EP1966364B1 - Improving the stability of detergents containing hypochlorite - Google Patents

Improving the stability of detergents containing hypochlorite Download PDF

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Publication number
EP1966364B1
EP1966364B1 EP06829421.4A EP06829421A EP1966364B1 EP 1966364 B1 EP1966364 B1 EP 1966364B1 EP 06829421 A EP06829421 A EP 06829421A EP 1966364 B1 EP1966364 B1 EP 1966364B1
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EP
European Patent Office
Prior art keywords
hydrogen
alkali metal
hypochlorite
ammonium
tetra
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EP06829421.4A
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German (de)
French (fr)
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EP1966364A1 (en
Inventor
Carlos Malet
Miguel Osset
Mercedes Mendoza Cruz
Nuria Montaner
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Henkel AG and Co KGaA
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Henkel AG and Co KGaA
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Priority to PL06829421T priority Critical patent/PL1966364T3/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
    • C11D3/395—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
    • C11D3/16—Organic compounds
    • C11D3/36—Organic compounds containing phosphorus
    • C11D3/364—Organic compounds containing phosphorus containing nitrogen
    • 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 aqueous liquid detergents containing 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 relates to the use of diethylenetriaminepentamethylenephosphonic acid and / or its alkali metal salt for stabilizing optical brighteners in aqueous liquid detergents which contain alkali metal hypochlorite.
  • hypochlorite-containing liquid agents With the addition of diethylenetriamine penta-methylenephosphonic acid and / or their alkali metal salts to hypochlorite-containing liquid agents, the stability of optical brighteners contained in these agents is increased and also the hypochlorite is degraded less rapidly during storage than without this addition of Case is.
  • Diethylenetriamine penta-methylenephosphonic acid is commercially available, for example, under the trade name Dequest® 2066.
  • the agent may contain any alkali salts of diethylenetriamine penta-methylenephosphonic acid. Preference is given to the use of the mono-, di-, tri-, tetra- or penta-sodium salt which can be used as such in the preparation of the compositions or in situ from the diethylenetriamine-penta-methylenephosphonic acid and alkali used instead forms.
  • 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
  • the preparations are particularly suitable and very effective as a bleaching or bleaching detergent for white textiles.
  • Such an agent 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, ie if it has been stored for a long time after its production.
  • a further advantage of using 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 those of corresponding blended fabrics.
  • a liquid composition using 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 laundry detergent or alone as a detergent, but it can additionally or alternatively also undiluted on the Textile are applied, for example as a liquid pretreatment agent or stain remover.
  • a bleaching agent in the form of hypochlorite is an integral part of 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 be readily used to prepare such agents, 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 are normally alkaline and may contain for this purpose from about 0.1% to 2%, more preferably from 0.1% to 1.1%, by weight, alkali metal hydroxide.
  • 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 those of the general formula IX, 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.
  • 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 preferably included in the compositions in amounts of up to 20% by weight, in particular from 0.1% by weight to 15% by weight.
  • the preparations may optionally contain, in addition to the diethylenetriamine penta-methylenephosphonic acid and / or their alkali metal salt, further sequestering agents, preferably 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 are also known in the art may be in the form of their alkali metal salts.
  • amine oxide phosphonic acids having at least one amine oxide substituent on the alkyl group
  • polyacrylic acids and / or polyoxyacids containing phosphono groups which are also known in the art may be in the form of their alkali metal salts.
  • Amine oxide phosphonic acids are normally prepared by oxidation of aminoalkyl phosphonic acids.
  • amine oxide phosphonic acids are the amine oxide based on aminotrimethylene phosphonic acid.
  • R 18 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
  • y is 0 or 1.
  • R 18 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
  • y is 0 or 1.
  • the more preferred amine oxide phosphonic acids is the amine oxide based on aminotrimethylene phosphonic acid.
  • from 0.01% to 2% by weight of such additional sequestering agents are present.
  • the preparations 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 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.
  • complex compounds of nickel, cobalt, cuprous, iron and / or manganese are preferred; particularly preferred are copper phthalocyanine dyes.
  • alkali iodide in particular potassium iodide
  • 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 Are potassium.
  • the starting materials for producing, for example, the hypohalite bleach may include by-products, for example, carbonate, which may result in levels of such by-products in the agents of optionally up to 0.4% by weight.
  • the aqueous compositions normally have viscosities in the range of about 25 mPa.s to 1500 mPa.s, in particular from 50 mPa.s to 1100 mPa.s.
  • a composition may be used, in dilute or undiluted form, to remove stains and stains on textiles by allowing the composition and the textile to contact one another for a time sufficient to bleach the fabric, and thereafter the fabric Water washes.
  • the textile may also be washed using such an agent by hand or in a machine washing process in which such agent is metered into a conventional washing machine.

