EP0334372B1 - Liquid, anionic storage-stable detergents containing amphoteric distyryl derivatives - Google Patents
Liquid, anionic storage-stable detergents containing amphoteric distyryl derivatives Download PDFInfo
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- EP0334372B1 EP0334372B1 EP89105275A EP89105275A EP0334372B1 EP 0334372 B1 EP0334372 B1 EP 0334372B1 EP 89105275 A EP89105275 A EP 89105275A EP 89105275 A EP89105275 A EP 89105275A EP 0334372 B1 EP0334372 B1 EP 0334372B1
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- detergent composition
- fluorescent whitening
- anionic
- distyryl
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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 application relates to storage-stable anionic liquid detergents which contain amphoteric distyryl derivatives as optical brighteners and anionic surfactants.
- optical brighteners in liquid detergents is known. They soak on the items to be washed during treatment and, thanks 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.
- amphoteric brighteners in cationic liquid detergents is known (EP-A-59684), the use of amphoteric brighteners in anionic liquid detergents has not been described to date.
- amphoteric distyre brighteners can also be incorporated into anionic, liquid detergents and that the formation of light spots combined with excellent brightening effect and detergent stability can be prevented.
- Amphoteric distyryl brighteners of the formula (III) are preferably used, wherein R1, R2, R3 ', Y1, Y2, Q and n have the meaning given above and, above all, but amphoteric Distyrylaufleller of formula (IV) wherein y1 'C1-C4 alkylene means and R1, R2 and n have the meaning given above, for example the compound of the formula (V)
- amphoteric distyryl brighteners of the formulas (I) to (V) are known and can be prepared by known methods (see, for example, EP-A-59 684).
- Anionic liquid detergents are known and commercially available detergents with an overall anionic character, as are described, for example, in EP-A-167 205 or US Pat. No. 4,507,219.
- the liquid detergents contain nonionic and zwitterionic surfactants and optionally small amounts of 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-C22) - Fatty acids, in particular saturated (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 enzymes, enzyme stabilizers, antioxidants, preservatives and disinfectants, fragrances and dyes, complexing agents or sequestering agents and solvents.
- customary detergent additives such as enzymes, enzyme stabilizers, antioxidants, preservatives and disinfectants, fragrances and dyes, complexing agents or sequestering agents and solvents.
- Anionic surfactants used are, for example, water-soluble salts of alkyl and / or aryl group-containing organic sulfur compounds, sulfonic acids or sulfonic acid esters with 10 to 20 carbon atoms in the alkyl group, such as alkyl sulfates, preferably those obtained by sulfating higher alcohols (10-18 carbon atoms ) linear or branched alkylbenzenesulfonates with 9 to 15 carbon atoms in the alkyl groups, preferably linear alkylbenzenesulfonates with 11 to 14 carbon atoms in the alkyl groups, paraffin sulfonates with 8 to 24, preferably 12 to 18 carbon atoms, alkylglyceryl ether sulfonates with 8 to 18 C atoms, alkylphenol
- the nonionic surfactants used are, for example, ethoxylated nonionic compounds of the formula R '(OC2H4) n OH, in which R' is an alkyl group with 10 to 16 C atoms or an alkylphenyl group with an alkyl group with 8 to 12 C atoms, n is a number 3 to 9 and the HLB (hydrophilic-lipophilic balance) of these surfactants 10 to 13.
- R' is an alkyl group with 10 to 16 C atoms or an alkylphenyl group with an alkyl group with 8 to 12 C atoms
- n is a number 3 to 9
- the HLB hydrophilic-lipophilic balance
- 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 polycarboxylated compounds mentioned in US Pat. Nos. 4,321,165 and 4,284,532, such as, for example, water-soluble amino, cycloalkane, ether, alkyl, epoxy, tetrahydrofuran, benzene and polyacetal polycarboxylates, preferably sodium - and potassium salts of ethylenediaminetetraacetate, nitrilotriacetate and phytic acid, water-soluble polymers and copolymers of itaconic acid, aconitic acid, maleic acid, fumaric acid, mesaconic acid, methylmalonic acid and citric acid, and the sodium and potassium salts of mellitic acid, pyromellitic acid, benzene pentacarboxylic acid, carboxymethyloxoxyacid, carboxymethyloxoxanoic acid, carboxymethyloxoxanoic acid, carboxymethyloxoxoxyacid, carboxymethyloxox
- the liquid detergents are produced by simply mixing the individual components and used for washing and pretreating textile fabrics.
