EP1957620A1 - Increasing the stability of liquid hypochlorite-containing washing and cleaning compositions - Google Patents

Increasing the stability of liquid hypochlorite-containing washing and cleaning compositions

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Publication number
EP1957620A1
EP1957620A1 EP06828979A EP06828979A EP1957620A1 EP 1957620 A1 EP1957620 A1 EP 1957620A1 EP 06828979 A EP06828979 A EP 06828979A EP 06828979 A EP06828979 A EP 06828979A EP 1957620 A1 EP1957620 A1 EP 1957620A1
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EP
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Prior art keywords
hypochlorite
weight
alkali
use according
composition
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Granted
Application number
EP06828979A
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German (de)
French (fr)
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EP1957620B1 (en
Inventor
Carlos Malet
Carlos Perez
Miguel Osset
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Henkel AG and Co KGaA
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Henkel AG and Co KGaA
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Publication of EP1957620A1 publication Critical patent/EP1957620A1/en
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Publication of EP1957620B1 publication Critical patent/EP1957620B1/en
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Classifications

    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
    • C11D3/16—Organic compounds
    • C11D3/20—Organic compounds containing oxygen
    • C11D3/2068—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
    • C11D3/395—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
    • C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
    • C11D3/40—Dyes ; Pigments

Definitions

  • the present invention relates to the stabilization of hypochlorite-containing liquid detergents and / or cleaning agents for hard surfaces in households, for example for cleaning tiles.
  • Sodium hypochlorite is known as a highly effective bleaching agent and has been used for a long time, optionally together with soaps and / or synthetic surfactants, to remove stains and all types of soiling when washing textiles and when cleaning hard surfaces. It is usually sold in concentrations of about 2% to 10% by weight in water for household use.
  • Liquid detergent preparations or corresponding preparations of cleaning agents for hard surfaces which contain hypochlorite as the bleaching component, are susceptible to loss of activity in the case of prolonged storage, in particular because of the degradation of the hypochlorite which then takes place.
  • the ingredients that are desirable in washing and cleaning agents from the point of view of use or for aesthetic reasons include, in addition to the active ingredients that decisively influence the performance of such agents, in particular hypochlorite in this case, also coloring agents which are intended to give liquid preparations in particular a pleasant visual appearance.
  • Dyes in particular are usually slightly oxidatively attacked by hypochlorite, so that in addition to the loss of the bleaching agent, the color impression of hypochlorite-containing liquid agents also changes rapidly during storage.
  • fragrances which are attacked by the strong oxidizing agent hypochlorite in a large number of cases so that the fragrance impression of perfumed agents changes in an unacceptable manner when stored.
  • the invention therefore relates to the use of p-methoxybenzyl alcohol for stabilizing hypochlorite-containing aqueous liquid compositions which contain colored metal pigment.
  • a second subject of the invention is therefore the joint use of p-methoxybenzyl alcohol and an alkali iodide for stabilizing hypochlorite-containing aqueous liquid compositions which contain colored metal pigment.
  • Another object of the invention is an aqueous liquid bleaching agent containing alkali hypochlorite and colored metal pigment, which is characterized in that it additionally contains p-methoxybenzyl alcohol, optionally in combination with akali iodide.
  • p-Methoxybenzyl alcohol is also known as anise alcohol. It is commercially available and has so far been used, for example, as a component of fragrance.
  • the liquid agent stabilized according to the invention contains 0.5% by weight to 5% by weight of alkali hypochlorite, in particular sodium hypochlorite.
  • compositions are particularly suitable and very effective as cleaning agents for hard surfaces, for example for use on walls, work surfaces, floors and the like.
  • the compositions particularly because of their hypochlorite content, are particularly suitable for removing soiling that occurs in kitchens or bathrooms, including the greasy soiling that can occur after the use of bathtubs, shower cubicles and wash basins.
  • a bleaching agent in the form of hypochlorite is an essential component of the agents according to the invention.
