder eine Gruppe R4CO-NH-(CH2)n- ist, R2 Wasserstoff oder eine Alkylgruppe mit 1 bis 4 Kohlenstoffatomen ist, R3 Wasserstoff oder eine Alkylgruppe mit 1 bis 4 Kohlenstoffatomen ist, R4 eine Alkyl- oder Alkenylgruppe mit 6 bis 22 Kohlenstoffatomen ist, m eine Zahl von 1 bis 6 und n eine Zahl von 1 bis 3 ist. Beispiele fĆ¼r besonders geeignete Vertreter dieser Klasse von Tensiden umfassen C12-18-Alkyl-dimethylbetain, kommerziell erhƤltlich als KokosnuƟbetain, und C10-16-Alkyl-dimethylbetain, kommerziell erhƤltlich als Laurylbetain.If desired, the cleaning agent may contain up to 5% by weight of additional bleach-stable surfactant. Preference is given to betaines, in particular those of the general formula I,
Figure imgb0001
 wherein R 1 is an alkyl or alkenyl group having 6 to 22 carbon atoms or a group R 4 is CO-NH- (CH 2 ) n -, R 2 is hydrogen or an alkyl group having 1 to 4 carbon atoms, R 3 is hydrogen or an alkyl group with 1 to 4 carbon atoms, R 4 is an alkyl or alkenyl group having 6 to 22 carbon atoms, m is a number from 1 to 6 and n is a number from 1 to 3. Examples of particularly suitable members of this class of surfactants include C 12-18 alkyl dimethyl betaine, commercially available as coconut betaine, and C 10-16 alkyl dimethyl betaine, commercially available as lauryl betaine.

Die Zubereitungen kƶnnen zusƤtzlich Sequestriermittel enthalten, vorzugsweise Phosphate, Alkylphosphate, AlkylphosphonsƤuren und unter diesen insbesondere solche mit zumindest einem Aminoxid-Substituenten an der Alkylgruppe, hier als AminoxidphosphonsƤuren bezeichnet, PolyacrylsƤuren und/oder Phosphonogruppen-aufweisende PolyacrysƤuren, die auch in der Form ihrer Alkalisalze vorliegen kƶnnen. Die Einarbeitung derartiger Komplexbildner fĆ¼hrt Ć¼berraschenderweise zu besonders gutem Glanzerhalt der behandelten harten OberflƤchen. Dies wird nicht beobachtet, wenn man stattdessen andere Komplexbildner, beispielsweise MethylglycindiessigsƤure oder NitrilotriessigsƤure, einsetzt. AminoxidphosphonsƤuren werden normalerweise durch Oxidation von AminoalkylphosphonsƤuren hergestellt. Sie gehƶren vorzugsweise zur Gruppe von Verbindungen gemƤƟ allgemeiner Formel (II),

Figure imgb0002
in der R5 Wasserstoff, eine Gruppe -(CH2)x(CHCH3)y-NH2->O oder ein Alkalimetall ist, x eine Zahl von 1 bis 4 und y 0 oder 1 ist. Unter den besonders bevorzugten AminoxidphosphonsƤuren ist das Aminoxid auf der Basis der AminotrimethylenphosphonsƤure. Vorzugsweise sind 0,01 Gew.-% bis 2 Gew.-% solcher Sequestriermittel vorhanden.The preparations may additionally contain sequestering agents, preferably phosphates, alkyl phosphates, alkylphosphonic acids and among these in particular those having at least one amine oxide substituent on the alkyl group, referred to herein as AminoxidphosphonsƤuren, polyacrylic acids and / or phosphono-containing polyacrylic acids, which are also present in the form of their alkali metal salts can. The incorporation of such complexing leads surprisingly to a particularly good gloss retention of the treated hard surfaces. This is not observed if instead other complexing agents, for example methylglycinediacetic acid or nitrilotriacetic acid, are used. Amine oxide phosphonic acids are normally prepared by oxidation of aminoalkyl phosphonic acids. They preferably belong to the group of compounds according to general formula (II),
Figure imgb0002
 wherein R 5 is hydrogen, a group - (CH 2 ) x (CHCH 3 ) y -NH 2 -> O or an alkali metal, x is a number from 1 to 4 and y is 0 or 1. Among the most preferred Amine oxide phosphonic acids is the amine oxide based on aminotrimethylene phosphonic acid. Preferably, from 0.01% to 2% by weight of such sequestering agents are present.