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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)
  • Detergent Compositions (AREA)

Description

Die vorliegende Erfindung betrifft die Stabilisierung hypochlorit-haltiger wässeriger flüssiger Waschmittel, die optischen Aufheller enthalten.The present invention relates to the stabilization of hypochlorite-containing aqueous liquid detergents containing 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 den Nachteil aufweisen, dass 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, which both contain, after storage, in addition to the resulting loss of the bleaching agent also have the disadvantage that the for the optical whiteness 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, hypohalogenithaltigen Bleichmitteln, die optischen Aufheller enthalten, Radikalfänger zuzusetzen, um die optischen Aufheller zu stabilisieren.In the international patent application WO 99/15616 It is proposed to add free-radical scavengers to hypohalite-containing bleaching agents containing optical brighteners 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 Diethylentriamin-pentamethylenphosphonsäure und/oder deren Alkalisalz zur Stabilisierung optischer Aufheller in wäßrigen Flüssigwaschmitteln, die Alkalihypochlorit enthalten.The present invention relates to the use of diethylenetriaminepentamethylenephosphonic acid and / or its alkali metal salt for stabilizing optical brighteners in aqueous liquid detergents which contain alkali metal hypochlorite.

Überraschenderweise wurde jetzt festgestellt, daß bei Zusatz von Diethylentriamin-penta-methylenphosphonsäure und/oder deren Alkalisalzen 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.Surprisingly, it has now been found that with the addition of diethylenetriamine penta-methylenephosphonic acid and / or their alkali metal salts to hypochlorite-containing liquid agents, the stability of optical brighteners contained in these agents is increased and also the hypochlorite is degraded less rapidly during storage than without this addition of Case is.

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 Diethylentriamin-penta-methylenphösphonsäure und/oder deren Alkalisalz in dem zu stabilisierenden flüssigen Mittel enthalten ist. Diethylentriamin-penta-methylenphosphonsäure ist beispielsweise unter dem Handelsnamen Dequest® 2066 kommerziell erhältlich.Normally, it is sufficient if more than 0 wt .-% to about 1 wt .-%, in particular about 0.01 wt .-% to about 0.5 wt .-% of diethylene triamine penta-methylene phosphonic acid and / or whose alkali metal salt is contained in the liquid agent to be stabilized. Diethylenetriamine penta-methylenephosphonic acid is commercially available, for example, under the trade name Dequest® 2066.

Das Mittel kann beliebige Alkalisalze der Diethylentriamin-penta-methylenphosphonsäure enthalten. Bevorzugt ist der Einsatz des Mono-, Di-, Tri-, Tetra- oder Penta-Natriumsalzes, das im Rahmen der Herstellung der Mittel als solches eingesetzt werden kann oder sich aus der stattdessen eingesetzten freien Diethylentriamin-penta-methylenphosphonsäure und Alkali in-situ bildet.The agent may contain any alkali salts of diethylenetriamine penta-methylenephosphonic acid. Preference is given to the use of the mono-, di-, tri-, tetra- or penta-sodium salt which can be used as such in the preparation of the compositions or in situ from the diethylenetriamine-penta-methylenephosphonic acid and alkali used instead forms.

