EP0394998A2 - Liquid detergent - Google Patents

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Publication number
EP0394998A2
EP0394998A2 EP90107835A EP90107835A EP0394998A2 EP 0394998 A2 EP0394998 A2 EP 0394998A2 EP 90107835 A EP90107835 A EP 90107835A EP 90107835 A EP90107835 A EP 90107835A EP 0394998 A2 EP0394998 A2 EP 0394998A2
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EP
European Patent Office
Prior art keywords
liquid detergent
formula
hydrogen
alkyl
optical brightener
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EP90107835A
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German (de)
French (fr)
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EP0394998B1 (en
EP0394998A3 (en
Inventor
Claude Dr. Eckhardt
Kurt Dr. Weber
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BASF Schweiz AG
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Ciba Geigy AG
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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
    • C11D3/40—Dyes ; Pigments
    • C11D3/42—Brightening agents ; Blueing agents

Definitions

  • the present invention relates to new liquid detergents containing targeted disulfonated dibenzfuranylbiphenyls as optical brighteners, their preparation and their use.
  • optical brighteners in liquid detergents is known. They soak on the items to be washed during treatment and, due to their special light absorption / emission properties, lead to an elimination of the yellowish tones or an improvement in the degree of whiteness.
  • EP-A-167 205 proposes to use monosulfonated stilbene triazolyl, triazine or distyrylbiphenyl brighteners in anionic liquid detergents.
  • X is a sulfonic acid residue, hydrogen or C1-C4-alkyl
  • Y and Z independently of one another a sulfonic acid residue, hydrogen, C1-C4-alkyl, C1-C4-alkoxy, halogen, CN, phenoxy, benzyloxy, with the condition that either X or Y or Z is a sulfonic acid residue and the remaining substituents are not a sulfonic acid residue.
  • halogens are fluorine, chlorine and bromine, but especially chlorine.
  • C1-C4-alkyl or C1-C4-alkoxy
  • C1-C4-alkyl or C1-C4-alkoxy
  • alkyl (or alkoxy) residues can in turn be substituted with e.g. Aryl (phenyl, naphthyl), C1-C4 alkyl, C1-C4 alkoxy, OH or CN groups.
  • M in the meaning of a non-chromophoric cation preferably represents alkali metal such as lithium, sodium, potassium and optionally substituted ammonium such as ammonium, mono-, di- or triethanolammonium, mono-, di- or tripropanolammonium or tri- or tetramethylammonium.
  • R3 is independently hydrogen, methyl or ethyl and M is preferably sodium or potassium.
  • SO3 / base complex are to be understood as addition compounds of SO3 with organic bases, for example dioxane, preferably nitrogen-containing bases, such as triethylamine, N-ethyldiisopropylamine, dimethylformamide (DMF) and in particular pyridine.
  • organic bases for example dioxane, preferably nitrogen-containing bases, such as triethylamine, N-ethyldiisopropylamine, dimethylformamide (DMF) and in particular pyridine.
  • DMF dimethylformamide
  • pyridine dimethylformamide
  • SO3 / base complexes are known and can be prepared by known methods (EE Gilbert, EP Jones, Ind. Enging. Chem. 49, No. 9, Part II, pp. 1553 ff (1957); Beilstein 20, III / IV , 2232).
  • Inert organic solvents are for example, saturated aliphatic hydrocarbons such as gasoline, petroleum ether and ligroin, halogenated aliphatic hydrocarbons such as chloroform, carbon tetrachloride, dichloroethane, trichloroethane, tetrachloroethane, dichloropropane, trichloropropane, dichlorodifluoromethane and dichlorotetrafluoroethane, chlorobenzenes such as mono-, di- and trichlorobenzene, nitrobenzenes as Nitrobenzene and nitrotoluene as well as dicyclic hydrocarbons such as cyclohexane, methylcyclohexane and decalin.
  • saturated aliphatic hydrocarbons such as gasoline, petroleum ether and ligroin
  • halogenated aliphatic hydrocarbons such as chloroform, carbon tetrachloride, dichloroe
  • the etherification in process d) takes place at temperatures from 60 ° to 140 ° C. and in particular 100 ° to 120 ° C. in a known manner by means of an equivalent of a base, such as a tert. Amine or a base mentioned in the following cyclization, or by already using the compounds of the formula XI or XII as the phenolate of this base.
  • the process is carried out in a polar, aprotic solvent or solvent mixture, such as, for example, dimethylformamide, N-methylpyrrolidone, hexamethylphosphoric triamide, tetramethylurea or preferably dimethyl sulfoxide.
  • the cyclization in process d) likewise takes place in a polar, aprotic solvent, preferably in the same one in which the etherification also takes place, at slightly elevated temperatures compared to the etherification and in the presence of a base, such as quaternary ammonium bases, alkaline earth metal hydroxides, alkali amides, alkali metal hydrides , Alkali metal carbonates, but preferably alkali metal alcoholates such as potassium t-butoxide and sodium methylate, and in particular alkali metal hydroxides such as sodium, potassium and lithium hydroxide.
  • the basic condensing agents are in at least stoichiometric amounts, preferably in excess. It is advantageous to work in the absence of atmospheric oxygen and an inert gas atmosphere.
  • Liquid detergents are understood to mean known and commercially available detergents such as are described, for example, in EP-A-167 205 or US-4,507,219 or GB 8712430.
  • the optical brightener content in the liquid detergents is 0.01-2%, in particular 0.01-1%, particularly preferably 0.03-0.3%.
  • the liquid detergents contain 1 to 60 anionic, nonionic, zwitterionic and optionally cationic surfactants and 25 to 65%, preferably 40 to 55%, water.
  • the detergent contains 3 to 50% preferably 15 to 25% anionic surfactants, 2 to 30% preferably 4 to 15% nonionic surfactants, 3 to 30% preferably 5 to 20% optionally ethoxylated (C10-C14) - Fatty acids such as capric, lauric, myristic, coconut and palm kernel acid and mixtures thereof, 1 to 25% preferably 1 to 10% detergent builders and optionally 1 to 10% preferably 1 to 5% zwitterionic surfactants, 0.5 to 3% preferably 0.7 to 2% quaternary ammonium, amine or amine oxide surfactants, and 1 to 10% common detergent additives such as enzymes, enzyme stabilizers, antioxidants, preservatives and disinfectants, fragrances and dyes, complexing agents or sequestering
  • surfactants are described, for example, in U.S. 4,285,841, U.S. 3,929,678, U.S. 4,284,532 and GB 2,041,986.
  • the surfactants designated as preferred in EP-A-167 205 are used.
  • optionally used as anionic surfactants are ethoxylated C1ate-C18 alkyl sulfates, for example in the form of the triethanolamine salts, C10-C15 alkylbenzenesulfonates or mixtures thereof and as nonionic surfactants, condensation products from one mole of (C10-C15) fatty alcohol with 3 to 8 moles of ethylene oxide .
  • Suitable detergent builders are the preferably polycarboxylated compounds mentioned in US Pat. Nos. 4,321,165 and 4,284,532, such as citric acid.
  • Targeted liquid detergents containing sulfonated dibenzofuranylbiphenyls can also be used e.g. in GB 8712430, contain bleach.
  • Perborate is preferably used as the bleaching agent.
  • a liquid detergent is prepared 15 parts of C11-C13 alkylbenzenesulfonate 14 parts of C14-C15 polyethoxy fatty alcohol (7 ethylene oxide) 10 parts of soap 9 parts of ethanol 5 parts of triethanolamine 4 parts Na citrate 43 parts of water and 0.1 part of the optical brightener of the formula forth.
  • the stain test shows only a very slight formation of light stains with a very high degree of lightening.
  • the detergent formulation is stable on storage.
  • Example 1 a liquid detergent is prepared, but instead of compound (100) the compound of the formula contains.
  • the properties of the liquid detergent correspond to those from Example 1.
  • Example 1 a liquid detergent is prepared, but instead of compound (100) the compound of the formula contains.
  • the properties of the liquid detergent correspond to those from Example 1.
  • Example 1 a liquid detergent is prepared, but instead of compound (100) the compound of the formula contains.
  • the detergent formulation is very stable in storage.
  • the stain test shows only a very weak formation of light spots.
  • Example 1 a liquid detergent is prepared, but instead of compound (100) the compound of the formula contains.
  • the detergent formulation is very stable in storage.
  • the stain test shows only a slight formation of light stains with high lightening effects.
  • a liquid detergent is prepared 6.5 parts of triethanolamine 3.5 parts NaOH 6.5 parts of ethanol 1.5 parts of 1,2 propanediol 11.5 parts of C14-C15 polyethoxy fatty alcohol (7 ethylene oxide) 2.5 parts of coconut alkyl sulfate 10.5 parts of linear dodecylbenzenesulfonic acid 4.0 parts of oleic acid 10.5 parts of saturated C12-C14 acid 43.0 parts of deionized water and 0.1 part of the optical brightener of the formula forth.
  • the detergent is opaque, homogeneous and very stable in storage.
  • the stain test shows only a very slight formation of light stains with a very high degree of lightening.
  • Example 6 a liquid detergent is prepared, but instead of the compound (200) the compound of the formula contains.
  • the properties of the liquid detergent correspond to those from Example 6.

