EP1957620B1 - Increasing the stability of liquid hypochlorite-containing washing and cleaning compositions - Google Patents

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

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Publication number
EP1957620B1
EP1957620B1 EP06828979A EP06828979A EP1957620B1 EP 1957620 B1 EP1957620 B1 EP 1957620B1 EP 06828979 A EP06828979 A EP 06828979A EP 06828979 A EP06828979 A EP 06828979A EP 1957620 B1 EP1957620 B1 EP 1957620B1
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Prior art keywords
hypochlorite
alkali
use according
composition contains
metal pigment
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German (de)
French (fr)
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EP1957620A1 (en
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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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    • 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 cleaners for hard surfaces in households, for example for cleaning tiles.
  • 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.
  • Liquid detergent formulations or corresponding preparations of hard surface cleaners containing hypochlorite as a bleach component are susceptible to loss of activity upon prolonged storage, especially because of the then-degradation of the hypochlorite.
  • ingredients that are desirable from an application point of view or for aesthetic reasons in detergents and cleaners include, in addition to the performance of such agents crucial influencing agents, in particular hypochlorite, and colorants, which should give a pleasant visual appearance in particular liquid preparations.
  • dyes are attacked by hypochlorite usually slightly oxidative, so that in addition to the loss of the bleaching agent and the color impression of hypochlorite-containing liquid agent changes rapidly on storage.
  • fragrances which are attacked by the strong oxdating agent hypochlorite in a large number of cases, so that the fragrance impression of perfumed agents changes on storage in often unacceptable ways.
  • Thickened bleach compositions containing stabilizers such as anisic acid are known US 6,448,215 and EP 1 348 755 ,
  • the invention therefore relates to the use of p-methoxybenzyl alcohol for the stabilization of hypochlorite-containing aqueous liquid compositions containing colored metal pigment.
  • a second aspect of the invention is therefore the co-use of p-methoxybenzyl alcohol and an alkali iodide for stabilizing hypochlorite-containing aqueous liquid compositions containing colored metallic pigment.
  • Another object of the invention is an aqueous liquid bleach containing alkali hypochlorite and colored metal pigment, which is characterized in that it additionally contains p-methoxybenzyl alcohol, optionally in combination with Akalijodid.
  • p-methoxybenzyl alcohol is also referred to as anisalcohol. It is commercially available and has hitherto been used, for example, as a component of perfume mixtures.
  • the liquid agent stabilized according to the invention contains from 0.5% to 5% by weight alkali hypochlorite, especially sodium hypochlorite.
  • Such formulations are particularly suitable and very effective as hard surface cleaners, for example for use on walls, work surfaces, floors and the like.
  • the agents especially because of their hypochlorite content, are particularly suitable for removing stains such as occur in kitchens or bathrooms, including greasy stains that may occur after using bathtubs, shower cubicles and sinks.
  • a bleaching agent in the form of hypochlorite is an essential component of the compositions according to the invention.
  • Bleaches per se are well-known components of detergent compositions and are particularly successful in controlling mildew and mildew, soils that are commonly found in soap deposits or in association with them.
  • alkali metal hypochlorites such as potassium hypochlorite
  • sodium hypochlorite in stabilized compositions of this invention.