  • Bleaching agents in themselves are well known components of detergent compositions and are particularly successful in combating mildew and mold, soiling that can often be found in soap deposits or in association with them.
  • alkali hypochlorites such as, for example, potassium hypochlorite
  • chloride salts there are often considerable amounts of chloride salts contain. These can easily be used to produce agents according to the invention, so that one does not necessarily have to rely on the use of high-purity NaOCl.
  • the compositions contain 0.5% by weight to 4.5% by weight, in particular 1% by weight to 4% by weight, of alkali hypochlorite.
  • compositions preferably contain more than 0% by weight to approximately 0.01% by weight, in particular approximately 0.001% by weight to approximately 0.008% by weight, of colored, in particular blue and / or green, metal pigment.
  • complex compounds of nickel, cobalt, cupfer, iron and / or manganese are preferred; copper phthalocyanine dyes are particularly preferred.
  • the stability of both the colored metal pigment and the alkali hypochlorite is increased by the presence of alkali iodide.
  • alkali iodide There is preferably more than 0% by weight up to about 0.01% by weight, in particular about 0.001% by weight to about 0.006% by weight, of alkali iodide, in particular potassium iodide.
  • the agents stabilized according to the invention are normally alkaline and for this purpose can contain about 0.1% by weight to 2% by weight, in particular 0.1% by weight to 1.1% by weight, of alkali metal hydroxide.
  • the preferred alkali hydroxide is sodium hydroxide, and the alkali salts, which are mentioned in connection with the other ingredients of the compositions, are preferably the sodium salts.
  • the preparations can contain surfactants which are stable in the presence of the hypochlorite.
  • Betaines in particular of the general formula I, are preferred,
  • Examples of particularly suitable representatives of this class of surfactants include Ci 2- ig alkyl dimethyl betaine, commercially available as coconut betaine, and Ci 0- i 6 alkyl dimethyl betaine, commercially available as lauryl betaine.
  • alkyl ether sulfates which can be obtained by reacting alcohols (preferably having 6 to 22 carbon atoms) with alkylene oxides, in particular ethylene oxide, and subsequent sulfation and neutralization, in particular a C 1 -C 4 -fatty alcohol ether sulfate alkoxylated with 2 equivalents of ethylene oxide .
  • the corresponding cation is preferably sodium.
  • surfactants are preferably present in amounts up to 5% by weight, in particular from 0.01% by weight to 3% by weight, in agents stabilized according to the invention.
  • the preparations can additionally contain sequestering agents, preferably alkylphosphonic acids and among them in particular those with at least one amine oxide substituent on the alkyl group, here referred to as amine oxidephosphonic acids, polyacrylic acids and / or polyacrylic acids having phosphono groups, which may also be present in the form of their alkali metal salts.
  • sequestering agents preferably alkylphosphonic acids and among them in particular those with at least one amine oxide substituent on the alkyl group, here referred to as amine oxidephosphonic acids, polyacrylic acids and / or polyacrylic acids having phosphono groups, which may also be present in the form of their alkali metal salts.
  • amine oxidephosphonic acids preferably alkylphosphonic acids and among them in particular those with at least one amine oxide substituent on the alkyl group
  • polyacrylic acids and / or polyacrylic acids having phosphono groups which may also be present in the form of their alkali metal salts.
  • R 5 is hydrogen, a group - (CH 2 ) x (CHCH 3 ) y -NH 2 -> 0 or an alkali metal, x is a number from 1 to 4 and y is 0 or 1.
  • the amine oxide is based on aminotrimethylene phosphonic acid. Preferably 0.01 wt% to 2 wt% of such sequestering agents are present.
  • the preparations stabilized according to the invention can contain small amounts of one or more bleach-stable fragrances.
  • the fragrance component optionally contained in addition to the anise alcohol is preferably of higher relative volatility than the constituents which are possibly responsible for a smell of bleach.
  • the agents stabilized according to the invention can be prepared in a simple manner by mixing the above-mentioned ingredients in the stated amounts.
  • Preparations according to the invention (II, 12) with different pigment contents and, for comparison purposes, preparations of the same composition without anise alcohol and potassium iodide (Cl, C2) were prepared by mixing the ingredients with water.
  • the means were composed as follows [% by weight]:

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

Abstract

In hypochlorite-containing aqueous liquid washing and/or cleaning compositions which comprise colored metal pigment, the storage stability was to be improved. This was possible through the use of a particular aromatic fragrance.

