EP1966362A1 - Improving the stability of detergents containing hypochlorite - Google Patents

Improving the stability of detergents containing hypochlorite

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Publication number
EP1966362A1
EP1966362A1 EP06829425A EP06829425A EP1966362A1 EP 1966362 A1 EP1966362 A1 EP 1966362A1 EP 06829425 A EP06829425 A EP 06829425A EP 06829425 A EP06829425 A EP 06829425A EP 1966362 A1 EP1966362 A1 EP 1966362A1
Authority
EP
European Patent Office
Prior art keywords
hydrogen
cyclodextrin
hypochlorite
optical brightener
use according
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Granted
Application number
EP06829425A
Other languages
German (de)
French (fr)
Other versions
EP1966362B1 (en
Inventor
Carlos Malet
Mercedes Mendoza Cruz
Miguel Osset
Nuria Montaner
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Henkel AG and Co KGaA
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Henkel AG and Co KGaA
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Application filed by Henkel AG and Co KGaA filed Critical Henkel AG and Co KGaA
Priority to PL06829425T priority Critical patent/PL1966362T3/en
Publication of EP1966362A1 publication Critical patent/EP1966362A1/en
Application granted granted Critical
Publication of EP1966362B1 publication Critical patent/EP1966362B1/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
    • C11D3/22—Carbohydrates or derivatives thereof
    • C11D3/222—Natural or synthetic polysaccharides, e.g. cellulose, starch, gum, alginic acid or cyclodextrin
    • 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
    • C11D3/42—Brightening agents ; Blueing agents

Definitions

  • the present invention relates to the stabilization of hypochlorite-containing liquid detergents which contain optical brighteners.
  • 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, among which in particular the hypochlorite may be mentioned, also active ingredients, which rather the visual appearance of the so affect treated textiles.
  • active ingredients which rather the visual appearance of the so affect treated textiles.
  • optical brighteners to name, which raise during the washing process on the fibers of the textile material. These compounds are able to absorb light and emit light of shorter wavelength.
  • the present invention is the use of cyclodextrin for stabilizing optical brighteners in aqueous liquid detergents containing alkali metal hypochlorite.
  • Cyclodextrins also called cycloglucans, are formed in the degradation of starch by Bacillus macerans or B. circulans under the action of cyclodextrin glycosyltransferase.
  • the cyclodextrins consist of ring-shaped ⁇ -l, 4-linked glucose units, usually from 6, 7 or 8 glucose units; these are referred to as ⁇ -, ß- or ⁇ -cyclodextrin.
  • the use of cyclodextrins or their derivatives as active cleaning component is described, for example, in International Patent Application WO 94/10280.
  • hypochlorite-containing liquid agents on addition of cyclodextrins to hypochlorite-containing liquid agents, the stability of optical brighteners contained in these agents is increased and also that the hypochlorite is degraded less rapidly on storage than is the case without this addition.
  • a second object of the invention is an aqueous liquid bleach or bleaching detergent containing alkali hypochlorite and optical brightener, which is characterized in that it additionally contains cyclodextrin.
  • the agent according to the invention may contain any cyclodextrins, for example ⁇ -, ⁇ - or ⁇ -cyclodextrin.
  • ⁇ -cyclodextrin is preferred.
  • R 1 is hydrogen, -SO 3 M, -OR 13 , -CN, -Cl, -COOR 13 , -CON (R 13 ) 2
  • R 2 and R 3 are independently hydrogen, -R 13 or -Ar,
  • R 4 and R 5 are independently -OH, -Cl, -NH 2 , -OR 13 , -O-Ar, -NHR 13 , -N (R 13 ) 2 , -NR 13 R 14 , -N (R 14 ) 2 , -NH-Ar, a morpholino group, -SR 13 or -S-Ar,
  • R 6 is hydrogen, -Cl or -SO 3 M
  • R 7 is -CN, -SO 3 M, -SR 13 or -S-Ar,
  • R 8 is hydrogen, -R 13 , -Cl or -SO 3 M
  • R 9 and R 10 independently of one another are hydrogen, -R 13 , -Cl, -SO 3 M or -OR 13 ,
  • R 1 ' is hydrogen or -R 13 ,
  • R 12 is hydrogen, -R 13 , -CN, Cl, -COOR 13 , -CON (R 13 ) 2 , -Ar or -O-Ar,
  • R 13 is a branched or unbranched C 1 - to C 4 -alkyl group
  • R 14 is a branched or unbranched ci- to C 4 -hydroxyalkyl group
  • Ar is optionally substituted with -R 13 , -Cl, -SO 3 M or -OR 13
  • M is hydrogen, Na, K, Ca, Mg, ammonium, mono-, di-, tri- or tetra-R 13 -substituted ammonium, mono-, di-, tri- or tetra-R 14 -substituted ammonium or with a mixture from R 13 and R 14 mono-, di-, tri- or tetra-substituted ammonium.
  • optical brighteners which correspond to the formulas (I) or (II).
  • Optical brighteners are usually present only in small amounts, for example from 10 ppm to 0.5 wt .-%, in detergents or bleaches.
  • Preparations according to the invention are particularly suitable and very effective as bleaching agents or bleaching detergents for white textiles.
  • An agent of the present invention is effective against a variety of stains, including greasy soils such as sebum, makeup, or lipstick, enzymatically removable stains such as blood, grass or cocoa, and bleachable soils such as wine, coffee or tea, even after aging of the composition means if it has been stored for a long time after its production.