- liquid detergents according to the invention are stable for several months and do not cause bright spots when they come into direct contact with textile fabric.
- Example 1 A bleached cotton fabric is washed in a liquor ratio of 1:20 for 15 min in a 60 ° C. aqueous liquor which contains 3 g of one of the following liquid detergents a), b) or c) and 0.1% of one per liter Brightener of the formula based on the detergent. The cotton fabric is then rinsed in flowing water for 20 seconds and dried in a drying cabinet at 70 ° C. The fabric treated in this way has a high lightening effect even after the washing process has been repeated 5 to 10 times.
- Example 2 The stain test is carried out with the compounds of the formulas (1) - (5) and the respective liquid detergent a), b) or c). All compounds are stable in the three detergents for several months and show a good lightening effect and little or no formation of light spots.
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Description
Die vorliegende Anmeldung betrifft lagerstabile anionische Flüssigwaschmittel, die amphotere Distyrylderivate als optische Aufheller sowie anionische Tenside enthalten.The present application relates to storage-stable anionic liquid detergents which contain amphoteric distyryl derivatives as optical brighteners and anionic surfactants.
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, thanks 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 daher 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.
Desweiteren ist die Verwendung von amphoteren Aufhellern in kationischen Flüssigwaschmitteln bekannt (EP-A-59684), die Verwendung von amphoteren Aufhellern in anionischen Flüssigwaschmitteln wurde bislang nicht beschrieben.Furthermore, the use of amphoteric brighteners in cationic liquid detergents is known (EP-A-59684), the use of amphoteric brighteners in anionic liquid detergents has not been described to date.
Es hat sich nun gezeigt, dass amphotere Distyrylaufheller überraschenderweise auch in anionische, flüssige Waschmittel eingearbeitet werden können und dass damit die Bildung von hellen Flecken verbunden mit ausgezeichneter Aufhellwirkung und Waschmittelstabilität, verhindert werden kann.It has now been shown that, surprisingly, amphoteric distyre brighteners can also be incorporated into anionic, liquid detergents and that the formation of light spots combined with excellent brightening effect and detergent stability can be prevented.
Gegenstand der Anmeldung sind somit anionische Flüssigwaschmittel enthaltend optische Aufheller, dadurch gekennzeichnet, dass sie 1 bis 60 Gew %, bezogen auf das Gewicht des Waschmittels, eines anionischen Tensides enthalten, und dass die in einer Menge von 0,01 bis 2 % vorliegenden optischen Aufheller aus einem amphoteren Distyrylaufheller oder einer Mischung von Distyrylaufhellern der Formel I
bestehen, worin
- X
- Sauerstoff, Schwefel, die direkte Bindung, -SO₂N(R₅)̵ , -CON(R₅)̵ oder -COO ,
- Y₁ und Y₂
- unabhängig voneinander C₁-C₄-Alkylen oder Hydroxypropylen,
- R₁ und R₂
- unabhängig voneinander C₁-C₄-Alkyl oder zusammen mit dem N-Atom einen Pyrrolidin-, Piperidin-, Hexamethylenimin- oder Morpholinring und R₁ zusammen mit R₅ auch einen Piperazinring,
- R₃ und R₄
- unabhängig voneinander Wasserstoff, C₁-C₄-Alkyl, Halogen, C₁-C₄-Alkoxy, C₃-C₄-Alkenyl, -CN oder in o-Stellung zueinander zusammen eine Trimethylen-oder Tetramethylengruppe,
- R₅
- Wasserstoff, C₁-C₄-Alkyl, Cyanoäthyl oder zusammen mit R₁ einen Piperazinring,
- Q
- -COO oder -SO₃ und
- n
- die Zahl 1 oder 2
consist in what
- X
- Oxygen, sulfur, the direct bond, -SO₂N (R₅) ̵, -CON (R₅) ̵ or -COO,
- Y₁ and Y₂
- independently of one another C₁-C₄ alkylene or hydroxypropylene,
- R₁ and R₂