Description

Erhöhung der Stabilität flüssiger hypochlorithaltiger Wasch- und Reinifiungsmittel  Increasing the stability of liquid hypochlorite-containing detergents and cleaning agents
Die vorliegende Erfindung betrifft die Stabilisierung hypochlorit-haltiger flüssiger Waschmittel und/oder Reinigungsmittel für harte Oberflächen in Haushalten, zum Beispiel zur Reinigung von Kacheln. The present invention relates to the stabilization of hypochlorite-containing liquid detergents and / or cleaning agents for hard surfaces in households, for example for cleaning tiles.
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 Wäsche von Textilien wie auch beim Reinigen harter Oberflächen benutzt. Es wird normalerweise in Konzentrationen von etwa 2 Gew.-% bis 10 Gew.-% in Wasser für die Verwendung in Haushalten vertrieben. Sodium hypochlorite is known as a highly effective bleaching agent and has been used for a long time, optionally together with soaps and / or synthetic surfactants, to remove stains and all types of soiling when washing textiles and when cleaning hard surfaces. It is usually sold in concentrations of about 2% to 10% by weight in water for household use.
Flüssige Waschmittelzubereitungen oder entsprechende Zubereitungen von Reinigungsmitteln für harte Oberflächen, die Hypochlorit als Bleichkomponente enthalten, sind bei länger andauernder Lagerung anfällig gegen einen Verlust an Aktivität, insbesondere wegen des dann stattfindenden Abbaus des Hypochlorits. Zu den Inhaltstoffen, die unter Anwendungsgesichtspunkten oder aus ästhetischen Gründen in Wasch- und Reinigungsmitteln erwünscht sind, gehören neben den die Leistung solcher Mittel entscheidend beeinflussenden Wirkstoffen, hier insbesondere das Hypochlorit, auch Färbemittel, welche insbesondere flüssigen Zubereitungen eine angenehme optische Erscheinungsform geben sollen. Besonders Farbstoffe werden von Hypochlorit in aller Regel leicht oxidativ angegriffen, so dass sich zusätzlich zum Verlust des Bleichmittels auch der Farbeindruck hypochlorithaltiger flüssiger Mittel bei Lagerung rasch verändert. Gleiches gilt für Duftstoffe, die durch das starke Oxdationsmittel Hypochlorit in einer Vielzahl der Fälle angegriffen werden, so daß sich der Dufteindruck parfümierter Mittel bei Lagerung in oft unakzeptabler Weise verändert. Liquid detergent preparations or corresponding preparations of cleaning agents for hard surfaces, which contain hypochlorite as the bleaching component, are susceptible to loss of activity in the case of prolonged storage, in particular because of the degradation of the hypochlorite which then takes place. The ingredients that are desirable in washing and cleaning agents from the point of view of use or for aesthetic reasons include, in addition to the active ingredients that decisively influence the performance of such agents, in particular hypochlorite in this case, also coloring agents which are intended to give liquid preparations in particular a pleasant visual appearance. Dyes in particular are usually slightly oxidatively attacked by hypochlorite, so that in addition to the loss of the bleaching agent, the color impression of hypochlorite-containing liquid agents also changes rapidly during storage. The same applies to fragrances which are attacked by the strong oxidizing agent hypochlorite in a large number of cases, so that the fragrance impression of perfumed agents changes in an unacceptable manner when stored.
Obwohl es einige Vorschläge zur Stabilisierung von Alkalihypochlorit in wäßrigen Systemen gibt, sind dennoch alternative Lösungswege erstrebenswert. Die Europäische Patentanmeldung EP 0 903 403 schlägt zum Beispiel vor, ein Alkyl- (alkoxy)n-sulfat (mit n=0,5 bis 20), welches nur geringe Anteile an unsulfatiertem Material und sehr geringe Anteile an Metallverunreinigungen enthalten darf, zur Erhöhung der chemischen Stabilität flüssiger Bleichmittel, die ein Hypohalogenit enthalten, zu verwenden. Aus der internationalen Patentanmeldung WO 99/28427 ist bekannt, dass substituierte Benzole, welche einen Substituenten OCH3 oder CH=CHCOOM (wobei M Wasserstoff, ein Alkalimetall oder Ammonium ist) und gegebenenfalls bis zu drei weitere Substituenten OH, COOM, OCH3, CH3, CHO, CH2OH, COOCH3, COOC1-4H3-9, Ci-4H3-9, OCOCH3 oder NH2 oder Mischungen aus diesen aufweisen, in Mengen von 0,001 Gew.