  • bleaches according to the present invention are suitable for bleaching textiles of various materials, including those of natural fibers such as cotton or linen, but also those of synthetic material, such as synthetic polymer fibers, and also of corresponding ones mixed fabrics.
  • a liquid composition according to the present invention is advantageously applied to the textiles to be cleaned in diluted form, for example when it is used in manual or machine washing of textiles as a washing additive or as a detergent alone, but it can additionally or alternatively also undiluted to the textile be applied, for example, as a liquid pretreatment agent or stain remover.
  • 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 and cleaner compositions and, in particular, are also successful in controlling mildew and mildew and in disinfecting.
  • alkali metal hypochlorites such as potassium hypochlorite
  • sodium hypochlorite in stabilized compositions of this invention.
  • Commercially available aqueous sodium hypochlorite solutions often contain considerable amounts of chloride salts. These can readily for the production according to the invention Means are used, so that one does not necessarily rely on the use of high purity NaOCl.
  • the compositions contain 0.5% by weight to 5% by weight, in particular 1% by weight to 4% by weight, of alkali metal hypochlorite.
  • 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. Preference is given to betaines, in particular those of the general formula IX,
  • R 14 is an alkyl or alkenyl group having 6 to 22 carbon atoms or a group R 17 is CO-NH- (CH 2 ) n -
  • R 15 is hydrogen or an alkyl group having 1 to 4 carbon atoms
  • R 16 is hydrogen or an alkyl group with 1 to 4 carbon atoms
  • R 17 is an alkyl or alkenyl group having 6 to 22 carbon atoms
  • m is a number from 1 to 6
  • n is a number from 1 to 3.
  • particularly suitable representatives of this class of surfactants include Ci 2- ig-alkyl dimethyl betaine, coconut betaine commercially available as, and Ci 0- i 6 alkyl dimethyl betaine, commercially available as laurylbetaine.
  • alkyl ether sulfates which are obtainable 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 Ci 2 -H fatty alcohol ether sulfate alkoxylated with 2 equivalents of ethylene oxide , In the ether sulfates, the corresponding cation is preferred Sodium.
  • Surfactants if present, are preferably contained in amounts of up to 20% by weight, in particular of 0.1% by weight to 15% by weight, of stabilizers in accordance with the invention.
  • the formulations may additionally contain sequestering agents, preferably aminoalkylphosphonic acids, alkylphosphonic acids and alkylphosphonic acids 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 aminoalkylphosphonic acids, alkylphosphonic acids and alkylphosphonic acids 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 normally prepared by oxidation of corresponding aminoalkyl phosphonic acids. They preferably belong to the group of compounds according to general formula (X),
  • R 18 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.
  • phosphonic acids is diethylene triamine penta-methylene phosphonic acid and the amine oxide based on aminotrimethylene phosphonic acid.
  • the preparations stabilized according to the invention may contain small amounts of pH-buffering substances and / or 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 agents contain more than 0 wt .-% to about 0.01 wt .-%, in particular about 0.001 wt .-% to about 0.008 wt .-% of colored, in particular 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, therefore, more than 0 wt .-% to about 0.01 wt .-%, in particular about 0.001 wt .-% to about 0.006 wt .-% alkali metal iodide, in particular potassium iodide present in inventive compositions.
  • Useful pH buffering ingredients are preferably selected from the alkali carbonates, polycarbonates, sesquicarbonates, silicates, polysilicates, borates, phosphates, stannates, aluminates and mixtures thereof, the preferred alkali metals being sodium and potassium.
  • the starting materials for the preparation of, for example, the hypohalite bleach may contain by-products, for example, carbonate, which may result in a content of such by-products in the compositions of optionally up to 0.4% by weight.
  • aqueous compositions according to the invention normally have viscosities in the range from about 25 mPa.s to 1500 mPa.s, in particular from 50 mPa.s to HOO mPa.s.
  • a composition of the invention in dilute or undiluted form, can be used to remove soils and stains from fabrics by allowing the composition and fabric to contact each other for a time sufficient to bleach the fabric, and then the fabric rinsed with water.
  • the textile can also be washed using an agent according to the invention by hand or in a mechanical washing process in which an agent according to the invention is metered into a conventional washing machine. example

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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)
  • Molecular Biology (AREA)
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  • Detergent Compositions (AREA)

Abstract

Use of cyclodextrin for the stabilization of optical brightener in aqueous liquid detergent containing alkali hypochlorite. An independent claim is also included for an aqueous liquid bleaching agent containing alkali hypochlorite, optical brightener and cyclodextrin.

Description

Erhöhung der Stabilität hypochlorithaltiger Waschmittel Increasing the stability of hypochlorite-containing detergents
Die vorliegende Erfindung betrifft die Stabilisierung hypochlorit-haltiger flüssiger Waschmittel, die optischen Aufheller enthalten.The present invention relates to the stabilization of hypochlorite-containing liquid detergents which contain optical brighteners.