- independently of one another C₁-C₄-alkyl or together with the N atom a pyrrolidine, piperidine, hexamethyleneimine or morpholine ring and R₁ together with R₅ also a piperazine ring,
- R₃ and R₄
- independently of one another hydrogen, C₁-C₄-alkyl, halogen, C₁-C₄-alkoxy, C₃-C₄-alkenyl, -CN or together in the o-position to one another a trimethylene or tetramethylene group,
- R₅
- Hydrogen, C₁-C₄-alkyl, cyanoethyl or together with R₁ a piperazine ring,
- Q
- -COO or -SO₃ and
- n
- the number 1 or 2
Insbesondere werden amphotere Distyrylaufheller der Formel (II)
verwendet, worin R₁, R₂, Y₁, Y₂, Q und n die oben angegebene Bedeutung haben und X₁ Sauerstoff, die direkte Bindung, -CONH- oder -COO- und R₃' Wasserstoff, C₁-C₄-Alkyl, Methoxy oder Chlor bedeuten.In particular, amphoteric distyryl brighteners of the formula (II)
used wherein R₁, R₂, Y₁, Y₂, Q and n have the meaning given above and X₁ is oxygen, the direct bond, -CONH- or -COO- and R₃ 'is hydrogen, C₁-C₄-alkyl, methoxy or chlorine.
Vorzugsweise werden amphotere Distyrylaufheller der Formel (III)
verwendet, worin R₁, R₂, R₃', Y₁, Y₂, Q und n die oben angegebene Bedeutung haben und vor allem aber amphotere Distyrylaufheller der Formel (IV)
worin
y₁' C₁-C₄-Alkylen bedeutet und
R₁, R₂ und n die oben angegebene Bedeutung haben wie z.B. die Verbindung der Formel (V)
used, wherein R₁, R₂, R₃ ', Y₁, Y₂, Q and n have the meaning given above and, above all, but amphoteric Distyrylaufleller of formula (IV)
wherein
y₁ 'C₁-C₄ alkylene means and
R₁, R₂ and n have the meaning given above, for example the compound of the formula (V)
Die amphoteren Distyrylaufheller der Formeln (I) bis (V) sind bekannt und können nach bekannten Methoden hergestellt werden (siehe z.B. EP-A-59 684).The amphoteric distyryl brighteners of the formulas (I) to (V) are known and can be prepared by known methods (see, for example, EP-A-59 684).
Unter anionischen Flüssigwaschmitteln sind bekannte und handelsübliche Waschmittel mit insgesamt anionischem Charakter wie sie beispielsweise in der EP-A-167 205 oder US-4 507 219 beschrieben werden, zu verstehen.Anionic liquid detergents are known and commercially available detergents with an overall anionic character, as are described, for example, in EP-A-167 205 or US Pat. No. 4,507,219.
Insbesondere enthalten die Flüssigwaschmittel neben den genannten amphotereren Styryl-Derivaten und den 1 bis 60 % anionische Tensiden nichtionische und zwitterionische Tenside und gegebenenfalls geringe Mengen von kationischen Tensiden sowie 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-C₂₂)-Fettsäuren, insbesondere gesättigte (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 amphoteric styryl derivatives mentioned and the 1 to 60% anionic surfactants, the liquid detergents contain nonionic and zwitterionic surfactants and optionally small amounts of 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-C₂₂) - Fatty acids, in particular saturated (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 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-2 041 968 beschrieben. Als anionische Tenside verwendet man beispielsweise wasserlösliche Salze von alkyl- und/oder arylgruppenhaltigen organischen Schwefelverbindungen, Sulfonsäuren oder Sulfonsäureestern mit 10 bis 20 C-Atomen in der Alkylgruppe wie z.B. Alkylsulfate, vorzugsweise jene die durch Sulfatierung von höheren Alkoholen (10-18 C-Atomen) erhalten werden, lineare oder verzweigte Alkylbenzolsulfonate mit 9 bis 15 C-Atomen in den Alkylgruppen, vorzugsweise lineare Alkylbenzolsulfonate mit 11 bis 14 C-Atomen in den Alkylgruppen, Paraffinsulfonate mit 8 bis 24, vorzugsweise 12 bis 18 C-Atomen, Alkylglycerylethersulfonate mit 8 bis 18 C-Atomen, Alkylphenolethylenoxidethersulfate mit 1 bis 4 Mol Ethylenoxid pro Molekül und mit 8 