Weiterhin ist es bevorzugt, wenn die Mittel 0,1 Gew.-% bis 2 Gew.-% Carbonat, insbesondere Alkalicarbonat, enthalten.It is furthermore preferred if the agents contain 0.1% by weight to 2% by weight of carbonate, in particular alkali carbonate.

ZusƤtzlich zu den genannten Bestandteilen kƶnnen die erfindungsgemƤƟ korrosionsverbesserten Zubereitungen geringe Mengen an einem oder mehreren bleichstabilen Farb- oder Riechstoffen enthalten. Die gegebenenfalls enthaltene Duftstoffkomponente ist vorzugsweise von hƶherer relativer FlĆ¼chtigkeit als die Bestandteile, die gegebenenfalls fĆ¼r einen Bleichegeruch verantwortlich sind.In addition to the constituents mentioned, the corrosion-improved preparations according to the invention may contain small amounts of one or more pale-stable dyes or fragrances. The optional perfume component is preferably of higher relative volatility than the ingredients optionally responsible for a bleaching odor.

Die erfindungsgemƤƟ stabilisierten Mittel kƶnnen in einfacher Weise durch Vermischen der obengenannten Inhaltsstoffe in den angegebenen Mengen hergestellt werden. Sie werden nach VerdĆ¼nnen mit Wasser oder gewĆ¼nschtenfalls auch unverdĆ¼nnt angewendet.The stabilized compositions according to the invention can be prepared in a simple manner by mixing the above-mentioned ingredients in the indicated amounts. They are applied after dilution with water or, if desired, also undiluted.

Beispiele (nicht erfindungsgemƤss)Examples (not according to the invention)

Das Korrosionsverhalten hypochlorithaltiger Zubereitungen wurde untersucht. Dazu wurden BlƤttchen aus Stahlblech in die unverdĆ¼nnten Zubereitungen eingelegt und die relative Korrosionsrate nach 14 Tagen, 21 Tagen und 25 Tagen bestimmt. Das Aussehen der StahlblƤttchen ist in den Figuren 1 und 2 wiedergegeben, wobei Figur 1 die OberflƤche nach dem Einlegen in Natriumhypochlorit (2 Gew.-% in Wasser) zeigt und Figur 2 die OberflƤche nach dem Einlegen in ein wƤƟriges Mittel, das 2 Gew.-% Natriumhypochlorit, 1,5 Gew.-% NaOH, 3 Gew.-% Na-C14/16-Alkyl-(ethoxy)2-sulfat und 2 Gew.-% Natriumsilikat enthielt. Probe 3 ist dabei jeweils nach 14 Tagen, Probe 4 nach 21 Tagen und Probe 5 nach 25 Tagen erhalten worden. Man erkennt die deutlich geringere SchƤdigung der MetalloberflƤche durch die erfindungsgemƤƟe Verwendung der Kombination.The corrosion behavior of hypochlorite-containing preparations was investigated. For this purpose, sheets of sheet steel were placed in the undiluted preparations and the relative corrosion rate determined after 14 days, 21 days and 25 days. The appearance of the steel blades is in the Figures 1 and 2 reproduced, wherein FIG. 1 the surface after placing in sodium hypochlorite (2 wt .-% in water) shows and FIG. 2 the surface after placing in an aqueous medium, the 2 wt .-% sodium hypochlorite, 1.5 wt .-% NaOH, 3 wt .-% Na-C 14/16 alkyl (ethoxy) 2 sulfate and 2 wt % Sodium silicate. Sample 3 was obtained in each case after 14 days, sample 4 after 21 days and sample 5 after 25 days. One recognizes the significantly lower damage to the metal surface by the inventive use of the combination.