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 vertriebenSodium 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, unter denen hier insbesondere das Hypochlorit zu nennen ist, auch Wirkstoffe, welche eher die optische Erscheinungsform der damit behandelten Textilien beeinflussen. Hier sind in erster Linie optische Aufheller zu nennen, die beim Waschvorgang auf die Fasern des textilen Materials aufziehen. Diese Verbindungen sind in der Lage, Licht zu absorbieren und Licht kürzerer Wellenlänge abzustrahlen. Bei der Absorption von rot- und gelb-tonigem Licht und der Abgabe von blauem bis hin zu ultraviolettem Licht resultiert in der Summe eine Erhöhung der Intensität von als weiß empfundenen Licht, so daß ein entsprechend behandeltes Textil optisch heller wirkt. Bei weißer Wäsche ist dies ein sehr wünschenswerter Effekt; Waschmittel, die für den Einsatz zum Waschen farbiger Textilien vorgesehen sind, enthalten in der Regel keine optischen Aufheller. Optische Aufheller werden von Hypochlorit leicht oxidativ angegriffen, so dass entsprechende Mittel, die beide enthalten, nach Lagerung zusätzlich zum daraus resultierenden Verlust des Bleichmittels auch der für den optischen Weißeindruck mitverantwortliche Wirkstoff des optischen Aufhellers nicht mehr oder zumindest nicht mehr in vollem Umfang zur Verfügung steht.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, among which in particular the hypochlorite may be mentioned, also active ingredients, which rather the visual appearance of the so affect treated textiles. Here are primarily optical brighteners to name, which raise during the washing process on the fibers of the textile material. These compounds are able to absorb light and emit light of shorter wavelength. In the absorption of red and yellow-toned light and the emission of blue to ultraviolet light results in the sum of an increase in the intensity of perceived as white light, so that a correspondingly treated textile looks optically lighter. For white laundry, this is a very desirable effect; Detergents intended for use in washing colored textiles generally do not contain optical brighteners. Optical brighteners are easily oxidatively attacked by hypochlorite, so that corresponding agents, both containing, after storage, in addition to the resulting loss of the bleaching agent also for the optical White impression co-responsible active ingredient of the optical brightener is no longer or at least not fully available.
In der internationalen Patentanmeldung WO 99/15616 wird vorgeschlagen, hypohalogenit- haltigen Bleichmitteln, die optischen Aufheller enthalten, Radikalfänger zuzusetzen, um die optischen Aufheller zu stabilisieren.International Patent Application WO 99/15616 proposes adding free-radical scavengers to hypohalite-containing bleaching agents which contain optical brighteners in order to stabilize the optical brighteners.
Überraschenderweise wurde nun gefunden, dass auch bestimmte Verbindungen, die keine Radikalfänger sind, sehr wirksam zur Stabilisierung von optischen Aufhellern in hypochlorithaltigen Flüssigkeiten beitragen.Surprisingly, it has now been found that certain compounds which are not radical scavengers contribute very effectively to the stabilization of optical brighteners in hypochlorite-containing liquids.
Gegenstand der vorliegenden Erfindung ist die Verwendung von Cyclodextrin zur Stabilisierung optischer Aufheller in wäßrigen Flüssigwaschmitteln, die Alkalihypochlorit enthalten.The present invention is the use of cyclodextrin for stabilizing optical brighteners in aqueous liquid detergents containing alkali metal hypochlorite.
Der Einsatz von Cyclodextrinen auf dem Gebiet der Wasch- und Reinigungsmittel ist aus dem Stand der Technik bekannt. In der internationalen Patentanmeldung WO 94/10280 wird ein Reinigungsmittel beschrieben, das mindestens ein Cyclodextrin oder Cyclodextrinderivat als reinigungsaktive Komponente enthält. Das dort beschriebene Mittel wird insbesondere zum Entfernen von Ölen, Fetten, aliphatischen und aromatischen Kohlenwasserstoffen, Säuren, Estern und Ethern von beliebigen Oberflächen eingesetzt.The use of cyclodextrins in the field of detergents and cleaners is known from the prior art. International patent application WO 94/10280 describes a cleaning agent which contains at least one cyclodextrin or cyclodextrin derivative as the cleaning-active component. The agent described therein is used in particular for removing oils, fats, aliphatic and aromatic hydrocarbons, acids, esters and ethers from arbitrary surfaces.
In der internationalen Patentanmeldung WO 93/05136 wird ein Verfahren zur Herstellung von festen Teilchen aus wasserempfindlichen Materialien beschrieben, worin teilchenför- mige Komplexe aus Cyclodextrinen und Parfümstoffen mit einer Schutzhülle versehen werden.International patent application WO 93/05136 describes a process for the preparation of solid particles from water-sensitive materials in which particulate complexes of cyclodextrins and perfumes are provided with a protective coating.
Cyclodextrine, auch Cycloglucane genannt, werden bei dem Abbau von Stärke durch Bacillus macerans oder B. circulans unter Einwirkung von Cyclodextringlycosyltransferase gebildet. Die Cyclodextrine bestehen aus ringförmig miteinander α-l,4-verknüpften Glucose-Einheiten, in der Regel aus 6, 7 oder 8 Glucose-Einheiten; diese werden als α-, ß- oder γ-Cyclodextrin bezeichnet. Der Einsatz von Cyclodextrinen oder ihren Derivaten als aktive Reinigungskomponente wird beispielsweise in der internationalen Patentanmeldung WO 94/10280 beschrieben. Überraschenderweise wurde jetzt festgestellt, daß bei Zusatz von Cyclodextrinen zu hypochlorithaltigen flüssigen Mitteln die Stabilität von in diesen Mitteln enthaltenem optischen Aufheller erhöht ist und auch das Hypochlorit bei Lagerung weniger rasch abgebaut wird als dies ohne diesen Zusatz der Fall ist.Cyclodextrins, also called cycloglucans, are formed in the degradation of starch by Bacillus macerans or B. circulans under the action of cyclodextrin glycosyltransferase. The cyclodextrins consist of ring-shaped α-l, 4-linked glucose units, usually from 6, 7 or 8 glucose units; these are referred to as α-, ß- or γ-cyclodextrin. The use of cyclodextrins or their derivatives as active cleaning component is described, for example, in International Patent Application WO 94/10280. Surprisingly, it has now been found that on addition of cyclodextrins to hypochlorite-containing liquid agents, the stability of optical brighteners contained in these agents is increased and also that the hypochlorite is degraded less rapidly on storage than is the case without this addition.