-% bis 10 Gew.-% als die Rheologie stabilisierende Wirkstoffe in verdickten wäßrigen Zusammensetzungen, die 0,1 Gew.-% bis 50 Gew.-% Alkalihypohalogenit, 0,01 Gew.-% bis 10 Gew.-% polymeren Rheologiemodifizierer, alkalischen Pufferwirkstoff für einen pH- Wert von 2 bis 4 und als Rest Wasser enthalten, eingesetzt werden können. Although there are some suggestions for stabilizing alkali hypochlorite in aqueous systems, alternative approaches are still desirable. European patent application EP 0 903 403, for example, proposes to increase an alkyl (alkoxy) n sulfate (with n = 0.5 to 20), which may only contain small amounts of unsulfated material and very small amounts of metal impurities the chemical stability of liquid bleaches containing hypohalite. From international patent application WO 99/28427 it is known that substituted benzenes which have a substituent OCH 3 or CH = CHCOOM (where M is hydrogen, an alkali metal or ammonium) and optionally up to three further substituents OH, COOM, OCH 3 , CH 3 , CHO, CH 2 OH, COOCH 3 , COOC 1-4 H 3-9 , Ci -4 H 3-9 , OCOCH 3 or NH 2 or mixtures thereof, in amounts of 0.001% by weight to 10% .-% as rheology stabilizing agents in thickened aqueous compositions containing 0.1 wt .-% to 50 wt .-% alkali hypohalite, 0.01 wt .-% to 10 wt .-% polymeric rheology modifier, alkaline buffering agent for a pH - Value of 2 to 4 and contain water as the rest can be used.
Überraschenderweise wurde nun gefunden, dass bestimmte aromatische Duftstoffe in wäßrigen flüssigen Wasch- und Reinigungsmitteln einen ausgeprägten Stabilisierungseffekt sowohl auf Hypochlorit haben, wie auch auf Farbpigmente, die in solchen Mitteln normalerweise durch das Hypochlorit ansonsten rasch abgebaut werden. Surprisingly, it has now been found that certain aromatic fragrances in aqueous liquid detergents and cleaning agents have a pronounced stabilizing effect both on hypochlorite and on color pigments, which in such agents are normally rapidly degraded by the hypochlorite.
Gegenstand der Erfindung ist daher die Verwendung von p-Methoxybenzylalkohol zur Stabilisierung von Hypochlorit-enthaltenden wäßrigen flüssigen Zusammensetzungen, die farbiges Metallpigment enthalten. The invention therefore relates to the use of p-methoxybenzyl alcohol for stabilizing hypochlorite-containing aqueous liquid compositions which contain colored metal pigment.
Als weiterer Vorteil wurde beobachtet, dass ein synergistischer Effekt zwischen dem Duftstoff und Alkalijodiden dazu führt, dass man größere Mengen an Farbstoffen in hypochlorithaltige Mittel einarbeiten kann, als dass dies sonst möglich wäre. Another advantage was observed that a synergistic effect between the fragrance and alkali iodides means that larger amounts of dyes can be incorporated into agents containing hypochlorite than would otherwise be possible.
Ein zweiter Gegenstand der Erfindung ist daher die gemeinsame Verwendung von p- Methoxybenzylalkohol und einem Alkalijodid zur Stabilisierung von Hypochloritenthaltenden wäßrigen flüssigen Zusammensetzungen, die farbiges Metallpigment enthalten. Ein weiterer Gegenstand der Erfindung ist ein wäßriges flüssiges Bleichmittel, enthaltend Alkalihypochlorit und farbiges Metallpigment, welches dadurch gekennzeichnet ist, dass es zusätzlich p-Methoxybenzylalkohol, gegebenenfalls in Kombination mit Akalijodid, enthält. p-Methoxybenzylalkohol wird auch als Anisalkohol bezeichnet. Er ist kommerziell erhältlich und findet bisher zum Beispiel als Komponente von Duftstoff gern i sehen Verwendung. A second subject of the invention is therefore the joint use of p-methoxybenzyl alcohol and an alkali iodide for stabilizing hypochlorite-containing aqueous liquid compositions which contain colored metal pigment. Another object of the invention is an aqueous liquid bleaching agent containing alkali hypochlorite and colored metal pigment, which is characterized in that it additionally contains p-methoxybenzyl alcohol, optionally in combination with akali iodide. p-Methoxybenzyl alcohol is also known as anise alcohol. It is commercially available and has so far been used, for example, as a component of fragrance.