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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)

Abstract

Liquid detergents containing specifically disulphonated dibenzofuranylbiphenyls of the formula <IMAGE> in which X is a sulphonic acid radical, hydrogen or C1-C4-alkyl, Y and Z are, independently of one another, a sulphonic acid radical, hydrogen, C1-C4-alkyl, C1-C4-alkoxy, halogen, CN, phenoxy, benzyloxy, with the condition that either X or Y or Z is a sulphonic acid radical, and the remaining substituents are not a sulphonic acid radical, the preparation and use thereof are described; these detergents prevent the formation of pale spots on textile fabric when the latter comes directly into contact with the liquid detergent.

Description

Die vorliegende Erfindung betrifft neue flüssige Waschmittel enthaltend gezielt disulfonierte Dibenzfuranylbiphenyle als optische Aufheller deren Herstellung und deren Verwendung.The present invention relates to new liquid detergents containing targeted disulfonated dibenzfuranylbiphenyls as optical brighteners, their preparation and their use.

Die Verwendung von optischen Aufhellern in flüssigen Waschmitteln ist bekannt. Sie ziehen während der Behandlung auf das Waschgut auf und führen durch ihre spezielle Lichtabsorption/Emissionseigenschaft zu einer Elimination der gelblichen Töne bzw. zu einer Verbesserung des Weiss­grades.The use of optical brighteners in liquid detergents is known. They soak on the items to be washed during treatment and, due to their special light absorption / emission properties, lead to an elimination of the yellowish tones or an improvement in the degree of whiteness.

Dieser Effekt ist aber auch verantwortlich für das Auftreten von hellen Flecken wenn Textilgewebe z.B. bei einer Vorbehandlung direkt mit dem flüssigen Waschmittel in Kontakt gerät. In der EP-A-167 205 wird zur Lösung dieses Problems vorgeschlagen, monosulfonierte Stilbentriazolyl-, -triazin- oder Distyrylbiphenyl-Aufheller in anionischen Flüssigwasch­mitteln zu verwenden.This effect is also responsible for the appearance of light spots when textile fabrics e.g. comes into direct contact with the liquid detergent during pretreatment. To solve this problem, EP-A-167 205 proposes to use monosulfonated stilbene triazolyl, triazine or distyrylbiphenyl brighteners in anionic liquid detergents.

Ueberraschenderweise kann die Bildung heller Flecken, bei ausgezeichneter Aufhellwirkung und sehr gutem Lagerverhalten des flüssigen Waschmittels, auch durch optische Aufheller der Formel

Figure imgb0001
verhindert werden.Surprisingly, the formation of light spots, with an excellent lightening effect and very good storage behavior of the liquid detergent, can also be achieved by optical brighteners of the formula
Figure imgb0001
 be prevented.