  • chloride salts In commercial aqueous sodium hypochlorite solutions are often considerable amounts of chloride salts contain. These can readily be used for the production of agents according to the invention, so that it is not necessarily dependent 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 metal hypochlorite.
  • the compositions contain from more than 0 wt% to about 0.01 wt%, more preferably from about 0.001 wt% to about 0.008 wt% of colored, especially blue and / or green, metal pigment.
  • colored, especially blue and / or green, metal pigment especially blue and / or green, metal pigment.
  • complex compounds of nickel, cobalt, cuprous, iron and / or manganese are preferred; particularly preferred are copper phthalocyanine dyes.
  • alkali iodide Preferably, more than 0 wt% to about 0.01 wt%, more preferably from about 0.001 wt% to about 0.006 wt% alkali iodide, especially potassium iodide, is present.
  • the stabilized agents according to the invention are normally alkaline and may contain for this purpose about 0.1 wt .-% to 2 wt .-%, in particular 0.1 wt .-% to 1.1 wt .-% alkali metal hydroxide.
  • 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 formulations may contain surfactants that are stable in the presence of the hypochlorite.
  • betaines in particular of the general formula I, in which R 1 is an alkyl or alkenyl group having 6 to 22 carbon atoms or a group R 4 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 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.
  • surfactants examples include C 12-18 alkyl dimethyl betaine, commercially available as coconut betaine, and C 10-16 alkyl dimethyl betaine, commercially available as lauryl betaine.
  • Another class of particularly preferred surfactants are the alkyl ether sulfates obtainable by reacting alcohols (preferably having 6 to 22 carbon atoms) with alkylene oxides, especially ethylene oxide, followed by sulfation and neutralization, especially a C 12-14 fatty alcohol ether sulfate alkoxylated with 2 equivalents of ethylene oxide , In the ether sulfates, the corresponding cation is preferably sodium.
  • Surfactants are, if present, preferably in amounts up to 5 wt.%, In particular from 0.01 wt .-% to 3 wt .-% in accordance with the invention stabilized agents.
  • the preparations may additionally comprise sequestering agents, preferably alkylphosphonic acids, and among these in particular those having at least one amine oxide substituent on the alkyl group, referred to herein as amine oxide phosphonic acids, polyacrylic acids and / or polyoxyacids containing phosphono groups, which may also be in the form of their alkali metal salts.
  • sequestering agents preferably alkylphosphonic acids, and among these in particular those having at least one amine oxide substituent on the alkyl group, referred to herein as amine oxide phosphonic acids, polyacrylic acids and / or polyoxyacids containing phosphono groups, which may also be in the form of their alkali metal salts.
  • 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 preparations stabilized according to the invention may contain small amounts of one or more bleach-stable fragrances.
  • the fragrance component optionally present in addition to the anise alcohol is preferably of higher relative volatility than the ingredients which are 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.
  • compositions according to the invention I1, I2 with different pigment contents and preparations for otherwise identical composition without anisalcohol and potassium iodide ( C1, C2 ) were prepared by mixing the ingredients with water.
  • the compositions were composed as follows [wt%]: Table 1: Compositions I1 I2 C1 C2 sodium hypochlorite 3.4 3.4 3.4 C 12/14 fatty alcohol 2 EO sulfate, sodium salt 1.25 1.25 1.25 1.25 1.25 anisalcohol 0.08 0.08 - - potassium iodide 0,004 0,004 - - Cu phthalocyanine, blue 0,002 0.005 0,002 0.005 sodium hydroxide 1 1 1 1 1 Aminotrimethylenephosphonic acid-N-oxide 0.1 0.1 0.1 0.1 water on 100 on 100 on 100 on 100 on 100 on 100 on 100 on 100 on 100 on 100