Normalerweise ist es ausreichend, wenn mehr als 0 Gew.-% bis hin zu etwa 0,5 Gew.-%, insbesondere etwa 0,01 Gew.-% bis etwa 0,1 Gew.-% an p-Methoxybenzylalkohol in dem zu stabilisierenden flüssigen Mittel enthalten ist. It is normally sufficient if more than 0% by weight up to about 0.5% by weight, in particular about 0.01% by weight to about 0.1% by weight, of p-methoxybenzyl alcohol in the stabilizing liquid is included.
In einer bevorzugten Ausführungsform enthält das gemäß der Erfindung stabilisierte flüssige Mittel 0,5 Gew.-% bis 5 Gew.-% Alkalihypochlorit, insbesondere Natriumhypochlorit. In a preferred embodiment, the liquid agent stabilized according to the invention contains 0.5% by weight to 5% by weight of alkali hypochlorite, in particular sodium hypochlorite.
Derartige Zubereitungen sind insbesondere geeignet und sehr effektiv als Reinigungsmittel für harte Oberflächen, zum Beispiel zur Verwendung an Wänden, Arbeitsflächen, Fußböden und ähnlichem. Die Mittel sind, im wesentlichen wegen ihres Gehaltes an Hypochlorit, besonders geeignet zur Entfernung von Anschmutzungen, wie sie in Küchen oder Badezimmern auftreten, einschließlich der schmierigen Anschmutzungen, die nach der Benutzung von Badewannen, Duschkabinen und Waschbecken auftreten können. Such preparations are particularly suitable and very effective as cleaning agents for hard surfaces, for example for use on walls, work surfaces, floors and the like. The compositions, particularly because of their hypochlorite content, are particularly suitable for removing soiling that occurs in kitchens or bathrooms, including the greasy soiling that can occur after the use of bathtubs, shower cubicles and wash basins.
Ein Bleichmittel in Form von Hypochlorit ist ein wesentlicher Bestandteil der erfindungsgemäßen Mittel. Bleichmittel an sich sind durchaus bekannte Komponenten von Reinigungsmittelzusammensetzungen und sind insbesondere erfolgreich im Bekämpfen von Mehltau und Schimmel, Anschmutzungen, die sich in Seifenablagerungen oder in Gemeinschaft mit diesen häufig antreffen lassen. Obzwar auch andere Alkalihypochlorite, wie beispielsweise Kaliumhypochlorit, brauchbar sind, ist es doch bevorzugt, in erfindungsgemäß stabilisierten Mitteln Natriumhypochlorit einzusetzen. In handelsüblichen wäßrigen Natriumhypochlorit-Lösungen sind oft beträchtliche Mengen an Chlorid-Salzen enthalten. Diese können ohne weiteres zur Herstellung erfindungsgemäßer Mittel verwendet werden, so dass man auf den Einsatz von hochreinem NaOCl nicht notwendigerweise angewiesen ist. In einer bevorzugten Ausführungsform der Erfindung enthalten die Mittel 0,5 Gew.-% bis 4,5 Gew.-%, insbesondere 1 Gew.-% bis 4 Gew.-% Alkalihypochlorit. A bleaching agent in the form of hypochlorite is an essential component of the agents according to the invention. Bleaching agents in themselves are well known components of detergent compositions and are particularly successful in combating mildew and mold, soiling that can often be found in soap deposits or in association with them. Although other alkali hypochlorites, such as, for example, potassium hypochlorite, are also useful, it is preferred to use sodium hypochlorite in agents stabilized according to the invention. In commercial aqueous sodium hypochlorite solutions there are often considerable amounts of chloride salts contain. These can easily be used to produce agents according to the invention, so that one does not necessarily have to rely on the use of high-purity NaOCl. In a preferred embodiment of the invention, the compositions contain 0.5% by weight to 4.5% by weight, in particular 1% by weight to 4% by weight, of alkali hypochlorite.
Vorzugsweise enthalten die Mittel mehr als 0 Gew.-% bis etwa 0,01 Gew.-%, insbesondere etwa 0,001 Gew.-% bis etwa 0,008 Gew.-% an farbigem, insbesondere blauem und/oder grünem, Metallpigment. Unter diesen sind Komplexverbindungen des Nickels, Cobalts, Cupfers, Eisens und/oder Mangans bevorzugt; besonders bevorzugt sind Kupfer- Phthalocyanin-Farbstoffe. The compositions preferably contain more than 0% by weight to approximately 0.01% by weight, in particular approximately 0.001% by weight to approximately 0.008% by weight, of colored, in particular blue and / or green, metal pigment. Among them, complex compounds of nickel, cobalt, cupfer, iron and / or manganese are preferred; copper phthalocyanine dyes are particularly preferred.