Ein zweiter Gegenstand der Erfindung ist ein wäßriges flüssiges Bleichmittel beziehungsweise bleichendes Waschmittel, enthaltend Alkalihypochlorit und optischen Aufheller, welches dadurch gekennzeichnet ist, dass es zusätzlich Cyclodextrin enthält.A second object of the invention is an aqueous liquid bleach or bleaching detergent containing alkali hypochlorite and optical brightener, which is characterized in that it additionally contains cyclodextrin.
Normalerweise ist es ausreichend, wenn mehr als 0 Gew.-% bis hin zu etwa 1 Gew.-%, insbesondere etwa 0,01 Gew.-% bis etwa 0,5 Gew.-% an Cyclodextrin in dem zu stabilisierenden flüssigen Mittel enthalten ist.Usually, it is sufficient if more than 0 wt% to about 1 wt%, more preferably about 0.01 wt% to about 0.5 wt%, of cyclodextrin is included in the liquid agent to be stabilized is.
Das erfindungsgemäße Mittel kann beliebige Cyclodextrine, beispielsweise α-, ß- oder γ- Cyclodextrin, enthalten. Bevorzugt ist der Einsatz von ß-Cyclodextrin.The agent according to the invention may contain any cyclodextrins, for example α-, β- or γ-cyclodextrin. The use of β-cyclodextrin is preferred.
Der erfindungsgemäß stabilisierte optische Aufheller wird vorzugsweise aus einer Verbindung gemäß einer der folgenden Formeln (I) bis (VIII) oder deren Gemischen ausgewählt, wobei die Verbindungen mit dargestellter trans-konfigurierter C=C- Doppelbindung auch zumindest anteilsweise mit solcher in cis-Konfiguration vorliegen können:The optical brightener stabilized according to the invention is preferably selected from a compound according to one of the following formulas (I) to (VIII) or mixtures thereof, wherein the compounds with trans-configured C =C double bond shown are also at least partially present in cis configuration can:
(VII)(VII)
In diesen bedeutenIn these mean
R1 Wasserstoff, -SO3M, -OR13, -CN, -Cl, -COOR13, -CON(R13)2 R 1 is hydrogen, -SO 3 M, -OR 13 , -CN, -Cl, -COOR 13 , -CON (R 13 ) 2
R2 und R3 unabhängig voneinander Wasserstoff, -R13 oder -Ar,R 2 and R 3 are independently hydrogen, -R 13 or -Ar,
R4 und R5 unabhängig voneinander -OH, -Cl, -NH2, -OR13, -O-Ar, -NHR13, -N(R13)2, -NR13R14, -N(R14)2, -NH-Ar, eine Morpholino-Gruppe, -S-R13 oder -S-Ar,R 4 and R 5 are independently -OH, -Cl, -NH 2 , -OR 13 , -O-Ar, -NHR 13 , -N (R 13 ) 2 , -NR 13 R 14 , -N (R 14 ) 2 , -NH-Ar, a morpholino group, -SR 13 or -S-Ar,
R6 Wasserstoff, -Cl oder -SO3M,R 6 is hydrogen, -Cl or -SO 3 M,
R7 -CN, -SO3M, -S-R13 oder -S-Ar,R 7 is -CN, -SO 3 M, -SR 13 or -S-Ar,
R8 Wasserstoff, -R13, -Cl oder -SO3M,R 8 is hydrogen, -R 13 , -Cl or -SO 3 M,
R9 und R10 unabhängig voneinander Wasserstoff, -R13, -Cl, -SO3M oder -OR13,R 9 and R 10 independently of one another are hydrogen, -R 13 , -Cl, -SO 3 M or -OR 13 ,
R1 ' Wasserstoff oder -R13,R 1 'is hydrogen or -R 13 ,
R12 Wasserstoff, -R13, -CN, Cl, -COOR13, -CON(R13)2, -Ar oder -O-Ar,R 12 is hydrogen, -R 13 , -CN, Cl, -COOR 13 , -CON (R 13 ) 2 , -Ar or -O-Ar,
R13 eine verzweigte oder unverzweigte C1- bis C4-AlkylgruppeR 13 is a branched or unbranched C 1 - to C 4 -alkyl group
R14 eine verzweigte oder unverzweigte Ci- bis C4-Hydroxyalkylgruppe,R 14 is a branched or unbranched ci- to C 4 -hydroxyalkyl group,
Ar eine gegebenenfalls mit -R13, -Cl, -SO3M oder -OR13 substituierteAr is optionally substituted with -R 13 , -Cl, -SO 3 M or -OR 13
Phenyl-, Naphthyl-, Pyrindinyl-, Pyridazinyl-, Pyrimidinyl-, Pyrazinyl-, Triazinyl-, Indolyl-, Anthracenyl-, Phenanthrenyl- oder Benzonaphthylgruppe,Phenyl, naphthyl, pyrindinyl, pyridazinyl, pyrimidinyl, pyrazinyl, triazinyl, indolyl, anthracenyl, phenanthrenyl or benzonaphthyl group,
M Wasserstoff, Na, K, Ca, Mg, Ammonium, mono-, di-, tri- oder tetra-R13- substituiertes Ammonium, mono-, di-, tri- oder tetra-R14-substituiertes Ammonium oder mit einer Mischung aus R13 und R14 mono-, di-, tri- oder tetra-substituiertes Ammonium.M is hydrogen, Na, K, Ca, Mg, ammonium, mono-, di-, tri- or tetra-R 13 -substituted ammonium, mono-, di-, tri- or tetra-R 14 -substituted ammonium or with a mixture from R 13 and R 14 mono-, di-, tri- or tetra-substituted ammonium.