Im einzelnen bedeutet:
X ein Sulfonsäurerest, Wasserstoff oder C₁-C₄-Alkyl, Y und Z unabhängig voneinander ein Sulfonsäurerest, Wasserstoff, C₁-C₄-Alkyl, C₁-C₄-Alkoxy, Halogen, CN, Phenoxy, Benzyloxy, mit der Bedingung, dass entweder X oder Y oder Z ein Sulfonsäurerest ist und die restlichen Substituenten nicht ein Sulfonsäurerest sind.Specifically means:
X is a sulfonic acid residue, hydrogen or C₁-C₄-alkyl, Y and Z independently of one another a sulfonic acid residue, hydrogen, C₁-C₄-alkyl, C₁-C₄-alkoxy, halogen, CN, phenoxy, benzyloxy, with the condition that either X or Y or Z is a sulfonic acid residue and the remaining substituents are not a sulfonic acid residue.

Als Halogene kommen vor allem Fluor, Chlor und Brom in Frage, insbe­sondere jedoch Chlor.The most suitable halogens are fluorine, chlorine and bromine, but especially chlorine.

Als C₁-C₄-Alkylreste (bzw. C₁-C₄-Alkoxyreste) kommen unverzweigte oder verzweigte Alkyl- (bzw. Alkoxy-) reste in Betracht. Diese Alkyl- (bzw. Alkoxy-) reste können ihrerseits substituiert sein mit z.B. Aryl- (Phenyl-, Naphthyl-), C₁-C₄-Alkyl-, C₁-C₄-Alkoxy-, OH- oder CN-Gruppen.As C₁-C₄-alkyl (or C₁-C₄-alkoxy) are unbranched or branched alkyl (or alkoxy) into consideration. These alkyl (or alkoxy) residues can in turn be substituted with e.g. Aryl (phenyl, naphthyl), C₁-C₄ alkyl, C₁-C₄ alkoxy, OH or CN groups.

Bevorzugte Dibenzfuranylbiphenyle der Formel (1) sind solche der Formel

Figure imgb0002
worin
R₁ = Wasserstoff, C₁-C₄-Alkyl, Chlor, C₁-C₄-Alkoxy, Phenoxy oder Benzyl­oxy, R₂ = Wasserstoff oder C₁-C₄-Alkyl und M = Wasserstoff und/oder ein Aequivalent eines nicht chromophoren Kations bedeuten.Preferred dibenzfuranylbiphenyls of the formula (1) are those of the formula
Figure imgb0002
 wherein
R₁ = hydrogen, C₁-C₄-alkyl, chlorine, C₁-C₄-alkoxy, phenoxy or benzyloxy, R₂ = hydrogen or C₁-C₄-alkyl and M = hydrogen and / or an equivalent of a non-chromophoric cation.

M in der Bedeutung eines nicht-chromophoren Kations steht vorzugsweise für Alkalimetall wie Lithium, Natrium, Kalium sowie gegebenenfalls substituiertes Ammonium wie Ammonium, Mono-, Di- oder Triethanol­ammonium, Mono-, Di- oder Tripropanolammonium oder Tri- oder Tetra­methylammonium.M in the meaning of a non-chromophoric cation preferably represents alkali metal such as lithium, sodium, potassium and optionally substituted ammonium such as ammonium, mono-, di- or triethanolammonium, mono-, di- or tripropanolammonium or tri- or tetramethylammonium.

Von besonderem Interesse sind jedoch Verbindungen der Formel

Figure imgb0003
worin R₃ unabhängig voneinander für Wasserstoff, Methyl oder Ethyl steht und M vorzugsweise Natrium oder Kalium ist.However, compounds of the formula are of particular interest
Figure imgb0003
 wherein R₃ is independently hydrogen, methyl or ethyl and M is preferably sodium or potassium.

Die optischen Aufheller können hergestellt werden, indem man
a) ein Mol der Verbindung der Formel (X)

Figure imgb0004
die gegebenenfalls mehrfach mit Resten R = Wasserstoff, C₁-C₄-Alkyl, C₁-C₄-Alkoxy, Halogen, Phenoxy und Benzyloxy substituiert ist und wobei R₄ für Wasserstoff oder C₁-C₄-Alkyl steht, mit mindestens stöchio­metrischen Mengen eines SO₃/Basen-Komplexes, in einem inerten organischen Lösungsmittel, bei Temperaturen von 20°C bis zum Siedepunkt des ver­wendeten Lösungsmittels umsetzt oder
b) ein Mol der Verbindung der Formel (X) mit mindestens stöchiometrischen Mengen Chlorsulfonsäure, in einem inerten organischen Lösungsmittel, bei Temperaturen von 0° bis 40°C umsetzt oder
c) die Verbindung der Formel (X) mit konzentrierter Schwefelsäure oder mit Schwefelsäure/Eisessig bzw. Oleum/Eisessig auf Temperaturen von 40° bis 140°C erhitzt oder
d) ein Mol 4,4′-Bis-(halogenmethyl)-biphenyl mit mindestens 2 Mol Salicylaldehyd oder deren Anile der Formel (XI) bzw. (XII)
Figure imgb0005
 die gegebenenfalls mehrfach mit Resten R = Wasserstoff, C₁-C₄-Alkyl, C₁-C₄-Alkoxy, Halogen, Phenoxy und Benzyloxy substituiert sind und worin M = Wasserstoff und/oder ein Aequivalent eines nichtchromophoren Kations, und R₅ = Phenyl oder Chlorphenyl bedeuten, verethert und die erhaltenen Bisbenzylether der Formel (XIII) bzw. (XIV)
Figure imgb0006
 mit Basen cyclisiert.The optical brighteners can be made by
a) one mole of the compound of formula (X)
Figure imgb0004
 which is optionally substituted several times with radicals R = hydrogen, C₁-C₄-alkyl, C₁-C₄-alkoxy, halogen, phenoxy and benzyloxy and where R₄ is hydrogen or C₁-C₄-alkyl, with at least stoichiometric amounts of a SO₃ / base Complex, in an inert organic solvent, at temperatures from 20 ° C to the boiling point of the solvent used or
b) reacting one mole of the compound of formula (X) with at least stoichiometric amounts of chlorosulfonic acid, in an inert organic solvent, at temperatures from 0 ° to 40 ° C. or
c) the compound of formula (X) with concentrated sulfuric acid or with sulfuric acid / glacial acetic acid or oleum / glacial acetic acid to temperatures of 40 ° to 140 ° C or
d) one mole of 4,4'-bis (halogenomethyl) biphenyl with at least 2 moles of salicylaldehyde or their anils of the formula (XI) or (XII)
Figure imgb0005
 which are optionally substituted several times with radicals R = hydrogen, C₁-C₄-alkyl, C₁-C₄-alkoxy, halogen, phenoxy and benzyloxy and in which M = hydrogen and / or an equivalent of a non-chromophoric cation, and R₅ = phenyl or chlorophenyl, etherified and the bisbenzyl ethers of the formula (XIII) or (XIV) obtained
Figure imgb0006
 cyclized with bases.