Die Stabilität sowohl des farbigen Metallpigments wie auch des Alkalihypochlorits wird durch die Anwesenheit von Alkalijodid erhöht. Vorzugsweise sind mehr als 0 Gew.-% bis hin zu etwa 0,01 Gew.-%, insbesondere etwa 0,001 Gew.-% bis etwa 0,006 Gew.-% Alkalijodid, insbesondere Kaliumjodid, vorhanden. The stability of both the colored metal pigment and the alkali hypochlorite is increased by the presence of alkali iodide. There is preferably more than 0% by weight up to about 0.01% by weight, in particular about 0.001% by weight to about 0.006% by weight, of alkali iodide, in particular potassium iodide.
Die erfindungsgemäß stabilisierten Mittel sind normalerweise alkalisch und können zu diesem Zweck etwa 0,1 Gew.-% bis 2 Gew.-%, insbesondere 0,1 Gew.-% bis 1,1 Gew.-% Alkalihydroxid enthalten. Das bevorzugte Alkalihydroxid ist Natriumhydroxid, und auch die Alkalisalze, die im Zusammenhang mit den übrigen Inhaltsstoffen der Mittel genannt werden, sind vorzugsweise die Natriumsalze. The agents stabilized according to the invention are normally alkaline and for this purpose can contain about 0.1% by weight to 2% by weight, in particular 0.1% by weight to 1.1% by weight, of alkali metal hydroxide. The preferred alkali hydroxide is sodium hydroxide, and the alkali salts, which are mentioned in connection with the other ingredients of the compositions, are preferably the sodium salts.
Die Zubereitungen können Tenside enthalten, die in Gegenwart des Hypochlorits stabil sind. Bevorzugt sind Betaine, insbesondere der allgemeinen Formel I, The preparations can contain surfactants which are stable in the presence of the hypochlorite. Betaines, in particular of the general formula I, are preferred,
R1 R 1
R'-N+-(CH2)mCOO- (D R'-N + - (CH 2 ) m COO- (D
Rj 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 für besonders geeignete Vertreter dieser Klasse von Tensiden umfassen Ci2-ig-Alkyl-dimethylbetain, kommerziell erhältlich als Kokosnußbetain, und Ci0-i6-Alkyl-dimethylbetain, kommerziell erhältlich als Laurylbetain. Eine weitere Klasse besonders bevorzugter Tenside sind die Alkylethersulfate, die durch Umsetzung von Alkoholen (vorzugsweise mit 6 bis 22 Kohlenstoffatomen) mit Alkylenoxiden, insbesondere Ethylenoxid, und anschließende Sulfatierung und Neutralisation erhältlich sind, insbesondere ein mit 2 Equivalenten Ethylenoxid alkoxyliertes C^-π-Fettalkoholethersulfat. In den Ethersulfaten ist das korrespondierende Kation vorzugsweise Natrium. Tenside sind, falls anwesend, vorzugsweise in Mengen bis zu 5 Gew.-%, insbesondere von 0,01 Gew.-% bis 3 Gew.-% in erfindungsgemäß stabilisierten Mitteln enthalten. R j in which R 1 is an alkyl or alkenyl group with 6 to 22 carbon atoms or a group R 4 CO-NH- (CH 2 ) n -, R 2 is hydrogen or an alkyl group with 1 to 4 Is carbon atoms, R 3 is hydrogen or an alkyl group having 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 representatives of this class of surfactants include Ci 2- ig alkyl dimethyl betaine, commercially available as coconut betaine, and Ci 0- i 6 alkyl dimethyl betaine, commercially available as lauryl betaine. Another class of particularly preferred surfactants are the alkyl ether sulfates, which can be obtained by reacting alcohols (preferably having 6 to 22 carbon atoms) with alkylene oxides, in particular ethylene oxide, and subsequent sulfation and neutralization, in particular a C 1 -C 4 -fatty alcohol ether sulfate alkoxylated with 2 equivalents of ethylene oxide . In the ether sulfates, the corresponding cation is preferably sodium. If present, surfactants are preferably present in amounts up to 5% by weight, in particular from 0.01% by weight to 3% by weight, in agents stabilized according to the invention.