Besonders bevorzugt werden optische Aufheller eingesetzt, die den Formeln (I) oder (II) entsprechen. Beispielsweise ist die Verbindung gemäß Formel (I) mit R1 = M = H unter dem Namen Tinopal® CBS-X von Ciba-Geigy und die Verbindung gemäß Formel (II) mit R2 = M = H, R3 = Phenyl unter dem Namen Optiblanc® BRB von 3V Sigma erhältlich. Optische Aufheller sind üblicherweise nur in geringen Mengen, beispielsweise von 10 ppm bis 0,5 Gew.-%, in Wasch- beziehungsweise Bleichmitteln enthalten.Particular preference is given to using optical brighteners which correspond to the formulas (I) or (II). For example, the compound according to formula (I) with R 1 = M = H under the name Tinopal® CBS-X from Ciba-Geigy and the compound according to formula (II) with R 2 = M = H, R 3 = phenyl under the Name Optiblanc® BRB available from 3V Sigma. Optical brighteners are usually present only in small amounts, for example from 10 ppm to 0.5 wt .-%, in detergents or bleaches.
Erfindungsgemäße Zubereitungen sind insbesondere geeignet und sehr effektiv als Bleichmittel beziehungsweise bleichendes Waschmittel für weiße Textilien. Ein erfindungsgemäßes Mittel ist wirksam gegenüber einer Mehrzahl von Verfleckungen, einschließlich fettiger Anschmutzungen wie Sebum, Makeup, oder Lippenstift, enzymatisch entfernbarer Anschmutzungen wie Blut, Gras oder Kakao, und bleichbarer Anschmutzungen wie Wein, Kaffe oder Tee, auch nach Alterung der der Zusammensetzung, das heißt wenn sie nach ihrer Herstellung längere Zeit gelagert wurde.Preparations according to the invention are particularly suitable and very effective as bleaching agents or bleaching detergents for white textiles. An agent of the present invention is effective against a variety of stains, including greasy soils such as sebum, makeup, or lipstick, enzymatically removable stains such as blood, grass or cocoa, and bleachable soils such as wine, coffee or tea, even after aging of the composition means if it has been stored for a long time after its production.
Ein weiterer Vorteil von Bleichmitteln gemäß der vorliegenden Erfindung besteht darin, daß sie sich für das Bleichen von Textilien aus verschiedenen Materialien eignen, einschließlich solchen aus Naturfasern wie Baumwolle oder Leinen, aber auch solchen aus synthetischem Material, wie synthetischen Polymerfasern, und auch solchen aus entsprechenden Mischgeweben.Another advantage of bleaches according to the present invention is that they are suitable for bleaching textiles of various materials, including those of natural fibers such as cotton or linen, but also those of synthetic material, such as synthetic polymer fibers, and also of corresponding ones mixed fabrics.
Ein flüssiges Mittel gemäß der vorliegenden Erfindung wird vorteilhafterweise auf die zu reinigenden Textilien in verdünnter Form aufgebracht, beispielsweise wenn es beim manuellen oder maschinellen Waschen von Textilien als Waschadditiv oder allein als Waschmittel zum Einsatz kommt, es kann aber zusätzlich oder alternativ auch unverdünnt auf das Textil aufgetragen werden, beispielsweise als flüssiges Vorbehandlungsmittel oder Fleckentferner.A liquid composition according to the present invention is advantageously applied to the textiles to be cleaned in diluted form, for example when it is used in manual or machine washing of textiles as a washing additive or as a detergent alone, but it can additionally or alternatively also undiluted to the textile be applied, for example, as a liquid pretreatment agent or stain remover.
Ein Bleichmittel in Form von Hypochlorit ist ein wesentlicher Bestandteil der erfindungsgemäßen Mittel. Bleichmittel an sich sind durchaus bekannte Komponenten von Wasch- und Reiniungsmittelzusammensetzungen und sind insbesondere auch erfolgreich im Bekämpfen von Mehltau und Schimmel und bei der Desinfektion. 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 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 and cleaner compositions and, in particular, are also successful in controlling mildew and mildew and in disinfecting. 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. Commercially available aqueous sodium hypochlorite solutions often contain considerable amounts of chloride salts. These can readily for the production according to the invention Means are used, so that one does not necessarily rely on the use of high purity NaOCl. In a preferred embodiment of the invention, the compositions contain 0.5% by weight to 5% by weight, in particular 1% by weight to 4% by weight, of alkali metal hypochlorite.