Die Ausgangsverbindungen der Formel (X), (XI) und (XII) sind bekannt und können nach bekannten Methoden hergestellt werden. Vorteilhafterweise wird das Verfahren d) jedoch als Eintopfverfahren ohne Isolierung der Zwischenprodukte (XIII) und (XIV) durchgeführt.The starting compounds of the formulas (X), (XI) and (XII) are known and can be prepared by known methods. However, process d) is advantageously carried out as a one-pot process without isolation of the intermediates (XIII) and (XIV).

Im einzelnen werden nach dem Verfahren a) die Verbindungen der Formel (III) und (IV) hergestellt.In detail, the compounds of the formulas (III) and (IV) are prepared by process a).

Unter SO₃/Basen-Komplex sind Additionsverbindungen von SO₃ an organische Basen, z.B. Dioxan, vorzugsweise stickstoffhaltige Basen, wie zum Beispiel Triethylamin, N-Ethyldiisopropylamin, Dimethylformamid (DMF) und insbesondere Pyridin zu verstehen. Die Stabilität dieser Additionsver­bindungen ist dabei entscheidend für den Sulfonierungsgrad. So werden bei Verwendung von 2 bis 6, insbesondere 3 bis 5 Mol SO₃/Pyridin-Komplex (bezogen auf den SO₃-Gehalt) pro Mol der Verbindung der Formel (X) z.B. Verbindungen der Formel (III) und (V) hergestellt. SO₃/Basen-Komplexe sind bekannt und können nach bekannten Methoden hergestellt werden (E.E. Gilbert, E.P. Jones, Ind. Enging. Chem. 49, Nr. 9, Teil II, S. 1553 ff (1957); Beilstein 20, III/IV, 2232).SO₃ / base complex are to be understood as addition compounds of SO₃ with organic bases, for example dioxane, preferably nitrogen-containing bases, such as triethylamine, N-ethyldiisopropylamine, dimethylformamide (DMF) and in particular pyridine. The stability of these addition compounds is decisive for the degree of sulfonation. So when using 2 to 6, especially 3 to 5 moles of SO₃ / pyridine complex (based on the SO₃ content) per mole of the compound of formula (X), for example compounds of formula (III) and (V). SO₃ / base complexes are known and can be prepared by known methods (EE Gilbert, EP Jones, Ind. Enging. Chem. 49, No. 9, Part II, pp. 1553 ff (1957); Beilstein 20, III / IV , 2232).

Inerte organische Lösungsmittel sind beispielsweise gesättigte ali­phatische Kohlenwasserstoffe wie Gasolin, Petrolether und Ligroin, halogenierte, aliphatische Kohlenwasserstoffe wie Chloroform, Tetra­chlorkohlenstoff, Dichlorethan, Trichlorethan, Tetrachlorethan, Dichlor­propan, Trichlorpropan, Dichlordifluormethan und Dichlortetrafluorethan, Chlorbenzole wie Mono-, Di- und Trichlorbenzol, Nitrobenzole wie Nitro­benzol und Nitrotoluol sowie dicyclische Kohlenwasserstoffe wie Cyclo­hexan, Methylcyclohexan und Dekalin.Inert organic solvents are for example, saturated aliphatic hydrocarbons such as gasoline, petroleum ether and ligroin, halogenated aliphatic hydrocarbons such as chloroform, carbon tetrachloride, dichloroethane, trichloroethane, tetrachloroethane, dichloropropane, trichloropropane, dichlorodifluoromethane and dichlorotetrafluoroethane, chlorobenzenes such as mono-, di- and trichlorobenzene, nitrobenzenes as Nitrobenzene and nitrotoluene as well as dicyclic hydrocarbons such as cyclohexane, methylcyclohexane and decalin.

Nach dem Verfahren c) werden insbesondere die Verbindungen der Formel (II) und (IV) hergestellt.In particular, the compounds of the formulas (II) and (IV) are prepared by process c).

Die Veretherung bei Verfahren d) erfolgt bei Temperaturen von 60° bis 140°C und insbesondere 100° bis 120°C in bekannter Weise mittels einem Aequivalent einer Base, wie einem tert. Amin oder einer bei der folgenden Cyclisierung genannten Base, oder indem man die Verbindungen der Formel XI oder XII bereits als Phenolat dieser Base einsetzt. Man arbeitet in einem polaren, aprotischen Lösungsmittel oder Lösungsmittel­gemisch wie zum Beispiel Dimethylformamid, N-Methylpyrrolidon, Hexa­methylphosphorsäuretriamid, Tetramethylharnstoff oder vorzugsweise Dimethylsulfoxid.The etherification in process d) takes place at temperatures from 60 ° to 140 ° C. and in particular 100 ° to 120 ° C. in a known manner by means of an equivalent of a base, such as a tert. Amine or a base mentioned in the following cyclization, or by already using the compounds of the formula XI or XII as the phenolate of this base. The process is carried out in a polar, aprotic solvent or solvent mixture, such as, for example, dimethylformamide, N-methylpyrrolidone, hexamethylphosphoric triamide, tetramethylurea or preferably dimethyl sulfoxide.