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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)
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Abstract

The improvement of shelf stability in hypochlorite-containing aqueous liquid washing and/or cleaning agents that contain colored metal pigment is achieved by the use of a specific aromatic fragrance.

Description

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 cleaners 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 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.

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 formulations or corresponding preparations of hard surface cleaners containing hypochlorite as a bleach component are susceptible to loss of activity upon prolonged storage, especially because of the then-degradation of the hypochlorite. Among the ingredients that are desirable from an application point of view or for aesthetic reasons in detergents and cleaners include, in addition to the performance of such agents crucial influencing agents, in particular hypochlorite, and colorants, which should give a pleasant visual appearance in particular liquid preparations. In particular, dyes are attacked by hypochlorite usually slightly oxidative, so that in addition to the loss of the bleaching agent and the color impression of hypochlorite-containing liquid agent changes rapidly on storage. The same applies to fragrances which are attacked by the strong oxdating agent hypochlorite in a large number of cases, so that the fragrance impression of perfumed agents changes on storage in often unacceptable ways.

Obwohl es einige Vorschläge zur Stabilisierung von Alkalihypochlorit in wäßrigen Systemen gibt, sind dennoch alternative Lösungswege erstrebenswert.Although there are some proposals for stabilizing alkali hypochlorite in aqueous systems, alternative approaches are still desirable.

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, C1-4H3-9, 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.The European patent application EP 0 903 403 suggests, for example, an alkyl (alkoxy) n -sulfate (where n = 0.5 to 20), which may contain only small amounts of unsulfated material and very low levels of metal impurities, to increase the chemical stability of liquid bleaches a hypohalite containing. From the 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 , C 1-4 H 3-9 , OCOCH 3 or NH 2 or mixtures thereof, in amounts of from 0.001% to 10% by weight as the rheology stabilizing agent Active ingredients in thickened aqueous compositions containing from 0.1% to 50% by weight of alkali hypohalite, from 0.01% to 10% by weight of polymeric rheology modifier, alkaline buffering agent having a pH of from 2 to 4, and can be used as the remainder of water.

Verdickte Bleichmittelzusammensetzungen enthaltend Stabilisierungsmittel wie Anissäure sind bekannt aus US 6 448 215 und EP 1 348 755 .Thickened bleach compositions containing stabilizers such as anisic acid are known US 6,448,215 and EP 1 348 755 ,

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 cleaners have a pronounced stabilizing effect both on hypochlorite, as well as on color pigments, which are normally degraded rapidly in such agents by the hypochlorite otherwise.

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 the stabilization of hypochlorite-containing aqueous liquid compositions containing 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.As a further advantage, it has been observed that a synergistic effect between the fragrance and alkali iodides results in incorporating larger amounts of dyes into hypochlorite-containing agents than would otherwise be possible.

Ein zweiter Gegenstand der Erfindung ist daher die gemeinsame Verwendung von p-Methoxybenzylalkohol und einem Alkalijodid zur Stabilisierung von Hypochlorit-enthaltenden wäßrigen flüssigen Zusammensetzungen, die farbiges Metallpigment enthalten.A second aspect of the invention is therefore the co-use of p-methoxybenzyl alcohol and an alkali iodide for stabilizing hypochlorite-containing aqueous liquid compositions containing colored metallic pigment.

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.Another object of the invention is an aqueous liquid bleach containing alkali hypochlorite and colored metal pigment, which is characterized in that it additionally contains p-methoxybenzyl alcohol, optionally in combination with Akalijodid.

p-Methoxybenzylalkohol wird auch als Anisalkohol bezeichnet. Er ist kommerziell erhältlich und findet bisher zum Beispiel als Komponente von Duftstoffgemischen Verwendung.p-methoxybenzyl alcohol is also referred to as anisalcohol. It is commercially available and has hitherto been used, for example, as a component of perfume mixtures.

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.Normally it is sufficient if more than 0 wt .-% to about 0.5 wt .-%, in particular about 0.01 wt .-% to about 0.1 wt .-% of p-methoxybenzyl alcohol in the zu stabilizing liquid agent 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 from 0.5% to 5% by weight alkali hypochlorite, especially 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 formulations are particularly suitable and very effective as hard surface cleaners, for example for use on walls, work surfaces, floors and the like. The agents, especially because of their hypochlorite content, are particularly suitable for removing stains such as occur in kitchens or bathrooms, including greasy stains that may occur after using bathtubs, shower cubicles and sinks.

