EP0394998B1 - Liquid detergent - Google Patents
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- EP0394998B1 EP0394998B1 EP90107835A EP90107835A EP0394998B1 EP 0394998 B1 EP0394998 B1 EP 0394998B1 EP 90107835 A EP90107835 A EP 90107835A EP 90107835 A EP90107835 A EP 90107835A EP 0394998 B1 EP0394998 B1 EP 0394998B1
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- liquid detergent
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- detergent composition
- fluorescent whitening
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- 0 C*1=CCCC1 Chemical compound C*1=CCCC1 0.000 description 4
Classifications
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- C—CHEMISTRY; METALLURGY
- C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
- C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
- C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
- C11D3/40—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.
- This effect is also responsible for the appearance of light spots when textile fabrics e.g. comes into contact with the liquid detergent during pretreatment.
- EP-A-167 205 proposes to use monosulfonated stilbene triazolyl, triazine or distyrylbiphenyl brighteners in anionic liquid detergents.
- EP-A-364 027 discloses liquid bleaching agents and detergents which contain sulfonated benzofuranylbiphenyl brighteners
- EP-A-321 715 describes stable detergents which contain sulfonated benzofuranylbiphenyl brighteners
- US-A-4 002 423 discloses new sulfonated benzofuranylbiphenyl compounds which can be used as brighteners, particularly in detergents.
- none of these disclosures disclose liquid detergents which contain sulfonated benzofuranylbiphenyl brighteners with a C1-C4-alkyl substituent in the fur portion of the benzofuranylbiphenyl molecule.
- X is C1-C4-alkyl
- Y and Z independently of one another are a sulfonic acid residue, hydrogen, C1-C4-alkyl, C1-C4-alkoxy, halogen, CN, phenoxy, benzyloxy, with the condition that either 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 methyl or ethyl and M is preferably sodium or potassium.
- Process (a) in particular produces the compounds of the formula (III).
- SO3 / base complex Under SO3 / base complex are addition compounds of SO3 to organic bases, e.g. Dioxane, preferably nitrogen-containing bases, such as triethylamine, N-ethyldiisopropylamine, dimethylformamide (DMF) and in particular pyridine.
- 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 such as mono, chlorobenzenes such as chlorobenzene, nitrobenzene, chlorobenzene such as chlorobenzene, chlorobenzenes such as chlorobenzene and nitrobenzene, such as chlorobenzene and chlorobenzene, such as chlorobenzene and chlorobenzene, such as chlorobenzene and chlorobenzene, such as chlorobenzene and chlorobenzene, such as chlorobenzene and monobenzene, such as
- 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 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 at least stoichiometric Amounts, preferably in excess, are used. It is advantageous to work in the absence of atmospheric oxygen and an inert gas atmosphere.
- 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% customary detergent additives such as, for example, enzymes, enzyme stabilizers, antioxidants, preservatives and disinfectants, fragrances and colorants, complexing agents or se
- customary detergent additives such as, for example, enzymes, enzyme stabilizers,
- Useful surfactants are e.g. 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.
- the anionic surfactants used are optionally ethoxylated C1 z.B.-C18 alkyl sulfates, e.g. in the form of the triethanolamine salts, C10-C15 alkylbenzenesulfonates or mixtures thereof and as nonionic surfactants condensation products from one mole (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.
- 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 2 As in Example 1, a liquid detergent is prepared, but instead of the compound (200) the compound of the formula
- the properties of the liquid detergent correspond to those of Example 1.
- Example 3 As in Example 1, a liquid detergent is prepared, but instead of the compound (200) the compound of the formula
- the detergent formulation is very stable in storage.
- the stain test shows only a very weak formation of light stains.
- Example 4 As in Example 1, a liquid detergent is prepared, but instead of the compound (200) the compound of the formula
- the detergent formulation is very stable in storage.
- the stain test shows only a slight formation of light stains with high lightening effects.
- 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 As in Example 5, a liquid detergent is prepared, but instead of the compound (200) the compound of the formula
- the properties of the liquid detergent correspond to those from Example 5.
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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.This effect is also responsible for the appearance of light spots when textile fabrics e.g. comes into contact with the liquid detergent during pretreatment.
ln der EP-A-167 205 wird zur Lösung dieses Problems vorgeschlagen, monosulfonierte Stilbentriazolyl-, -triazin- oder Distyrylbiphenyl-Aufheller in anionischen Flüssigwaschmitteln zu verwenden.To solve this problem, EP-A-167 205 proposes to use monosulfonated stilbene triazolyl, triazine or distyrylbiphenyl brighteners in anionic liquid detergents.