Die Cyclisierung bei Verfahren d) erfolgt ebenfalls in einem polaren, aprotischen Lösungsmittel, vorzugsweise in demselben, in dem auch die Veretherung stattfindet, bei im Vergleich zur Veretherung leicht erhöhten Temperaturen und in Gegenwart einer Base, wie z.B. quaternären Ammonium­basen, Erdalkalihydroxiden, Alkaliamiden, Alkalihydriden, Alkali­carbonaten, vorzugsweise aber Alkalialkoholaten wie Kalium-t-butylat und Natriummethylat sowie insbesondere Alkalihydroxiden wie Natrium-, Kalium- und Lithiumhydroxid. Die basischen Kondensationsmittel werden in mindestens stöchiometrischen Mengen, vorzugsweise im Ueberschuss, eingesetzt. Vorteilhaft arbeitet man unter Luftsauerstoffausschluss und Inertgasatmosphäre.The cyclization in process d) likewise takes place in a polar, aprotic solvent, preferably in the same one in which the etherification also takes place, at slightly elevated temperatures compared to the etherification and in the presence of a base, such as quaternary ammonium bases, alkaline earth metal hydroxides, alkali amides, alkali metal hydrides , Alkali metal carbonates, but preferably alkali metal alcoholates such as potassium t-butoxide and sodium methylate, and in particular alkali metal hydroxides such as sodium, potassium and lithium hydroxide. The basic condensing agents are in at least stoichiometric amounts, preferably in excess. It is advantageous to work in the absence of atmospheric oxygen and an inert gas atmosphere.

Unter Flüssigwaschmitteln sind bekannte und handelsübliche Waschmittel wie sie beispielsweise in der EP-A-167 205 oder US-4 507 219 oder GB 8712430 beschrieben werden, zu verstehen.Liquid detergents are understood to mean known and commercially available detergents such as are described, for example, in EP-A-167 205 or US-4,507,219 or GB 8712430.

Der Gehalt an optischem Aufheller in den flüssigen Waschmitteln beträgt 0,01-2 %, insbesondere 0,01-1 %, besonders bevorzugt 0,03-0,3 %.The optical brightener content in the liquid detergents is 0.01-2%, in particular 0.01-1%, particularly preferably 0.03-0.3%.

Insbesondere enthalten die Flüssigwaschmittel neben den optischen Aufhellern 1 bis 60 anionische, nichtionische, zwitterionische und gegebenenfalls kationische Tenside und 25 bis 65 % vorzugsweise 40 bis 55 % Wasser. Im einzelnen enthält das Waschmittel neben dem optischen Aufheller 3 bis 50 % vorzugsweise 15 bis 25 % anionische Tenside, 2 bis 30 % vorzugsweise 4 bis 15 % nichtionische Tenside, 3 bis 30 % vorzugsweise 5 bis 20 % gegebenenfalls ethoxylierte (C₁₀-C₁₄)-Fettsäuren wie Kaprin-, Laurin-, Myristin-, Kokusnuss- und Palmkernsäure sowie Mischungen davon, 1 bis 25 % vorzugsweise 1 bis 10 % Waschmittelauf­baustoffe sowie gegebenenfalls 1 bis 10% vorzugsweise 1 bis 5 % zwitter­ionische Tenside, 0,5 bis 3 % vorzugsweise 0,7 bis 2 % quaternäre Ammonium-, Amin- oder Aminoxid-Tenside, und 1 bis 10 % übliche Wasch­mittelzusätze wie zum Beispiel Enzyme, Enzymstabilisatoren, Anti­oxidantien, Konservierungs- und Desinfektionsmittel, Duft- und Farb­stoffe, Komplexbildner bzw. Sequestriermittel und Lösungsmittel.In particular, in addition to the optical brighteners, the liquid detergents contain 1 to 60 anionic, nonionic, zwitterionic and optionally cationic surfactants and 25 to 65%, preferably 40 to 55%, water. In particular, in addition to the optical brightener, the detergent contains 3 to 50% preferably 15 to 25% anionic surfactants, 2 to 30% preferably 4 to 15% nonionic surfactants, 3 to 30% preferably 5 to 20% optionally ethoxylated (C₁₀-C₁₄) - Fatty acids such as capric, lauric, myristic, coconut and palm kernel acid and mixtures thereof, 1 to 25% preferably 1 to 10% detergent builders and optionally 1 to 10% preferably 1 to 5% zwitterionic surfactants, 0.5 to 3% preferably 0.7 to 2% quaternary ammonium, amine or amine oxide surfactants, and 1 to 10% common detergent additives such as enzymes, enzyme stabilizers, antioxidants, preservatives and disinfectants, fragrances and dyes, complexing agents or sequestering agents and solvents.

Brauchbare Tenside werden z.B. in der US-4 285 841, US-3 929 678, US-4 284 532 und GB-2 041 986 beschrieben. Insbesondere werden die in der EP-A-167 205 als bevorzugt bezeichneten Tenside eingesetzt. Vor allem verwendet man jedoch als anionische Tenside gegebenenfalls ethoxylierte C₁₀-C₁₈-Alkylsulfate z.B. in Form der Triethanolaminsalze, C₁₀-C₁₅-Alkyl­benzolsulfonate oder Mischungen davon und als nichtionische Tenside Kondensationsprodukte aus einem Mol (C₁₀-C₁₅)-Fettalkohol mit 3 bis 8 Mol Ethylenoxid.Useful surfactants are described, for example, in U.S. 4,285,841, U.S. 3,929,678, U.S. 4,284,532 and GB 2,041,986. In particular, the surfactants designated as preferred in EP-A-167 205 are used. Above all, however, optionally used as anionic surfactants are ethoxylated C₁ate-C₁₈ alkyl sulfates, for example in the form of the triethanolamine salts, C₁₀-C₁₅ alkylbenzenesulfonates or mixtures thereof and as nonionic surfactants, condensation products from one mole of (C₁₀-C₁₅) fatty alcohol with 3 to 8 moles of ethylene oxide .

Als Waschmittelaufbaustoffe kommen die in der US-4 321 165 und US-4 284 532 erwähnten vorzugsweise polycarboxylierte Verbindungen wie zum Beispiel Zitronensäure in Betracht.Suitable detergent builders are the preferably polycarboxylated compounds mentioned in US Pat. Nos. 4,321,165 and 4,284,532, such as citric acid.