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 compositions according to the invention. Bleaches per se are well-known components of detergent compositions and are particularly successful in controlling mildew and mildew, soils that are commonly found in soap deposits or in association with them. Although other alkali metal hypochlorites, such as potassium hypochlorite, are useful, it is still preferred to use sodium hypochlorite in stabilized compositions of this invention. In commercial aqueous sodium hypochlorite solutions are often considerable amounts of chloride salts contain. These can readily be used for the production of agents according to the invention, so that it is not necessarily dependent 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 metal 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.Preferably, the compositions contain from more than 0 wt% to about 0.01 wt%, more preferably from about 0.001 wt% to about 0.008 wt% of colored, especially blue and / or green, metal pigment. Among them, complex compounds of nickel, cobalt, cuprous, iron and / or manganese are preferred; particularly preferred are copper phthalocyanine dyes.

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 enhanced by the presence of alkali iodide. Preferably, more than 0 wt% to about 0.01 wt%, more preferably from about 0.001 wt% to about 0.006 wt% alkali iodide, especially potassium iodide, is present.

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 stabilized agents according to the invention are normally alkaline and may contain for this purpose about 0.1 wt .-% to 2 wt .-%, in particular 0.1 wt .-% to 1.1 wt .-% alkali metal hydroxide. 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.

Die Zubereitungen können Tenside enthalten, die in Gegenwart des Hypochlorits stabil sind. Bevorzugt sind Betaine, insbesondere 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 für besonders geeignete Vertreter dieser Klasse von Tensiden umfassen C12-18-Alkyl-dimethylbetain, kommerziell erhältlich als Kokosnußbetain, und C10-16-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 C12-14-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.The formulations may contain surfactants that are stable in the presence of the hypochlorite. Preference is given to betaines, in particular of the general formula I,
Figure imgb0001
 in which R 1 is an alkyl or alkenyl group having 6 to 22 carbon atoms or a group R 4 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 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 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. Another class of particularly preferred surfactants are the alkyl ether sulfates obtainable by reacting alcohols (preferably having 6 to 22 carbon atoms) with alkylene oxides, especially ethylene oxide, followed by sulfation and neutralization, especially a C 12-14 fatty alcohol ether sulfate alkoxylated with 2 equivalents of ethylene oxide , In the ether sulfates, the corresponding cation is preferably sodium. Surfactants are, if present, preferably in amounts up to 5 wt.%, In particular from 0.01 wt .-% to 3 wt .-% in accordance with the invention stabilized agents.

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),

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 Aminoxidphosphonsäuren ist das Aminoxid auf der Basis der Aminotrimethylenphosphonsäure. Vorzugsweise sind 0,01 Gew.-% bis 2 Gew.-% solcher Sequestriermittel vorhanden.The preparations may additionally comprise sequestering agents, preferably alkylphosphonic acids, and among these in particular those having at least one amine oxide substituent on the alkyl group, referred to herein as amine oxide phosphonic acids, polyacrylic acids and / or polyoxyacids containing phosphono groups, which may also be in the form of their alkali metal salts. 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 more 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.

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 may contain small amounts of one or more bleach-stable fragrances. The fragrance component optionally present in addition to the anise alcohol is preferably of higher relative volatility than the ingredients which are optionally responsible for a bleaching odor.

Die erfindungsgemäß stabilisierten Mittel können in einfacher Weise durch Vermischen der obengenannten Inhaltsstoffe in den angegebenen Mengen hergestellt werden.The stabilized compositions according to the invention can be prepared in a simple manner by mixing the above-mentioned ingredients in the indicated amounts.