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:

Figure imgb0001
Figure imgb0002
Figure imgb0003
Figure imgb0004
Figure imgb0005
Figure imgb0006
Figure imgb0007
Figure imgb0008
 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 having the trans configured C =C double bond shown may also be present at least in part with those in cis configuration :
Figure imgb0001
Figure imgb0002
Figure imgb0003
Figure imgb0004
Figure imgb0005
Figure imgb0006
Figure imgb0007
Figure imgb0008

In diesen bedeuten

R1
Wasserstoff, -SO3M, -OR13, -CN, -Cl, -COOR13, -CON(R13)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,
R7
-CN, -SO3M, -S-R13 oder -S-Ar,
R8
Wasserstoff, R13, -Cl oder -SO3M,
R9 und R10
unabhängig voneinander Wasserstoff, -R13, -Cl, -SO3M oder -OR13,
R11
Wasserstoff oder -R13,
R12
Wasserstoff, -R13, -CN, Cl, -COOR13, -CON(R13)2, -Ar oder -O-Ar,
R13
eine verzweigte oder unverzweigte C1- bis C4-Alkylgruppe
R14
eine verzweigte oder unverzweigte C1- bis C4-Hydroxyalkylgruppe,
Ar
eine gegebenenfalls mit -R13, -Cl, -SO3M oder -OR13 substituierte Phenyl-, Naphthyl-, Pyrindinyl-, Pyridazinyl-, Pyrimidinyl-, Pyrazinyl-, Triazinyl-, Indolyl-, Anthracenyl-, Phenanthrenyl- oder Benzonaphthylgruppe,
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.
In these mean
R 1
Hydrogen, -SO 3 M, -OR 13 , -CN, -Cl, -COOR 13 , -CON (R 13 ) 2
R 2 and R 3
independently of one another hydrogen, -R 13 or -Ar,
R 4 and R 5
independently of one another -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
Hydrogen, -Cl or -SO 3 M,
R 7
-CN, -SO 3 M, -SR 13 or -S-Ar,
R 8
Hydrogen, R 13 , -Cl or -SO 3 M,
R 9 and R 10
independently of one another hydrogen, -R 13 , -Cl, -SO 3 M or -OR 13 ,
R 11
Hydrogen or -R 13 ,
R 12
Hydrogen, -R 13 , -CN, Cl, -COOR 13 , -CON (R 13 ) 2 , -Ar or -O-Ar,
R 13
a branched or unbranched C 1 - to C 4 alkyl group
R 14
a branched or unbranched C 1 - to C 4 -hydroxyalkyl group,
Ar
an optionally substituted with -R 13 , -Cl, -SO 3 M or -OR 13 substituted phenyl, naphthyl, pyrindinyl, pyridazinyl, pyrimidinyl, pyrazinyl, triazinyl, indolyl, anthracenyl, phenanthrenyl or Benzonaphthylgruppe .
M
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 of 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 enthaltenParticular 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 by 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

Die Zubereitungen sind insbesondere geeignet und sehr effektiv als Bleichmittel beziehungsweise bleichendes Waschmittel für weiße Textilien. Ein solches 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 Zusammensetzung, das heißt wenn sie nach ihrer Herstellung längere Zeit gelagert wurde.The preparations are particularly suitable and very effective as a bleaching or bleaching detergent for white textiles. Such an agent 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, ie if it has been stored for a long time after its production.

Ein weiterer Vorteil der Verwendung 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.A further advantage of using 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 those of corresponding blended fabrics.

Ein flüssiges Mittel unter Verwendung 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 using 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 laundry detergent or alone as a detergent, but it can additionally or alternatively also undiluted on the Textile are applied, for example as a liquid pretreatment agent or stain remover.