Gezielt sulfonierte Dibenzofuranylbiphenyle enthaltende flüssige Wasch­mittel können auch, wie z.B. in GB 8712430 beschrieben, Bleichmittel enthalten. Als Bleichmittel wird vorzugsweise Perborat verwendet.Targeted liquid detergents containing sulfonated dibenzofuranylbiphenyls can also be used e.g. in GB 8712430, contain bleach. Perborate is preferably used as the bleaching agent.

Die folgenden Beispiele dienen zur Erläuterung der Erfindung; Teile bedeuten Gewichtsteile und Prozente Gewichtsprozente; der Fleckentest wird folgendermassen durchgeführt:

  • a) Aufheller/Waschmittel-Formulierung:
    0,1 % (100 % Aktivsubstanz) optischer Aufheller oder Aufhellergemisch werden in einem flüssigen Waschmittel gelöst. 0,6 g dieses Aufheller enthaltenden Waschmittels (A) wird mit 400 ml Wasser (10°-12° dH) bei einer Temperatur von 30°C verdünnt (Waschflotte B).
  • b) Ein 20 g Stück gebleichtes Baumwollgewebe wird auf einem Spannrahmen befestigt.
  • c) Auf eine vormarkierte, runde Fläche (5 cm Durchmesser) dieses Baum­wollgewebes werden mit einer Pipette 0,6 ml der Waschmittellösung (A) gleichmässig aufgetragen, nach 30 Sekunden Einwirkzeit in die vor­bereitete Waschflotte (B) gegeben und während 15 Minuten bei 30°C gewaschen. Anschliessend wird mit kaltem Wasser gespült und bei 70°C getrocknet.
  • d) Der Unterschied des Weissgrades nach Ganz zwischen der Auftragsfläche und der Umgebung ist ein Mass für das sogenannte Spotting-Verhalten (Bildung von hellen Flecken) und wird bei einfacher Textillage mit einem RFC3-Photometer von Zeiss bestimmt.
The following examples serve to illustrate the invention; Parts mean parts by weight and percentages percentages by weight; The stain test is carried out as follows:
  • a) Brightener / detergent formulation:
    0.1% (100% active substance) optical brightener or brightener mixture are dissolved in a liquid detergent. 0.6 g of this detergent (A) containing brightener is diluted with 400 ml of water (10 ° -12 ° dH) at a temperature of 30 ° C (wash liquor B).
  • b) A 20 g piece of bleached cotton fabric is attached to a tenter.
  • c) 0.6 ml of the detergent solution (A) are evenly applied to a pre-marked, round surface (5 cm in diameter) of this cotton fabric, added to the prepared wash liquor (B) after 30 seconds of exposure and for 15 minutes at 30 ° C washed. It is then rinsed with cold water and dried at 70 ° C.
  • d) The difference in whiteness according to Ganz between the application area and the surroundings is a measure of the so-called spotting behavior (formation of light spots) and is determined with a simple textile layer using an RFC3 photometer from Zeiss.

Beispiel 1: Example 1 :

Man stellt ein flüssiges Waschmittel enthaltend
15 Teile C₁₁-C₁₃ Alkylbenzolsulfonat
14 Teile C₁₄-C₁₅ Polyethoxyfettalkohol (7 Ethylenoxid)
10 Teile Seife
9 Teile Ethanol
5 Teile Triethanolamin
4 Teile Na-Citrat
43 Teile Wasser
und 0,1 Teile des optischen Aufhellers der Formel

Figure imgb0007
her.A liquid detergent is prepared
15 parts of C₁₁-C₁₃ alkylbenzenesulfonate
14 parts of C₁₄-C₁₅ polyethoxy fatty alcohol (7 ethylene oxide)
10 parts of soap
9 parts of ethanol
5 parts of triethanolamine
4 parts Na citrate
43 parts of water
and 0.1 part of the optical brightener of the formula
Figure imgb0007
 forth.

Der Fleckentest zeigt nur eine sehr geringe Bildung heller Flecken, bei sehr hohem Aufhellgrad.The stain test shows only a very slight formation of light stains with a very high degree of lightening.

Die Waschmittelformulierung ist lagerstabil.The detergent formulation is stable on storage.

Beispiel 2: Example 2 :

Wie im Beispiel 1 wird ein flüssiges Waschmittel hergestellt, welches jedoch anstelle der Verbindung (100) die Verbindung der Formel

Figure imgb0008
enthält.As in Example 1, a liquid detergent is prepared, but instead of compound (100) the compound of the formula
Figure imgb0008
 contains.

Das flüssige Waschmittel entspricht in seinen Eigenschaften demjenigen aus Beispiel 1.The properties of the liquid detergent correspond to those from Example 1.

Beispiel 3: Example 3 :

Wie im Beispiel 1 wird ein flüssiges Waschmittel hergestellt, welches jedoch anstelle der Verbindung (100) die Verbindung der Formel

Figure imgb0009
enthält.As in Example 1, a liquid detergent is prepared, but instead of compound (100) the compound of the formula
Figure imgb0009
 contains.

Das flüssige Waschmittel entspricht in seinen Eigenschaften demjenigen aus Beispiel 1.The properties of the liquid detergent correspond to those from Example 1.

Beispiel 4: Example 4 :

Wie im Beispiel 1 wird ein flüssiges Waschmittel hergestellt, welches jedoch anstelle der Verbindung (100) die Verbindung der Formel

Figure imgb0010
enthält.As in Example 1, a liquid detergent is prepared, but instead of compound (100) the compound of the formula
Figure imgb0010
 contains.

Die Waschmittelformulierung ist sehr lagerstabil. Der Fleckentest zeigt nur eine sehr schwache Bildung heller Flecken.The detergent formulation is very stable in storage. The stain test shows only a very weak formation of light spots.

Beispiel 5: Example 5 :

Wie im Beispiel 1 wird ein flüssiges Waschmittel hergestellt, welches jedoch anstelle der Verbindung (100) die Verbindung der Formel

Figure imgb0011
enthält.As in Example 1, a liquid detergent is prepared, but instead of compound (100) the compound of the formula
Figure imgb0011
 contains.