Ausserdem sind in der EP-A-364 027 flüssige Bleich- und Waschmittel offenbart, die sulfonierte Benzofuranylbiphenyl-Aufheller enthalten; in der EP-A-321 715 sind stabile Waschmittel beschrieben, die sulfonierte Benzofuranylbiphenyl-Aufheller enthalten; und in der US-A-4 002 423 sind neue sulfonierte Benzofuranylbiphenyl-Verbindungen offenbart, die Verwendung als Aufheller, insbesondere in Waschmitteln finden können. In keiner dieser Offenbarungen aber sind flüssige Waschmittel offenbart, die sulfonierte Benzofuranylbiphenyl-Aufheller mit einem C₁-C₄-Alkyl Substituent in dem Furanteil des Benzofuranylbiphenylmoleküls enthalten.In addition, EP-A-364 027 discloses liquid bleaching agents and detergents which contain sulfonated benzofuranylbiphenyl brighteners; EP-A-321 715 describes stable detergents which contain sulfonated benzofuranylbiphenyl brighteners; and US-A-4 002 423 discloses new sulfonated benzofuranylbiphenyl compounds which can be used as brighteners, particularly in detergents. However, none of these disclosures disclose liquid detergents which contain sulfonated benzofuranylbiphenyl brighteners with a C₁-C₄-alkyl substituent in the fur portion of the benzofuranylbiphenyl molecule.
Ueberraschenderweise kann die Bildung heller Flecken, bei ausgezeichneter Aufhellwirkung und sehr gutem Lagerverhalten des flüssigen Waschmittels, auch durch optische Aufheller der Formel
Im einzelnen bedeutet: X 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 Y oder Z ein Sulfonsäurerest ist und die restlichen Substituenten nicht ein Sulfonsäurerest sind.Specifically: X is C₁-C₄-alkyl, Y and Z independently of one another are a sulfonic acid residue, hydrogen, C₁-C₄-alkyl, C₁-C₄-alkoxy, halogen, CN, phenoxy, benzyloxy, with the condition that either 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 (I) sind solche der Formel
- R₁ = Wasserstoff, C₁-C₄-Alkyl, Chlor, C₁-C₄-Alkoxy, Phenoxy oder Benzyloxy,
- R₂ = C₁-C₄-Alkyl und M = Wasserstoff und/oder ein Aequivalent eines nicht chromophoren Kations bedeuten.
- R₁ = hydrogen, C₁-C₄-alkyl, chlorine, C₁-C₄-alkoxy, phenoxy or benzyloxy,
- R₂ = 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
Die optischen Aufheller können hergestellt werden, indem man
- a) ein Mol der Verbindung der Formel (X)
- 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)
- a) one mole of the compound of formula (X)
- b) reacting a 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)
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).
Nach dem Verfahren (a) werden insbesondere die Verbindungen der Formel (III) hergestellt.Process (a) in particular produces the compounds of the formula (III).
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) 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).Under SO₃ / base complex are addition compounds of SO₃ to organic bases, e.g. 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 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). 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 such as mono, chlorobenzenes such as chlorobenzene, nitrobenzene, chlorobenzene such as chlorobenzene, chlorobenzenes such as chlorobenzene and nitrobenzene, such as chlorobenzene and chlorobenzene, such as chlorobenzene and chlorobenzene, such as chlorobenzene and chlorobenzene, such as chlorobenzene and monobenzene, such as chlorobenzene and chlorobenzene 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 (III) hergestellt.In particular, the compounds of the formulas (II) and (III) 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 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 at least stoichiometric Amounts, preferably in excess, are used. 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 (=EP-A-293 040) beschrieben werden, zu verstehen.Liquid detergents are known and commercially available detergents, as are described, for example, in EP-A-167 205 or US-4 507 219 or GB 8712430 (= EP-A-293 040).
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 Farb- stoffe, 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% customary detergent additives such as, for example, enzymes, enzyme stabilizers, antioxidants, preservatives and disinfectants, fragrances and colorants, complexing agents or sequestering agents and Solvent.
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 e.g. 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, the anionic surfactants used are optionally ethoxylated C₁ z.B.-C₁₈ alkyl sulfates, e.g. in the form of the triethanolamine salts, C₁₀-C₁₅ alkylbenzenesulfonates or mixtures thereof and as nonionic surfactants condensation products from one mole (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 (=EP-A-293 040) beschrieben, Bleichmittel enthalten. Als Bleichmittel wird vorzugsweise Perborat verwendet.Targeted liquid detergents containing sulfonated dibenzofuranylbiphenyls can also be used e.g. in GB 8712430 (= EP-A-293 040), contain bleaching agents. 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.
- 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 area (5 cm 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.
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
- 15
- Parts of C₁₁-C₁₃ alkylbenzenesulfonate
- 14
- Parts of C₁₄-C₁₅ polyethoxy fatty alcohol (7 ethylene oxide)
- 10th
- Parts of soap
- 9
- Parts of ethanol
- 5
- Parts of triethanolamine
- 4th
- Parts of Na citrate
- 43
- Parts of water
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.
Das flüssige Waschmittel entspricht in seinen Eigenschaften demjenigen aus Beispiel 1.The properties of the liquid detergent correspond to those of Example 1.
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 stains.
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.
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
- 6.5
- Parts of triethanolamine
- 3.5
- Parts of NaOH
- 6.5
- Parts of ethanol
- 1.5
- Parts 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
- Parts of the optical brightener of the formula
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.