Ein Bleichmittel in Form von Hypochlorit ist ein wesentlicher Bestandteil der Erfindungs. 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 solcher 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 integral part of 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 be readily used to prepare such agents, 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 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 are normally alkaline and may contain for this purpose from about 0.1% to 2%, more preferably from 0.1% to 1.1%, by weight, 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,

Figure imgb0009
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 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 vorzugsweise in Mengen bis zu 20 Gew.-%, insbesondere von 0,1 Gew.-% bis 15 Gew.-% in den Mitteln enthalten.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,
Figure imgb0009
 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 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 preferably included in the compositions in amounts of up to 20% by weight, in particular from 0.1% by weight to 15% by weight.

Die Zubereitungen können gegebenenfalls zusätzlich zu der Diethylentriamin-penta-methylenphosphonsäure und/oder deren Alkalisalz weitere Sequestriermittel enthalten, vorzugsweise Alkylphosphonsäuren 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 guter Stabilität des Hypochlorits. Aminoxidphosphonsäuren werden normalerweise durch Oxidation von Aminoalkylphosphonsäuren hergestellt. Sie gehören vorzugsweise zur Gruppe von Verbindungen gemäß allgemeiner Formel (X),

Figure imgb0010
in der R18 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 zusätzlicher Sequestriermittel vorhanden.The preparations may optionally contain, in addition to the diethylenetriamine penta-methylenephosphonic acid and / or their alkali metal salt, further sequestering agents, preferably 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 are also known in the art may 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 aminoalkyl phosphonic acids. They preferably belong to the group of compounds according to general formula (X),
Figure imgb0010
 in which R 18 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 additional sequestering agents are present.

Zusätzlich zu den genannten Bestandteilen können die Zubereitungen geringe Mengen an pH-puffernden Substanzen und/oder an einem oder mehreren bleichstabilen Farb- 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 KupferPhthalocyanin-Farbstoffe. Die Stabilität sowohl des farbigen Metallpigments wie auch des Alkalihypochlorits wird durch die Anwesenheit von Alkalijodid erhöht. Vorzugsweise sind in den 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 den Mitteln von gegebenenfalls bis zu 0,4 Gew.-% führen kann.In addition to the constituents mentioned, the preparations 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 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. 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 iodide, in particular potassium iodide, are present in the agents. 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 Are potassium. The starting materials for producing, for example, the hypohalite bleach may include by-products, for example, carbonate, which may result in levels of such by-products in the agents of optionally up to 0.4% by weight.

Die wäßrigen Zusammensetzungen haben normalerweise Viskositäten im Bereich von etwa 25 mPa.s bis 1500 mPa.s, insbesondere von 50 mPa.s bis 1100 mPa.s.The aqueous compositions normally have viscosities in the range of about 25 mPa.s to 1500 mPa.s, in particular from 50 mPa.s to 1100 mPa.s.

Eine 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 solchen Mittels mit der Hand oder in einem maschinellen Waschverfahren, bei dem ein solchen Mittel in eine übliche Waschmaschine eindosiert wird, gewaschen werden.A composition may be used, in dilute or undiluted form, to remove stains and stains on textiles by allowing the composition and the textile to contact one another for a time sufficient to bleach the fabric, and thereafter the fabric Water washes. Alternatively, or alternatively to rinsing with water, the textile may also be washed using such an agent by hand or in a machine washing process in which such agent is metered into a conventional washing machine.

Beispielexample

Bei einer wäßrigen Zusammensetzung, enthaltend 1,43 mmol/l NaOCl, 8 ·10-4 mmol/l Tinopal® CBS-X und 0,36 mmol/l Dequest® 2066, betrug die Abnahme der Fluoreszenz des optischen Aufhellers nach Lagerung über 1 Stunde 16 %, wohingegen sie bei einer ansonsten identischen Zusammensetzung, welcher die Diethylentriamin-penta-methylenphosphonsäure fehlte und die unter den gleichen Bedingungen gelagert wurde, 94 % betrug.For an aqueous composition containing 1.43 mmol / l NaOCl, 8 × 10 -4 mmol / l Tinopal® CBS-X, and 0.36 mmol / l Dequest® 2066, the decrease in fluorescence of the optical brightener after storage was greater than 1 16% whereas they were 94% in an otherwise identical composition lacking the diethylenetriamine penta-methylene phosphonic acid and stored under the same conditions.