Die Waschmittelformulierung ist sehr lagerstabil. Der Fleckentest zeigt eine nur geringe Bildung heller Flecken, bei hohen Aufhelleffekten.The detergent formulation is very stable in storage. The stain test shows only a slight formation of light stains with high lightening effects.

Beispiel 6:Example 6:

Man stellt ein flüssiges Waschmittel enthaltend
6.5 Teile Triethanolamin
3.5 Teile NaOH
6.5 Teile Ethanol
1.5 Teile 1,2 Propandiol
11.5 Teile C₁₄-C₁₅ Polyethoxyfettalkohol (7 Ethylenoxid)
2.5 Teile Coconutalkylsulfat
10.5 Teile Lineare Dodecylbenzolsulfonsäure
4.0 Teile Oelsäure
10.5 Teile Gesättigte C₁₂-C₁₄ säure
43.0 Teile Deionisiertes Wasser
und 0.1 Teile des optischen Aufhellers der Formel

Figure imgb0012
her.A liquid detergent is prepared
6.5 parts of triethanolamine
3.5 parts NaOH
6.5 parts of ethanol
1.5 parts of 1,2 propanediol
11.5 parts of C₁₄-C₁₅ polyethoxy fatty alcohol (7 ethylene oxide)
2.5 parts of coconut alkyl sulfate
10.5 parts of linear dodecylbenzenesulfonic acid
4.0 parts of oleic acid
10.5 parts of saturated C₁₂-C₁₄ acid
43.0 parts of deionized water
and 0.1 part of the optical brightener of the formula
Figure imgb0012
 forth.

Das Waschmittel ist opak, homogen und sehr lagerstabil. Der Fleckentest zeigt nur eine sehr geringe Bildung heller Flecken, bei sehr hohem Aufhellgrad.The detergent is opaque, homogeneous and very stable in storage. The stain test shows only a very slight formation of light stains with a very high degree of lightening.

Beispiel 7: Example 7 :

Wie im Beispiel 6 wird ein flüssiges Waschmittel hergestellt, welches jedoch anstelle der Verbindung (200) die Verbindung der Formel

Figure imgb0013
enthält.As in Example 6, a liquid detergent is prepared, but instead of the compound (200) the compound of the formula
Figure imgb0013
 contains.

Das flüssige Waschmittel entspricht in seinen Eigenschaften demjenigen aus Beispiel 6.The properties of the liquid detergent correspond to those from Example 6.

Claims (10)

1. Flüssigwaschmittel enthaltend optische Aufheller, dadurch gekenn­zeichnet, dass die in einer Menge von 0,01 bis 2 %, bezogen auf das Gewicht des Waschmittels, vorliegenden optischen Aufheller der Formel
Figure imgb0014
 entsprechen, worin X ein Sulfonsäurerest, Wasserstoff oder C₁-C₄-Alkyl, Y und Z unabhängig voneinander ein Sulfonsäurerest, Wasserstoff, C₁-C₄-Alkyl, C₁-C₄-Alkoxy, Halogen, CN, Phenoxy, Benzyloxy, mit der Bedingung, dass entweder X oder Y oder Z ein Sulfonsäurerest ist und die restlichen Substituenten nicht ein Sulfonsäurerest sind, bedeuten.1. Liquid detergent containing optical brighteners, characterized in that the optical brighteners of the formula present in an amount of 0.01 to 2%, based on the weight of the detergent
Figure imgb0014
 correspond in which X is a sulfonic acid radical, hydrogen or C₁-C₄-alkyl, Y and Z independently of one another a sulfonic acid radical, hydrogen, C₁-C₄-alkyl, C₁-C₄-alkoxy, halogen, CN, phenoxy, benzyloxy, with the condition that either X or Y or Z is a sulfonic acid residue and the remaining substituents are not a sulfonic acid residue. 2. Flüssigwaschmittel gemäss Anspruch 1, dadurch gekennzeichnet, dass das Flüssigwaschmittel einen optischen Aufheller der Formel
Figure imgb0015
 worin
R₁ = Wasserstoff, C₁-C₄-Alkyl, Chlor, C₁-C₄-Alkoxy, Phenoxy oder Benzyl­oxy, R₂ = Wasserstoff oder C₁-C₄-Alkyl und M = Wasserstoff und/oder ein Aequivalent eines nicht chromophoren Kations bedeuten, enthält.2. Liquid detergent according to claim 1, characterized in that the liquid detergent is an optical brightener of the formula
Figure imgb0015
 wherein
R₁ = hydrogen, C₁-C₄-alkyl, chlorine, C₁-C₄-alkoxy, phenoxy or benzyloxy, R₂ = hydrogen or C₁-C₄-alkyl and M = hydrogen and / or an equivalent of a non-chromophoric cation. 3. Flüssigwaschmittel gemäss Anspruch 1, dadurch gekennzeichnet, dass das Flüssigwaschmittel einen optischen Aufheller der Formel
Figure imgb0016
 worin R₃ unabhängig voneinander für Wasserstoff, Methyl oder Ethyl steht und M vorzugsweise Natrium oder Kalium ist enthält.3. Liquid detergent according to claim 1, characterized in that the liquid detergent is an optical brightener of the formula
Figure imgb0016
 wherein R₃ is independently hydrogen, methyl or ethyl and M preferably contains sodium or potassium. 4. Flüssigwaschmittel gemäss Anspruch 1, dadurch gekennzeichnet, dass das Flüssigwaschmittel einen optischen Aufheller der Formel
Figure imgb0017
 enthält.4. Liquid detergent according to claim 1, characterized in that the liquid detergent is an optical brightener of the formula
Figure imgb0017
 contains. 5. Flüssigwaschmittel gemäss Anspruch 1, dadurch gekennzeichnet, dass das Flüssigwaschmittel einen optischen Aufheller der Formel
Figure imgb0018
 enthält.5. Liquid detergent according to claim 1, characterized in that the liquid detergent is an optical brightener of the formula
Figure imgb0018
 contains. 6. Flüssigwaschmittel gemäss Anspruch 1, dadurch gekennzeichnet, dass das Flüssigwaschmittel einen optischen Aufheller der Formel
Figure imgb0019
 enthält.6. Liquid detergent according to claim 1, characterized in that the liquid detergent is an optical brightener of the formula
Figure imgb0019
 contains. 7. Flüssigwaschmittel gemäss Anspruch 1, dadurch gekennzeichnet, dass das Flüssigwaschmittel einen optischen Aufheller der Formel
Figure imgb0020
 enthält,7. Liquid detergent according to claim 1, characterized in that the liquid detergent is an optical brightener of the formula
Figure imgb0020
 contains 8. Flüssigwaschmittel gemäss Anspruch 1, dadurch gekennzeichnet, dass das Flüssigwaschmittel einen optischen Aufheller der Formel
Figure imgb0021
 enthält,8. Liquid detergent according to claim 1, characterized in that the liquid detergent is an optical brightener of the formula
Figure imgb0021
 contains 9. Verwendung der Flüssigwaschmittel gemäss einem der Ansprüche 1-8 zum Waschen und Vorbehandeln von textilen Geweben.9. Use of the liquid detergent according to one of claims 1-8 for washing and pretreating textile fabrics. 10. Herstellung der Flüssigwaschmittel gemäss einem der Ansprüche 1-8 durch Mischen und Homogenisieren von optischem Aufheller, Tensiden, Hilfs- und Aufbaustoffen, gegebenenfalls einem Bleichsystem, und Wasser.10. Production of the liquid detergent according to any one of claims 1-8 by mixing and homogenizing optical brighteners, surfactants, auxiliaries and builders, optionally a bleaching system, and water.
EP90107835A 1989-04-28 1990-04-25 Liquid detergent Expired - Lifetime EP0394998B1 (en)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
CH163089 1989-04-28
CH1630/89 1989-04-28