bis 12 C-Atomen in den Alkylgruppen, Alkylethylenoxidethersulfate mit 1 bis 4 Mol Ethylenoxid pro Molekül und mit 10 bis 20 C-Atomen in den Alkylgruppen, wasserlösliche Salze oder Ester von alpha-sulfonierten Fettsäuren mit 6 bis 20 C-Atomen in der Fettsäure und 1 bis 10 C-Atomen in der Estergruppe, wasserlösliche Salze von 2-Acyloxy-alkan-1-sulfonsäure mit 2 bis 9 C-Atomen in der Acylgruppe und mit 9 bis 23 C-Atomen im Alkanteil, wasserlösliche Salze von Olefinsulfonaten mit 12 bis 24 C-Atomen und beta-Alkyloxy-alkansulfonate mit 1 bis 3 C-Atomen in den Alkylgruppen und mit 8 bis 20 C-Atomen im Alkanteil. Als nichtionische Tenside verwendet man beispielsweise ethoxylierte nichtionische Verbindungen der Formel R' (OC₂H₄)nOH, worin R' eine Alkylgruppe mit 10 bis 16 C-Atomen oder eine Alkylphenylgruppe mit einer Alkylgruppe mit 8 bis 12 C-Atomen, n eine Zahl von 3 bis 9 und der HLB (hydrophile-lipophile balance) dieser Tenside 10 bis 13 ist. 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 2,041,968. Anionic surfactants used are, for example, water-soluble salts of alkyl and / or aryl group-containing organic sulfur compounds, sulfonic acids or sulfonic acid esters with 10 to 20 carbon atoms in the alkyl group, such as alkyl sulfates, preferably those obtained by sulfating higher alcohols (10-18 carbon atoms ) linear or branched alkylbenzenesulfonates with 9 to 15 carbon atoms in the alkyl groups, preferably linear alkylbenzenesulfonates with 11 to 14 carbon atoms in the alkyl groups, paraffin sulfonates with 8 to 24, preferably 12 to 18 carbon atoms, alkylglyceryl ether sulfonates with 8 to 18 C atoms, alkylphenol ethylene oxide ether sulfates with 1 to 4 moles of ethylene oxide per molecule and with 8 to 12 C atoms in the alkyl groups, alkyl ethylene oxide ether sulfates with 1 to 4 moles of ethylene oxide per molecule and with 10 to 20 C atoms in the alkyl groups, water-soluble salts or esters of alpha-sulfonated fatty acids with 6 to 20 carbon atoms in the fatty acid and 1 to 10 carbon atoms in the ester group, water-soluble salts of 2-acyloxyalkane-1-sulfonic acid with 2 to 9 carbon atoms in the acyl group and with 9 to 23 carbon atoms Atoms in the alkane portion, water-soluble salts of olefin sulfonates with 12 to 24 carbon atoms and beta-alkyloxy alkane sulfonates with 1 to 3 carbon atoms in the alkyl groups and with 8 to 20 carbon atoms in the alkane portion. The nonionic surfactants used are, for example, ethoxylated nonionic compounds of the formula R '(OC₂H₄) n OH, in which R' is an alkyl group with 10 to 16 C atoms or an alkylphenyl group with an alkyl group with 8 to 12 C atoms, n is a number 3 to 9 and the HLB (hydrophilic-lipophilic balance) of these surfactants 10 to 13. 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 polycarboxylierten Verbindungen wie zum Beispiel wasserlösliche Amino-, Cycloalkan-, Ether-, Alkyl-, Epoxy-, Tetrahydrofuran-, Benzol- und Polyacetal-polycarboxylate, vorzugsweise die Natrium- und Kaliumsalze von Ethylendiamintetraacetat, Nitrilotriacetat und Phytinsäure, wasserlösliche Polymere und Copolymere von Itakonsäure, Akonitsäure, Maleinsäure, Fumarsäure, Mesakonsäure, Methylmalonsäure und Zitrakonsäure sowie die Natrium- und Kaliumsalze von Mellithsäure, Pyromellithsäure, Benzolpentacarbonsäure, Oxydiessigsäure, Carboxymethyloxybernsteinsäure, Carboxymethyloxymalonsäure, cis-Cyclohexanhexacarbonsäure, cis-Cyclopentantetracarbonsäure, Oxydibernsteinsäure und vor allem Zitronensäure und Zitrate in Betracht.Suitable detergent builders are the polycarboxylated compounds mentioned in US Pat. Nos. 4,321,165 and 4,284,532, such as, for example, water-soluble amino, cycloalkane, ether, alkyl, epoxy, tetrahydrofuran, benzene and polyacetal polycarboxylates, preferably