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 solche der allgemeinen Formel IX,The formulations may contain surfactants that are stable in the presence of the hypochlorite. Preference is given to betaines, in particular those of the general formula IX,
R15 R 15
R14-N+-(CH2)mCOO" (IX)R 14 -N + - (CH 2 ) m COO " (IX)
R16 R 16
in der R14 eine Alkyl- oder Alkenylgruppe mit 6 bis 22 Kohlenstoffatomen oder eine Gruppe R17CO-NH-(CH2)n- ist, R15 Wasserstoff oder eine Alkylgruppe mit 1 bis 4 Kohlenstoffatomen ist, R16 Wasserstoff oder eine Alkylgruppe mit 1 bis 4 Kohlenstoffatomen ist, R17 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 Ci2-H- Fettalkoholethersulfat. In den Ethersulfaten ist das korrespondierende Kation vorzugsweise Natrium. Tenside sind, falls anwesend, vorzugsweise in Mengen bis zu 20 Gew.-%, insbesondere von 0,1 Gew.-% bis 15 Gew.-% in erfindungsgemäß stabilisierten Mitteln enthalten.wherein R 14 is an alkyl or alkenyl group having 6 to 22 carbon atoms or a group R 17 is CO-NH- (CH 2 ) n -, R 15 is hydrogen or an alkyl group having 1 to 4 carbon atoms, R 16 is hydrogen or an alkyl group with 1 to 4 carbon atoms, R 17 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, coconut betaine commercially available as, and Ci 0- i 6 alkyl dimethyl betaine, commercially available as laurylbetaine. Another class of particularly preferred surfactants are the alkyl ether sulfates which are obtainable 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 Ci 2 -H fatty alcohol ether sulfate alkoxylated with 2 equivalents of ethylene oxide , In the ether sulfates, the corresponding cation is preferred Sodium. Surfactants, if present, are preferably contained in amounts of up to 20% by weight, in particular of 0.1% by weight to 15% by weight, of stabilizers in accordance with the invention.
Die Zubereitungen können zusätzlich Sequestriermittel enthalten, vorzugsweise Aminoalkylphosphonsäuren, Alkylphosphonsäuren und Alkylphosphonsäuren mit zumindest einem Aminoxid-Substituenten an der Alkylgruppe, hier als Aminoxidphosphon- säuren bezeichnet, Polyacrylsäuren und/oder Phosphonogruppen-aufweisende Polyacrysäuren, die auch in der Form ihrer Alkalisalze vorliegen können. Die Einarbeitung derartiger Komplexbildner führt überraschenderweise zu besonders guter Stabilität des Hypochlorits. Aminoxidphosphonsäuren werden normalerweise durch Oxidation von entsprechenden Aminoalkylphosphonsäuren hergestellt. Sie gehören vorzugsweise zur Gruppe von Verbindungen gemäß allgemeiner Formel (X),The formulations may additionally contain sequestering agents, preferably aminoalkylphosphonic acids, alkylphosphonic acids and alkylphosphonic acids 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 particularly good stability of the hypochlorite. Amine oxide phosphonic acids are normally prepared by oxidation of corresponding aminoalkyl phosphonic acids. They preferably belong to the group of compounds according to general formula (X),
O CH3 HO CH 3 H
HO-P-(CH2)x(CH)y-N->O (X)HO-P- (CH 2 ) x (CH) y -N-> O (X)
OR18 HOR 18 H
in der R18 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 Phosphonsäuren ist Diethylentriamin-penta-methylenphosphonsäure und das Aminoxid auf der Basis der Aminotrimethylenphosphonsäure. Vorzugsweise sind 0,01 Gew.-% bis 2 Gew.-% solcher Sequestriermittel vorhanden.in which R 18 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 phosphonic acids is diethylene triamine penta-methylene phosphonic acid and 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 pH-puffernden Substanzen und/oder an einem oder mehreren bleichstabilen Färb- oder Riechstoffen enthalten. Die gegebenenfalls enthaltene Duftstoffkomponente ist vorzugsweise von höherer relativer Flüchtigkeit als die Bestandteile, die gegebenenfalls für einen Bleichegeruch verantwortlich sind. 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. Die Stabilität sowohl des farbigen Metallpigments wie auch des Alkalihypochlorits wird durch die Anwesenheit von Alkalijodid erhöht. Vorzugsweise sind in erfindungsgemäßen Mitteln daher 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. Brauchbare pH- Wert puffernde Inhaltsstoffe werden vorzugsweise ausgewählt aus den Alkalicarbonaten, -polycarbonaten, -sesquicarbonaten, -Silikaten, -polysilicaten, -boraten, -phosphaten, -stannaten, -aluminaten und Mischungen aus diesen, wobei die bevorzugten Alkalimetalle Natrium und Kalium sind. Die Ausgangsmaterialien zur Herstellung beispielsweise des Hypohalogenit-Bleichmittels können Nebenprodukte, zum Beispiel Carbonat, enthalten, was zu einem Gehalt solcher Nebenprodukte in erfindungsgemäßen Mitteln von gegebenenfalls bis zu 0,4 Gew.-% führen kann.In addition to the constituents mentioned, the preparations stabilized according to the invention may contain small amounts of pH-buffering substances and / or 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. Preferably, the agents contain more than 0 wt .-% to about 0.01 wt .-%, in particular about 0.001 wt .-% to about 0.008 wt .-% of colored, in particular 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. The stability of both the colored metal pigment and the alkali hypochlorite is enhanced by the presence of alkali iodide. Preferably, therefore, more than 0 wt .-% to about 0.01 wt .-%, in particular about 0.001 wt .-% to about 0.006 wt .-% alkali metal iodide, in particular potassium iodide present in inventive compositions. Useful pH buffering ingredients are preferably selected from the alkali carbonates, polycarbonates, sesquicarbonates, silicates, polysilicates, borates, phosphates, stannates, aluminates and mixtures thereof, the preferred alkali metals being sodium and potassium. The starting materials for the preparation of, for example, the hypohalite bleach may contain by-products, for example, carbonate, which may result in a content of such by-products in the compositions of optionally up to 0.4% by weight.