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EP0394998A3 EP0394998A3 (en) 1991-01-09
EP0394998B1 EP0394998B1 (en) 1996-03-27

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AU (1) AU628539B2 (en)
CA (1) CA2015565A1 (en)
DE (1) DE59010228D1 (en)
ES (1) ES2085296T3 (en)
NZ (1) NZ233443A (en)

Cited By (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0548019A2 (en) * 1991-12-19 1993-06-23 Ciba-Geigy Ag Storage-stable bleach dispersion
WO1994011485A1 (en) * 1992-11-17 1994-05-26 Unilever N.V. Liquid detergent compositions
EP0601967A1 (en) * 1992-11-17 1994-06-15 Ciba-Geigy Ag Liquid detergent composition
US5604194A (en) * 1992-11-17 1997-02-18 The Procter & Gamble Company Stable liquid detergent compositions comprising specific brightener and PVP to inhibit dye transfer
DE19859575B4 (en) * 1997-12-30 2011-12-22 Kay Chemical Co. Soaking agent with optical brightener

Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4002423A (en) * 1971-08-13 1977-01-11 Hoechst Aktiengesellschaft Benzofuran derivatives process for their preparation and their use as optical brighteners
DE2843850A1 (en) * 1978-10-07 1980-05-22 Bayer Ag DYE LASER
EP0321715A2 (en) * 1987-12-23 1989-06-28 Ciba-Geigy Ag Stable detergents containing optical brighteners
DE3900651A1 (en) * 1988-01-14 1989-07-27 Ciba Geigy Ag Stable bleaching composition containing optical brighteners
EP0364027A2 (en) * 1988-10-14 1990-04-18 Unilever N.V. Bleaching and detergent composition

Family Cites Families (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
ES2065328T3 (en) * 1987-11-26 1995-02-16 Ciba Geigy Ag STABLE DETERGENTS CONTAINING OPTIC BLEACHES.

Patent Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4002423A (en) * 1971-08-13 1977-01-11 Hoechst Aktiengesellschaft Benzofuran derivatives process for their preparation and their use as optical brighteners
DE2843850A1 (en) * 1978-10-07 1980-05-22 Bayer Ag DYE LASER
EP0321715A2 (en) * 1987-12-23 1989-06-28 Ciba-Geigy Ag Stable detergents containing optical brighteners
DE3900651A1 (en) * 1988-01-14 1989-07-27 Ciba Geigy Ag Stable bleaching composition containing optical brighteners
EP0364027A2 (en) * 1988-10-14 1990-04-18 Unilever N.V. Bleaching and detergent composition

Cited By (9)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0548019A2 (en) * 1991-12-19 1993-06-23 Ciba-Geigy Ag Storage-stable bleach dispersion
EP0548019A3 (en) * 1991-12-19 1995-06-14 Ciba Geigy Ag Storage-stable bleach dispersion
WO1994011485A1 (en) * 1992-11-17 1994-05-26 Unilever N.V. Liquid detergent compositions
EP0601967A1 (en) * 1992-11-17 1994-06-15 Ciba-Geigy Ag Liquid detergent composition
EP0672099A4 (en) * 1992-11-17 1995-08-03 Procter & Gamble Stable liquid detergent compositions inhibiting dye transfer.
EP0672099A1 (en) * 1992-11-17 1995-09-20 Procter & Gamble Stable liquid detergent compositions inhibiting dye transfer.
US5468884A (en) * 1992-11-17 1995-11-21 Ciba-Geigy Corporation Liquid detergent compositions
US5604194A (en) * 1992-11-17 1997-02-18 The Procter & Gamble Company Stable liquid detergent compositions comprising specific brightener and PVP to inhibit dye transfer
DE19859575B4 (en) * 1997-12-30 2011-12-22 Kay Chemical Co. Soaking agent with optical brightener

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JP2685329B2 (en) 1997-12-03
AU5453690A (en) 1990-11-01
ES2085296T3 (en) 1996-06-01
NZ233443A (en) 1992-04-28
DE59010228D1 (en) 1996-05-02
JPH02302498A (en) 1990-12-14
CA2015565A1 (en) 1990-10-28
EP0394998B1 (en) 1996-03-27
EP0394998A3 (en) 1991-01-09

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