Wenn man den genannten optischen Aufheller durch 1,5 ·10-4 mmol/l Hostalux® PCNX ersetzte, betrugen die Abnahmen 16 % und 71 %.When replacing the above optical brightener with 1.5 × 10 -4 mmol / L Hostalux® PCNX, the decreases were 16% and 71%.

Wenn man den genannten optischen Aufheller durch 7,5 ·10-4 mmol/l Optiblanc® BRB ersetzte und den Lösungen zusätzlich 0,018 mmol/l Fe2+ zusetzte, betrugen die Abnahmen 4 % und 97 %.When replacing the optical brightener by 7.5 × 10 -4 mmol / l Optiblanc® BRB and adding 0.018 mmol / l Fe 2+ to the solutions, the decreases were 4% and 97%.

Claims (6)

  1. Use of diethylenetriaminepentamethylenephosphonic acid and/or the alkali metal salt thereof for stabilizing optical brighteners in aqueous liquid laundry detergents which contain alkali metal hypochlorite.
  2. The use as claimed in claim 1, wherein the alkali metal salt is a sodium salt.
  3. The use as claimed in claim 1 or claim 2, wherein the composition contains more than 0 wt.% up to 0.5 wt.%, in particular 0.01 wt.% to 0.1 wt.% of diethylenetriaminepentamethylenephosphonic acid and/or the alkali metal salt thereof.
  4. The use as claimed in any one of claims 1 to 3, wherein the optical brightener is selected from a compound according to one of the following formulae (I) to (VIII) or mixtures thereof,
    Figure imgb0019
    Figure imgb0020
    Figure imgb0021
    Figure imgb0022
    Figure imgb0023
    Figure imgb0024
    Figure imgb0025
    Figure imgb0026
     in which
    R1 means hydrogen, -SO3M, -OR13, -CN, -Cl, -COOR13, -CON(R13)2
    R2 and R3 mutually independently mean hydrogen, -R13 or -Ar,
    R4 and R5 mutually independently mean -OH, -Cl, -NH2, -OR13, -O-Ar, -NHR13, -N(R13)2, -NR13R14, -N(R14)2, -NH-Ar, a morpholino group, -S-R13 or -S-Ar, R6 means hydrogen, -Cl or -SO3M,
    R7 means -CN, -SO3M, -S-R13 or -S-Ar,
    R8 means hydrogen, -R13, -Cl or -SO3M,
    R9 and R10 mutually independently mean hydrogen, -R13, -Cl, -SO3M or -OR13,
    R11 means hydrogen or -R13,
    R12 means hydrogen, -R13, -CN, Cl, -COOR13, -CON(R13)2, -Ar or -O-Ar,
    R13 means a branched or unbranched C1 to C4 alkyl group
    R14 means a branched or unbranched C1 to C4 hydroxyalkyl group,
    Ar means a phenyl, naphthyl, pyrindinyl, pyridazinyl, pyrimidinyl, pyrazinyl, triazinyl, indolyl, anthracenyl, phenanthrenyl or benzonaphthyl group optionally substituted with -R13, -Cl, -SO3M or -OR,
    M means hydrogen, Na, K, Ca, Mg, ammonium, mono-, di-, tri- or tetra-R13-substituted ammonium, mono-, di-, tri- or tetra-R14-substituted ammonium or ammonium mono-, di-, tri- or tetra-substituted with a mixture of R13 and R14.
  5. The use as claimed in any one of claims 1 to 4, wherein the composition contains 0.5 wt.% to 5 wt.% of alkali metal hypochlorite, in particular sodium hypochlorite.
  6. The use as claimed in any one of claims 1 to 5, wherein the composition contains up to 20 wt.% of bleach-stable surfactant, in particular betaine and/or alkyl ether sulfate.
EP06829421.4A 2005-12-30 2006-12-08 Improving the stability of detergents containing hypochlorite Not-in-force EP1966364B1 (en)

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