Das flüssige Waschmittel entspricht in seinen Eigenschaften demjenigen aus Beispiel 5.The properties of the liquid detergent correspond to those from Example 5.
Claims (9)
- A liquid detergent composition comprising a sulfonated dibenzofuranylbiphenyl as fluorescent whitening agent, wherein the fluorescent whitening agent present in an amount of 0.01 to 2%, based on the weight of the detergent composition, has the formula
- A liquid detergent composition according to claim 1 which contains a fluorescent whitening agent of the formula
- A liquid detergent composition according to claim 1 which contains a fluorescent whitening agent of the formula
- A liquid detergent composition according to claim 1 which contains a fluorescent whitening agent of the formula
- A liquid detergent composition according to claim 1 which contains a fluorescent whitening agent of the formula
- A liquid detergent composition according to claim 1 which contains a fluorescent whitening agent of the formula
- A liquid detergent composition according to claim 1 which contains a fluorescent whitening agent of the formula
- Use of a liquid detergent composition according to any one of claims 1-7 for washing and pretreating textile fabrics.
- Preparation of a liquid detergent composition according to any one of claims 1-7 by mixing and homogenizing fluorescent whitening agents, surfactants, auxiliaries and builders, if desired a bleaching system, and water.
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CH163089 | 1989-04-28 | ||
| CH1630/89 | 1989-04-28 |
Publications (3)
| Publication Number | Publication Date |
|---|---|
| EP0394998A2 EP0394998A2 (en) | 1990-10-31 |
| EP0394998A3 EP0394998A3 (en) | 1991-01-09 |
| EP0394998B1 true EP0394998B1 (en) | 1996-03-27 |
Family
ID=4214937
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| EP90107835A Expired - Lifetime EP0394998B1 (en) | 1989-04-28 | 1990-04-25 | Liquid detergent |
Country Status (7)
| Country | Link |
|---|---|
| EP (1) | EP0394998B1 (en) |
| JP (1) | JP2685329B2 (en) |
| AU (1) | AU628539B2 (en) |
| CA (1) | CA2015565A1 (en) |
| DE (1) | DE59010228D1 (en) |
| ES (1) | ES2085296T3 (en) |
| NZ (1) | NZ233443A (en) |
Families Citing this family (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| MX9207050A (en) * | 1991-12-19 | 1993-06-01 | Ciba Geigy Ag | STABLE BLEACH DISPERSION DURING STORAGE |
| CH684485A5 (en) * | 1992-11-17 | 1994-09-30 | Ciba Geigy Ag | Liquid detergent. |
| GB9224052D0 (en) * | 1992-11-17 | 1993-01-06 | Unilever Plc | Non aqueous 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 |
| US6099589A (en) * | 1997-12-30 | 2000-08-08 | Kay Chemical Company | Presoak detergent with optical brightener |
Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP0364027A2 (en) * | 1988-10-14 | 1990-04-18 | Unilever N.V. | Bleaching and detergent composition |
Family Cites Families (5)
| 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 |
| DE2843850C2 (en) * | 1978-10-07 | 1987-02-12 | Bayer Ag, 5090 Leverkusen | Dye laser |
| ES2065328T3 (en) * | 1987-11-26 | 1995-02-16 | Ciba Geigy Ag | STABLE DETERGENTS CONTAINING OPTIC BLEACHES. |
| ES2054775T3 (en) * | 1987-12-23 | 1994-08-16 | Ciba Geigy Ag | STABLE DETERGENTS CONTAINING OPTIC BLEACHES. |
| CH678585B5 (en) * | 1988-01-14 | 1992-04-15 | Ciba Geigy Ag |
-
1990
- 1990-04-25 EP EP90107835A patent/EP0394998B1/en not_active Expired - Lifetime
- 1990-04-25 DE DE59010228T patent/DE59010228D1/en not_active Expired - Fee Related
- 1990-04-25 ES ES90107835T patent/ES2085296T3/en not_active Expired - Lifetime
- 1990-04-26 CA CA 2015565 patent/CA2015565A1/en not_active Abandoned
- 1990-04-26 NZ NZ23344390A patent/NZ233443A/en unknown
- 1990-04-27 JP JP2115021A patent/JP2685329B2/en not_active Expired - Lifetime
- 1990-04-27 AU AU54536/90A patent/AU628539B2/en not_active Ceased
Patent Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP0364027A2 (en) * | 1988-10-14 | 1990-04-18 | Unilever N.V. | Bleaching and detergent composition |
Also Published As
| Publication number | Publication date |
|---|---|
| JP2685329B2 (en) | 1997-12-03 |
| AU5453690A (en) | 1990-11-01 |
| EP0394998A2 (en) | 1990-10-31 |
| DE59010228D1 (en) | 1996-05-02 |
| CA2015565A1 (en) | 1990-10-28 |
| JPH02302498A (en) | 1990-12-14 |
| NZ233443A (en) | 1992-04-28 |
| AU628539B2 (en) | 1992-09-17 |
| EP0394998A3 (en) | 1991-01-09 |
| ES2085296T3 (en) | 1996-06-01 |
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