Claims (11)

  1. Use of a combination of alkali metal hydroxide, alkali metal silicate and alkyl-(alkoxy)n sulfate with n = 0.5 to 10 and alkyl phosphate in a hypochlorite-containing aqueous liquid cleaning agent for reducing the corrosivity of hypochlorite on metal surfaces.
  2. Use according to claim 1, characterised in that the metal surface is a steel surface.
  3. Use according to claim 1 or 2, characterised in that the cleaning agent comprises 0.5 wt % to 10 wt %, in particular 2 wt % to 5.5 wt % alkali metal hypochlorite, especially sodium hypochlorite.
  4. Use according to one of the claims 1 to 3, characterised in that the cleaning agent comprises more than 0 wt % up to 5 wt %, in particular 0.1 wt % to 2 wt % alkali metal hydroxide.
  5. Use according to one of the claims 1 to 4, characterised in that the cleaning agent comprises more than 0 wt % up to 5 wt %, in particular 0.1 wt % to 2.5 wt % alkali metal silicate.
  6. Use according to one of the claims 1 to 5, characterised in that the cleaning agent comprises more than 0 wt % up to 5 wt %, alkyl-(alkoxy)n sulfate.
  7. Use according to one of the claims 1 to 6, characterised in that the cleaning agent comprises alkyl-(alkoxy)n sulfate with a C8-18 alkyl group, in particular C12-16 alkyl group, -OCH2CH2- and/or -OCHCH3CH2- alkoxy group(s), in which n is a number from 1 to 6, in particular 2 to 5 and which possess an alkali metal counter ion for the sulfate group.
  8. Use according to one of the claims 1 to 7, characterised in that the alkali metal hydroxide is sodium hydroxide, the alkali metal silicate is sodium silicate and/or the alkali metal counter ion is the sodium ion.
  9. Use according to one of the claims 1 to 8, characterised in that the cleaning agent comprises up to 5 wt % of additional bleach-stable surfactant, in particular betaine.
  10. Use according to one of the claims 1 to 9, characterised in that the cleaning agent additionally comprises 0.01 wt % to 2 wt % alkylphosphonic acid and/or phosphonate, in particular amine oxide phosphonic acid, polyacrylic acid that exhibits phosphono groups and/or the alkali metal salt of one or both of these acids, and/or 0.1 wt % to 2 wt % carbonate, in particular alkali metal carbonate.
  11. Method for cleaning metal surfaces, in particular steel surfaces, characterised by the use of a hypochlorite-containing aqueous liquid cleaning agent that comprises a combination of alkali metal hydroxide, alkali metal silicate, alkyl-(alkoxy)n sulfate with n = 0.5 to 10 and alkyl phosphate.
EP06819024A 2005-12-29 2006-12-13 Inhibiting the corrosive properties of liquid cleaning agents containing hypochlorite Active EP1966363B1 (en)

Priority Applications (1)

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PL06819024T PL1966363T3 (en) 2005-12-29 2006-12-13 Inhibiting the corrosive properties of liquid cleaning agents containing hypochlorite

Applications Claiming Priority (2)

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DE102005063065A DE102005063065A1 (en) 2005-12-29 2005-12-29 Corrosion inhibition of liquid hypochlorite detergent
PCT/EP2006/011960 WO2007079881A1 (en) 2005-12-29 2006-12-13 Inhibiting the corrosive properties of liquid cleaning agents containing hypochlorite

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EP1966363A1 EP1966363A1 (en) 2008-09-10
EP1966363B1 true EP1966363B1 (en) 2012-10-24

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EP (1) EP1966363B1 (en)
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WO (1) WO2007079881A1 (en)

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ES2394363T3 (en) 2013-01-31
WO2007079881A1 (en) 2007-07-19
DE102005063065A1 (en) 2007-07-12
EP1966363A1 (en) 2008-09-10
US20080274934A1 (en) 2008-11-06
PL1966363T3 (en) 2013-03-29

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