BeispieleExamples

Erfindungsgemäße Zubereitungen (I1, I2) mit verschieden hohem Pigmentgehalt und zu Vergleichszwecken ansonsten gleich zusammengesetzte Zubereitungen ohne Anisalkohol und Kaliumjodid (C1, C2) wurden durch Vermischen der Inhaltsstoffe mit Wasser hergestellt. Die Mittel waren wie folgt zusammengesetzt [Gew.-%]: Tabelle 1: Zusammensetzungen I1 I2 C1 C2 Natriumhypochlorit 3,4 3,4 3,4 3,4 C12/14-Fettalkohol 2 EO sulfat, Natriumsalz 1,25 1,25 1,25 1,25 Anisalkohol 0,08 0,08 - - Kaliumjodid 0,004 0,004 - - Cu-Phthalocyanin, blau 0,002 0,005 0,002 0,005 Natriumhydroxid 1 1 1 1 Aminotrimethylenphosphonsäure-N-Oxid 0,1 0,1 0,1 0,1 Wasser auf 100 auf 100 auf 100 auf 100 Compositions according to the invention ( I1, I2 ) with different pigment contents and preparations for otherwise identical composition without anisalcohol and potassium iodide ( C1, C2 ) were prepared by mixing the ingredients with water. The compositions were composed as follows [wt%]: Table 1: Compositions I1 I2 C1 C2 sodium hypochlorite 3.4 3.4 3.4 3.4 C 12/14 fatty alcohol 2 EO sulfate, sodium salt 1.25 1.25 1.25 1.25 anisalcohol 0.08 0.08 - - potassium iodide 0,004 0,004 - - Cu phthalocyanine, blue 0,002 0.005 0,002 0.005 sodium hydroxide 1 1 1 1 Aminotrimethylenephosphonic acid-N-oxide 0.1 0.1 0.1 0.1 water on 100 on 100 on 100 on 100

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: Tabelle 2: Restgehalt NaClO nach Lagerung (in % des Ausgangsgehaltes) Mittel NaClO C1 46 C2 28 I1 90 I2 88 All agents were bottled in plastic bottles and stored for 12 weeks at 20 ° C. In the preparations according to the invention, the hypochlorite content after storage was significantly higher than in the preparations tested for comparison: Table 2: Residual NaClO content after storage (% of initial content) medium NaClO C1 46 C2 28 I1 90 I2 88

Claims (11)

  1. Use of p-methoxybenzyl alcohol to stabilize hypochlorite-containing aqueous liquid compositions that contain colored metal pigment
  2. Use of p-methoxybenzyl alcohol, together with an alkali iodide, to stabilize hypochlorite-containing aqueous liquid compositions that contain colored metal pigment.
  3. Use according to Claim 1 or 2, characterized in that the composition contains more than 0 wt% to 0.5 wt%, in particular 0.01 wt% to 0.1 wt%, p-methoxybenzyl alcohol.
  4. Use according to one of Claims 1 to 3, characterized in that the composition contains more than 0 wt% to 0.01 wt%, in particular 0.001 wt% to 0.006 wt%, alkali iodide, in particular potassium iodide.
  5. Use according to one of Claims 1 to 4, characterized in that the composition contains more than 0 wt% to 0.01 wt%, in particular 0.001 wt% to 0.008 wt%, colored metal pigment.
  6. Use according to one of Claims 1 to 5, characterized in that the metal pigment is a copper phthalocyanine dye.
  7. Use according to one of Claims 1 to 6, characterized in that the composition contains 0.5 wt% to 5 wt% alkali hypochlorite, in particular sodium hypochlorite.
  8. Use according to one of Claims 1 to 7, characterized in that the composition contains up to 5 wt% bleach-stable surfactant, in particular betaine and/or alkyl ether sulfate.
  9. Use according to one of Claims 1 to 8, characterized in that the composition contains 0.01 wt% to 2 wt% alkylphosphonic acid and/or alkylphosphonate, in particular amine oxide phosphonic acid, polyacrylic acid, polyacrylic acid containing phosphono groups, and/or an alkali salt of one, two, or all three of said acids.
  10. An aqueous liquid bleaching agent containing alkali hypochlorite and colored metal pigment, characterized in that it additionally contains p-methoxybenzyl alcohol.
  11. Agent according to Claim 10, characterized in that it additionally contains alkali 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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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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JP2013199390A (en) * 2012-03-23 2013-10-03 Kurita Water Ind Ltd Method for preserving sodium hypochlorite
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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ATE467675T1 (en) 2010-05-15
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ES2344225T3 (en) 2010-08-20

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