sodium - and potassium salts of ethylenediaminetetraacetate, nitrilotriacetate and phytic acid, water-soluble polymers and copolymers of itaconic acid, aconitic acid, maleic acid, fumaric acid, mesaconic acid, methylmalonic acid and citric acid, and the sodium and potassium salts of mellitic acid, pyromellitic acid, benzene pentacarboxylic acid, carboxymethyloxoxyacid, carboxymethyloxoxanoic acid, carboxymethyloxoxanoic acid, carboxymethyloxoxoxyacid, carboxymethyloxoxanooxyacid, carboxymethylhexoxanoic acid, , cis-cyclopentanetetracarboxylic acid, oxydisuccinic acid and especially citric acid and citrates.
Die Flüssigwaschmittel werden durch einfaches Mischen der einzelnen Komponenten hergestellt und zum Waschen und Vorbehandeln von textilen Geweben verwendet.The liquid detergents are produced by simply mixing the individual components and used for washing and pretreating textile fabrics.
Die erfindungsgemässen Flüssigwaschmittel sind mehrere Monate stabil und rufen keine hellen Flecken bei einem direkten Kontakt mit Textilgewebe hervor.The liquid detergents according to the invention are stable for several months and do not cause bright spots when they come into direct contact with textile fabric.
Die folgenden Beispiele dienen zur Erläuterung der Erfindung; Teile bedeuten Gewichtsteile und Prozente Gewichtsprozente; der Fleckentest wird folgendermassen durchgeführt: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) Aufheller Waschmittel-Formulierung:
0,1 % (100 % Aktivsubstanz) optischer Aufheller oder Aufhellergemisch werden in einem flüssigen Waschmittel gelöst. 0,6 g dieser Waschmittellösung (A) wird mit 400 ml Wasser (10°-12° dH) bei einer Temperatur von 30°C verdünnt (Waschflotte B).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 solution (A) is diluted with 400 ml of water (10 ° -12 ° dH) at a temperature of 30 ° C (wash liquor B). - b) Ein 20 g Stück gebleichtes Baumwollgewebe wird auf einem Spannrahmen befestigt.b) A 20 g piece of bleached cotton fabric is attached to a tenter.
- 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 Min. bei 30°C gewaschen. Anschliessend wird mit kaltem Wasser gespült und bei 70°C getrocknet.c) 0.6 ml of the detergent solution (A) is evenly applied to a pre-marked, round surface (5 cm diameter) of this cotton fabric, added to the prepared wash liquor (B) after 30 seconds of exposure and at 30 ° C washed. It is then rinsed with cold water and dried at 70 ° C.
- d) Der Unterschied des Weissgrads nach Ganz zwischen der Auftragsfläche und der Umgebung ist eine Mass für das sogenannte Spotting-Verhalten (Bildung von hellen Flecken) und wird bei einfacher Textillage bestimmt.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 for simple textile layers.
Beispiel 1: Ein gebleichtes Baumwollgewebe wird im Flottenverhältnis 1:20 während 15 min in einer 60°C warmen, wässrigen Flotte gewaschen, die pro Liter 3 g eines der folgenden flüssigen Waschmittel a), b) oder c) und 0,1 % eines Aufhellers der Formel
bezogen auf das Waschmittel, enthält. Anschliessend wird das Baumwollgewebe während 20 Sekunden im fliessenden Wasser gespült und bei 70°C im Trockenschrank getrocknet. Das so behandelte Gewebe weist auch nach 5-bis 10-fach wiederholtem Waschprozess einen hohen Aufhelleffekt auf. Example 1 : A bleached cotton fabric is washed in a liquor ratio of 1:20 for 15 min in a 60 ° C. aqueous liquor which contains 3 g of one of the following liquid detergents a), b) or c) and 0.1% of one per liter Brightener of the formula
based on the detergent. The cotton fabric is then rinsed in flowing water for 20 seconds and dried in a drying cabinet at 70 ° C. The fabric treated in this way has a high lightening effect even after the washing process has been repeated 5 to 10 times.