Die Zubereitungen können zusätzlich Sequestriermittel enthalten, vorzugsweise Alkylphosphonsäuren und unter diesen insbesondere solche mit zumindest einem Aminoxid-Substituenten an der Alkylgruppe, hier als Aminoxidphosphonsäuren bezeichnet, Polyacrylsäuren und/oder Phosphonogruppen-aufweisende Polyacrysäuren, die auch in der Form ihrer Alkalisalze vorliegen können. Die Einarbeitung derartiger Komplexbildner führt überraschenderweise zu besonders gutem Glanzerhalt der behandelten harten Oberflächen. Dies wird nicht beobachtet, wenn man stattdessen andere Komplexbildner, beispielsweise Methylglycindiessigsäure oder Nitrilotriessigsäure, einsetzt. Aminoxidphosphonsäuren werden normalerweise durch Oxidation von Aminoalkylphosphonsäuren hergestellt. Sie gehören vorzugsweise zur Gruppe von Verbindungen gemäß allgemeiner Formel (II), The preparations can additionally contain sequestering agents, preferably alkylphosphonic acids and among them in particular those with at least one amine oxide substituent on the alkyl group, here referred to as amine oxidephosphonic acids, polyacrylic acids and / or polyacrylic acids having phosphono groups, which may also be present in the form of their alkali metal salts. The incorporation of such complexing agents surprisingly leads to particularly good gloss retention of the treated hard surfaces. This is not observed if other complexing agents, for example methylglycinediacetic acid or nitrilotriacetic acid, are used instead. Amine oxide phosphonic acids are usually made by oxidation of aminoalkylphosphonic acids. They preferably belong to the group of compounds of the general formula (II)
O CH3 H O CH 3 H
Il I I  Il I I
HO-P-(CH2)x(CH)y-N->O (II) HO-P- (CH 2 ) x (CH) y -N-> O (II)
OR5 H in der R5 Wasserstoff, eine Gruppe -(CH2)x(CHCH3)y-NH2->0 oder ein Alkalimetall ist, x eine Zahl von 1 bis 4 und y 0 oder 1 ist. Unter den besonders bevorzugten Aminoxidphosphonsäuren ist das Aminoxid auf der Basis der Aminotrimethylenphosphon- säure. Vorzugsweise sind 0,01 Gew.-% bis 2 Gew.-% solcher Sequestriermittel vorhanden. OR 5 H in which R 5 is hydrogen, a group - (CH 2 ) x (CHCH 3 ) y -NH 2 -> 0 or an alkali metal, x is a number from 1 to 4 and y is 0 or 1. Among the particularly preferred amine oxide phosphonic acids, the amine oxide is based on aminotrimethylene phosphonic acid. Preferably 0.01 wt% to 2 wt% of such sequestering agents are present.
Zusätzlich zu den genannten Bestandteilen können die erfindungsgemäß stabilisierten Zubereitungen geringe Mengen an einem oder mehreren bleichstabilen Riechstoffen enthalten. Die gegebenenfalls zusätzlich zu dem Anisalkohol enthaltene Duftstoffkomponente ist vorzugsweise von höherer relativer Flüchtigkeit als die Bestandteile, die gegebenenfalls für einen Bleichegeruch verantwortlich sind. In addition to the constituents mentioned, the preparations stabilized according to the invention can contain small amounts of one or more bleach-stable fragrances. The fragrance component optionally contained in addition to the anise alcohol is preferably of higher relative volatility than the constituents which are possibly responsible for a smell of bleach.
Die erfindungsgemäß stabilisierten Mittel können in einfacher Weise durch Vermischen der obengenannten Inhaltsstoffe in den angegebenen Mengen hergestellt werden. The agents stabilized according to the invention can be prepared in a simple manner by mixing the above-mentioned ingredients in the stated amounts.
Beispiele Examples
Erfindungsgemäße Zubereitungen (II, 12) mit verschieden hohem Pigmentgehalt und zu Vergleichszwecken ansonsten gleich zusammengesetzte Zubereitungen ohne Anisalkohol und Kaliumjodid (Cl, C2) wurden durch Vermischen der Inhaltsstoffe mit Wasser hergestellt. Die Mittel waren wie folgt zusammengesetzt [Gew.-%]: Preparations according to the invention (II, 12) with different pigment contents and, for comparison purposes, preparations of the same composition without anise alcohol and potassium iodide (Cl, C2) were prepared by mixing the ingredients with water. The means were composed as follows [% by weight]:
Tabelle 1 : Zusammensetzungen Table 1: Compositions
Alle Mittel wurden in Plastikflaschen abgefüllt und 12 Wochen bei 20 °C gelagert. In den erfindungsgemäßen Zubereitungen war der Hypochloritgehalt nach Lagerung deutlich höher als in den zum Vergleich getesteten Zubereitungen:  All agents were filled into plastic bottles and stored at 20 ° C for 12 weeks. In the preparations according to the invention, the hypochlorite content after storage was significantly higher than in the preparations tested for comparison:
Tabelle 2: Restgehalt NaClO nach Lagerung (in % des Ausgangsgehaltes) Table 2: Residual NaClO content after storage (in% of the initial content)