Die wäßrigen Zusammensetzungen gemäß der Erfindung haben normalerweise Viskositäten im Bereich von etwa 25 mPa.s bis 1500 mPa.s, insbesondere von 50 mPa.s bis HOO mPa.s.The aqueous compositions according to the invention normally have viscosities in the range from about 25 mPa.s to 1500 mPa.s, in particular from 50 mPa.s to HOO mPa.s.
Eine erfindungsgemäße Zusammensetzung kann, in verdünnter oder unverdünnter Form, zum Entfernen von Anschmutzungen und Flecken von Textilien verwendet werden, indem man die Zusammensetzung und das Textil über einen Zeitraum, der zur Bleiche des Textils ausreicht, miteinander in Kontakt treten läßt, und danach das Textil mit Wasser spült. Alternativ dazu oder alternativ zu dem Spülen mit Wasser kann das Textil auch unter Einsatz eines erfindungsgemäßen Mittels mit der Hand oder in einem maschinellen Waschverfahren, bei dem ein erfindungsgemäßes Mittel in eine übliche Waschmaschine eindosiert wird, gewaschen werden. BeispielA composition of the invention, in dilute or undiluted form, can be used to remove soils and stains from fabrics by allowing the composition and fabric to contact each other for a time sufficient to bleach the fabric, and then the fabric rinsed with water. Alternatively, or alternatively to rinsing with water, the textile can also be washed using an agent according to the invention by hand or in a mechanical washing process in which an agent according to the invention is metered into a conventional washing machine. example
Bei einer wäßrigen Zusammensetzung, enthaltend 1,43 mmol/1 NaOCl, 8 10"4 mmol/1 Tinopal® CBS-X und 5 mmol/1 ß-Cyclodextrin, lag die Intensität der Fluoreszenz des optischen Aufhellers nach Lagerung über 1 Stunde 20 % höher als bei einer ansonsten identischen Zusammensetzung, welcher das ß-Cyclodextrin fehlte und die unter den gleichen Bedingungen gelagert wurde.For an aqueous composition containing 1.43 mmol / l NaOCl, 8 10 "4 mmol / l Tinopal® CBS-X and 5 mmol / l β-cyclodextrin, the fluorescence intensity of the optical brightener after storage for 1 hour was 20%. higher than an otherwise identical composition lacking the β-cyclodextrin and stored under the same conditions.
Wenn man den genannten optischen Aufheller durch 1,5 10"4 mmol/1 Hostalux® PCNX ersetzte, lag der Wert um 21 % höher als bei der Zusammensetzung, welcher das ß- Cyclodextrin fehlte.Replacing the above optical brightener with 1.5 10 "4 mmol / l Hostalux® PCNX, the value was 21% higher than the composition lacking the β-cyclodextrin.
Wenn man den genannten optischen Aufheller durch 7,5 10"4 mmol/1 Optiblanc® BRB ersetzte, lag der Wert um 54 % höher als bei der Zusammensetzung, welcher das ß- Cyclodextrin fehlte. Replacing the above optical brightener with 7.5 10 "4 mmol / l Optiblanc® BRB, the value was 54% higher than the composition lacking the β-cyclodextrin.

Claims

Patentansprüche claims
1. Verwendung von Cyclodextrin zur Stabilisierung optischer Aufheller in wäßrigen Flüssigwaschmitteln, die Alkalihypochlorit enthalten.1. The use of cyclodextrin for stabilizing optical brighteners in aqueous liquid detergents containing alkali metal hypochlorite.
2. Verwendung nach Anspruch 1, dadurch gekennzeichnet, dass das Cyclodextrin ß- Cyclodextrin ist.2. Use according to claim 1, characterized in that the cyclodextrin is β-cyclodextrin.