Das verwendete flüssige Waschmittel wird durch Mischen der folgenden Komponenten hergestellt (Gew-%):
- a) 15 % C₁₁-C₁₃-Alkylbenzolsulfonat
14 % C₁₄-C₁₅-Polyethoxyfettalkohol (Ethylenoxid 7)
10 % Seifenflocken
9 % Ethanol
4 % Na-Citrat
5 % Triethanolamin
43 % Wasser - b) 7,5 % C₁₃-Alkylbenzolsulfonat
12 % C₁₄-C₁₅-Alkylpolyethoxysulfonat (Ethylenoxid 2.25)
15 % C₁₁-C₁₃-Fettsäure-Kaliumsalz
10 % C₁₂-C₁₃-Polyethoxyfettalkohol (Ethylenoxid 8)
5,5 % Na-Citrat
12 % 1:1 Mischung von Isopropylalkohol und Spiritus
0,7 % C₁₂-Alkyltrimethylammoniumchlorid
37,3 % Wasser
- c) 11,5 % C₁₁-C₁₃-Alkylbenzolsulfonat
3,8 % Triethanolaminlaurylsulfat
15,5 % Kalium-Seife
15 % C₁₄-C₁₅-Polyethoxyfettalkohol (Ethylenoxid 7)
5 % Triethanolamin
10 % Ethanol
39,2 % Wasser.
- a) 15% C₁₁-C₁₃ alkylbenzenesulfonate
14% C₁₄-C₁₅ polyethoxy fatty alcohol (ethylene oxide 7)
10% soap flakes
9% ethanol
4% Na citrate
5% triethanolamine
43% water - b) 7.5% C₁₃ alkylbenzenesulfonate
12% C₁₄-C₁₅ alkyl polyethoxysulfonate (ethylene oxide 2.25)
15% C₁₁-C₁₃ fatty acid potassium salt
10% C₁₂-C₁₃ polyethoxy fatty alcohol (ethylene oxide 8)
5.5% Na citrate
12% 1: 1 mixture of isopropyl alcohol and alcohol
0.7% C₁₂ alkyl trimethyl ammonium chloride
37.3% water
- c) 11.5% C₁₁-C₁₃ alkylbenzenesulfonate
3.8% triethanolamine lauryl sulfate
15.5% potassium soap
15% C₁₄-C₁₅ polyethoxy fatty alcohol (ethylene oxide 7)
5% triethanolamine
10% ethanol
39.2% water.
Beispiel 2: Der Fleckentest wird mit den Verbindungen der Formel (1)-(5) und dem jeweiligen flüssigen Waschmittel a), b) oder c) durchgeführt. Alle Verbindungen sind über mehrere Monate in den drei Waschmitteln beständig und zeigen gute Aufhellwirkung und keine oder lediglich geringe Bildung von hellen Flecken. Example 2 : The stain test is carried out with the compounds of the formulas (1) - (5) and the respective liquid detergent a), b) or c). All compounds are stable in the three detergents for several months and show a good lightening effect and little or no formation of light spots.
Claims (7)
- An anionic liquid detergent composition containing fluorescent whitening agents which contains 1 to 60 % by weight, based on the weight of the detergent composition, of an anionic surfactant and wherein the fluorescent whitening agents present in an amount of from 0.01 to 2 %, based on the weight of the detergent composition, consist of an amphoteric distyryl fluorescent whitening agent or a mixture of distyryl fluorescent whitening agents of formula (I)
X is oxygen, sulfur, a direct bond, -SO₂N(R₅)-, -CON(R₅)- or -COO-, Y₁ and Y₂ are each independently of the other C₁-C₄alkylene or hydroxypropylene,
R₁ and R₂ are each independently of the other C₁-C₄alkyl or together with the N atom are a pyrrolidine, piperidine, hexamethyleneimine or morpholine ring, and R₁ together with R₅ is also a piperazine ring,
R₃ and R₄ are each independently of the other hydrogen, C₁-C₄alkyl, halogen, C₁-C₄alkoxy, C₃-C₄alkenyl, -CN or, in ortho-position to each other, together are a trimethylene or tetramethylene group.