Claims

Patentansprüche Claims
1. Verwendung von p-Methoxybenzylalkohol zur Stabilisierung von Hypochloritenthaltenden wäßrigen flüssigen Zusammensetzungen, die farbiges Metallpigment enthalten. 1. Use of p-methoxybenzyl alcohol for stabilizing hypochlorite-containing aqueous liquid compositions which contain colored metal pigment.
2. Verwendung von p-Methoxybenzylalkohol zusammen mit einem Alkalijodid zur Stabilisierung von Hypochlorit-enthaltenden wäßrigen flüssigen Zusammensetzungen, die farbiges Metallpigment enthalten. 2. Use of p-methoxybenzyl alcohol together with an alkali iodide for stabilizing hypochlorite-containing aqueous liquid compositions which contain colored metal pigment.
3. Verwendung nach Anspruch 1 oder 2, dadurch gekennzeichnet, dass die Zusammensetzung mehr als 0 Gew.-% bis zu 0,5 Gew.-%, insbesondere 0,01 Gew.-% bis 0,1 Gew.-% an p-Methoxybenzylalkohol enthält. 3. Use according to claim 1 or 2, characterized in that the composition of more than 0 wt .-% up to 0.5 wt .-%, in particular 0.01 wt .-% to 0.1 wt .-% -Methoxybenzyl alcohol contains.
4. Verwendung nach einem der Ansprüche 1 bis 3, dadurch gekennzeichnet, dass die Zusammensetzung mehr als 0 Gew.-% bis 0,01 Gew.-%, insbesondere 0,001 Gew.-% bis 0,006 Gew.-% Alkalijodid, insbesondere Kaliumjodid, enthält. 4. Use according to one of claims 1 to 3, characterized in that the composition more than 0 wt .-% to 0.01 wt .-%, in particular 0.001 wt .-% to 0.006 wt .-% alkali iodide, especially potassium iodide, contains.
5. Verwendung nach einem der Ansprüche 1 bis 4, dadurch gekennzeichnet, dass die Zusammensetzung von mehr als 0 Gew.-% bis 0,01 Gew.-%, insbesondere 0,001 Gew.-% bis 0,008 Gew.-% an farbigem Metallpigment enthält. 5. Use according to one of claims 1 to 4, characterized in that the composition of more than 0 wt .-% to 0.01 wt .-%, in particular 0.001 wt .-% to 0.008 wt .-% of colored metal pigment .
6. Verwendung nach einem der Ansprüche 1 bis 5, dadurch gekennzeichnet, dass das Metallpigment ein Kupfer-Phthalocyanin-Farbstoff ist. 6. Use according to any one of claims 1 to 5, characterized in that the metal pigment is a copper phthalocyanine dye.
7. Verwendung nach einem der Ansprüche 1 bis 6, dadurch gekennzeichnet, dass die Zusammensetzung 0,5 Gew.-% bis 5 Gew.-% Alkalihypochlorit, insbesondere Natriumhypochlorit, enthält. 7. Use according to one of claims 1 to 6, characterized in that the composition contains 0.5% by weight to 5% by weight of alkali hypochlorite, in particular sodium hypochlorite.
8. Verwendung nach einem der Ansprüche 1 bis 7, dadurch gekennzeichnet, dass die Zusammensetzung bis zu 5 Gew.-% bleichstabiles Tensid, insbesondere Betain und/oder Alkylethersulfat, enthält. 8. Use according to one of claims 1 to 7, characterized in that the composition contains up to 5% by weight of bleach-stable surfactant, in particular betaine and / or alkyl ether sulfate.
9. Verwendung nach einem der Ansprüche 1 bis 8, dadurch gekennzeichnet, dass die Zusammensetzung 0,01 Gew.-% bis 2 Gew.-% Alkylphosphonsäure und/oder -phosphonat, insbesondere Aminoxidphosphonsäure, Polyacrylsäure, Phosphono- gruppen-aufweisende Polyacrysäure und/oder Alkalisalz einer, zweier oder aller drei dieser Säuren enthält. 9. Use according to one of claims 1 to 8, characterized in that the composition 0.01% by weight to 2% by weight of alkylphosphonic acid and / or phosphonate, in particular amine oxide phosphonic acid, polyacrylic acid, phosphono group-containing polyacrylic acid and / or contains alkali salt of one, two or all three of these acids.
10. Wäßriges flüssiges Bleichmittel, enthaltend Alkalihypochlorit und farbiges Metallpigment, dadurch gekennzeichnet, dass es zusätzlich p-Methoxybenzylalkohol enthält. 10. Aqueous liquid bleaching agent containing alkali hypochlorite and colored metal pigment, characterized in that it additionally contains p-methoxybenzyl alcohol.
1 1. Mittel nach Anspruch 10, dadurch gekennzeichnet, dass es zusätzlich Akalijodid enthält. 1 1. Agent according to claim 10, characterized in that it additionally contains Akali iodide.
EP06828979A 2005-12-07 2006-11-09 Increasing the stability of liquid hypochlorite-containing washing and cleaning compositions Not-in-force EP1957620B1 (en)

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DE102005058642A DE102005058642B3 (en) 2005-12-07 2005-12-07 Increasing the stability of liquid hypochlorite-containing detergents and cleaners
PCT/EP2006/010743 WO2007065525A1 (en) 2005-12-07 2006-11-09 Increasing the stability of liquid hypochlorite-containing washing and cleaning compositions

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CN103146370A (en) * 2013-02-26 2013-06-12 中国石油大学(华东) Scale inhibitor for presetting in oil reservoir

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DE502006006949D1 (en) 2010-06-24
ES2344225T3 (en) 2010-08-20
EP1957620B1 (en) 2010-05-12

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