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.-% Cyclodextrin enthält.3. Use according to claim 1 or 2, characterized in that the composition contains more than 0 wt .-% up to 0.5 wt .-%, in particular 0.01 wt .-% to 0.1 wt .-% cyclodextrin ,
4. Verwendung nach einem der Ansprüche 1 bis 3, dadurch gekennzeichnet, dass der optische Aufheller aus einer Verbindung gemäß einer der folgenden Formeln (I) bis (VIII) oder deren Gemischen ausgewählt wird,4. Use according to one of claims 1 to 3, characterized in that the optical brightener is selected from a compound according to one of the following formulas (I) to (VIII) or mixtures thereof,
in denen bedeutenin which mean
R1 Wasserstoff, -SO3M, -OR13, -CN, -Cl, -COOR13, -CON(R13)2 R 1 is hydrogen, -SO 3 M, -OR 13 , -CN, -Cl, -COOR 13 , -CON (R 13 ) 2
R2 und R3 unabhängig voneinander Wasserstoff, -R13 oder -Ar, R4 und R5 unabhängig voneinander -OH, -Cl, -NH2, -OR13, -O-Ar, -NHR13, -N(R13)2, -NR13R14, -N(R14)2, -NH-Ar, eine Morpholino-Gruppe, -S-R13 oder -S-Ar, R6 Wasserstoff, -Cl oder -SO3M,R 2 and R 3 are independently hydrogen, -R 13 or -Ar, R 4 and R 5 are independently -OH, -Cl, -NH 2 , -OR 13 , -O-Ar, -NHR 13 , -N (R 13 ) 2 , -NR 13 R 14 , -N (R 14 ) 2 , -NH-Ar, a morpholino group, -SR 13 or -S-Ar, R 6 is hydrogen, -Cl or -SO 3 M,
R7 -CN, -SO3M, -S-R13 oder -S-Ar,R 7 is -CN, -SO 3 M, -SR 13 or -S-Ar,
R8 Wasserstoff, -R13, -Cl oder -SO3M,R 8 is hydrogen, -R 13 , -Cl or -SO 3 M,
R9 und R10 unabhängig voneinander Wasserstoff, -R13, -Cl, -SO3M oder -OR13,R 9 and R 10 independently of one another are hydrogen, -R 13 , -Cl, -SO 3 M or -OR 13 ,
R11 Wasserstoff oder -R13,R 11 is hydrogen or -R 13 ,
R12 Wasserstoff, -R13, -CN, Cl, -COOR13, -CON(R13)2, -Ar oder -O-Ar,R 12 is hydrogen, -R 13 , -CN, Cl, -COOR 13 , -CON (R 13 ) 2 , -Ar or -O-Ar,
R13 eine verzweigte oder unverzweigte C1- bis C4-AlkylgruppeR 13 is a branched or unbranched C 1 - to C 4 -alkyl group
R14 eine verzweigte oder unverzweigte Ci- bis C4-Hydroxyalkylgruppe,R 14 is a branched or unbranched ci- to C 4 -hydroxyalkyl group,
Ar eine gegebenenfalls mit -R13, -Cl, -SO3M oder -OR13 substituierteAr is optionally substituted with -R 13 , -Cl, -SO 3 M or -OR 13
Phenyl-, Naphthyl-, Pyrindinyl-, Pyridazinyl-, Pyrimidinyl-, Pyrazinyl-, Triazinyl-, Indolyl-, Anthracenyl-, Phenanthrenyl- oder Benzonaphthylgruppe,Phenyl, naphthyl, pyrindinyl, pyridazinyl, pyrimidinyl, pyrazinyl, triazinyl, indolyl, anthracenyl, phenanthrenyl or benzonaphthyl group,
M Wasserstoff, Na, K, Ca, Mg, Ammonium, mono-, di-, tri- oder tetra-R13- substituiertes Ammonium, mono-, di-, tri- oder tetra-RI4-substituiertes Ammonium oder mit einer Mischung aus R13 und R14 mono-, di-, tri- oder tetra-substituiertes Ammonium.M is hydrogen, Na, K, Ca, Mg, ammonium, mono-, di-, tri- or tetra-R 13 - substituted ammonium, mono-, di-, tri- or tetra-R I4 -substituted ammonium or with a mixture from R 13 and R 14 mono-, di-, tri- or tetra-substituted ammonium.
5. Verwendung nach einem der Ansprüche 1 bis 4, dadurch gekennzeichnet, dass die Zusammensetzung 0,5 Gew.-% bis 5 Gew.-% Alkalihypochlorit, insbesondere Natriumhypochlorit, enthält.5. Use according to one of claims 1 to 4, characterized in that the composition contains 0.5 wt .-% to 5 wt .-% alkali hypochlorite, in particular sodium hypochlorite.
6. Verwendung nach einem der Ansprüche 1 bis 5, dadurch gekennzeichnet, dass die Zusammensetzung bis zu 20 Gew.-% bleichstabiles Tensid, insbesondere Betain und/oder Alkylethersulfat, enthält.6. Use according to any one of claims 1 to 5, characterized in that the composition contains up to 20 wt .-% bleach-stable surfactant, in particular betaine and / or alkyl ether sulfate.
7. Wäßriges flüssiges Bleichmittel, enthaltend Alkalihypochlorit und optischen Aufheller, dadurch gekennzeichnet, dass es zusätzlich Cyclodextrin enthält.7. Aqueous liquid bleach containing alkali hypochlorite and optical brightener, characterized in that it additionally contains cyclodextrin.
8. Mittel nach Anspruch 7, dadurch gekennzeichnet, dass der optische Aufheller aus einer Verbindung gemäß einer der Formeln (I) bis (VIII) oder deren Gemischen ausgewählt wird. 8. A composition according to claim 7, characterized in that the optical brightener is selected from a compound according to one of the formulas (I) to (VIII) or mixtures thereof.
9. Mittel nach Anspruch 7 oder 8, dadurch gekennzeichnet, dass es 10 ppm bis 0,5 Gew. % optischen Aufheller enthält. 9. Composition according to claim 7 or 8, characterized in that it contains 10 ppm to 0.5 wt.% Optical brightener.
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ATE457342T1 (en) 2010-02-15
ES2339598T3 (en) 2010-05-21
EP1966362B1 (en) 2010-02-10
PL1966362T3 (en) 2010-07-30
DE502006006132D1 (en) 2010-03-25
WO2007079859A1 (en) 2007-07-19
US20080305981A1 (en) 2008-12-11
DE102005063181A1 (en) 2007-07-05

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