R₅ is hydrogen, C₁-C₄alkyl, cyanoethyl or, together with R₁, is a piperazine ring,
Q is -COO or SO₃, and
n is the number 1 or 2. - An anionic liquid detergent composition according to claim 1, which contains amphoteric distyryl fluorescent whitening agents of formula (II)
X₁ is oxygen, a direct bond, -CONH- or -COO-, and
R₃' is hydrogen, C₁-C₄alkyl, methoxy or chlorine. - An anionic liquid detergent composition according to claim 2, which contains amphoteric distyryl fluorescent whitening agents of formula (III)
- An anionic liquid detergent composition according to claim 3, which contains amphoteric distyryl fluorescent whitening agents of formula (IV)
- An anionic liquid detergent composition according to claim 4, which contains a distyryl fluorescent whitening agent of formula (V)
- An anionic liquid detergent composition according to claim 4, which contains a distyryl fluorescent whitening agent of formula
- Use of an anionic liquid detergent composition according to any one of claims 1 to 5 for washing and pretreating textile fabrics.
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CH114488 | 1988-03-25 | ||
| CH1144/88 | 1988-03-25 |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| EP0334372A1 EP0334372A1 (en) | 1989-09-27 |
| EP0334372B1 true EP0334372B1 (en) | 1993-01-20 |
Family
ID=4203519
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| EP89105275A Expired - Lifetime EP0334372B1 (en) | 1988-03-25 | 1989-03-23 | Liquid, anionic storage-stable detergents containing amphoteric distyryl derivatives |
Country Status (7)
| Country | Link |
|---|---|
| US (1) | US4940555A (en) |
| EP (1) | EP0334372B1 (en) |
| JP (1) | JPH01271497A (en) |
| AU (1) | AU621094B2 (en) |
| CA (1) | CA1317190C (en) |
| DE (1) | DE58903307D1 (en) |
| ES (1) | ES2053843T3 (en) |
Families Citing this family (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20050176617A1 (en) * | 2004-02-10 | 2005-08-11 | Daniel Wood | High efficiency laundry detergent |
| US7455725B2 (en) * | 2004-09-20 | 2008-11-25 | Mattel, Inc. | Washable marker ink composition |
Family Cites Families (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP0026013B1 (en) * | 1979-09-21 | 1983-09-07 | THE PROCTER & GAMBLE COMPANY | Washing and softening compositions and methods for their manufacture |
| ATE7898T1 (en) * | 1981-02-26 | 1984-06-15 | Ciba-Geigy Ag | AMPHOTERE STYRENE DERIVATIVES. |
| EP0235079A1 (en) * | 1986-01-29 | 1987-09-02 | Ciba-Geigy Ag | Process for the after-treatment of celluloric materials or materials containing cellulose, printed with reactive dyes |
-
1989
- 1989-03-15 US US07/323,707 patent/US4940555A/en not_active Expired - Fee Related
- 1989-03-23 DE DE8989105275T patent/DE58903307D1/en not_active Expired - Fee Related
- 1989-03-23 ES ES89105275T patent/ES2053843T3/en not_active Expired - Lifetime
- 1989-03-23 EP EP89105275A patent/EP0334372B1/en not_active Expired - Lifetime
- 1989-03-23 AU AU31707/89A patent/AU621094B2/en not_active Ceased
- 1989-03-23 CA CA000594727A patent/CA1317190C/en not_active Expired - Fee Related
- 1989-03-24 JP JP1070725A patent/JPH01271497A/en active Pending
Also Published As
| Publication number | Publication date |
|---|---|
| AU3170789A (en) | 1989-09-28 |
| CA1317190C (en) | 1993-05-04 |
| DE58903307D1 (en) | 1993-03-04 |
| EP0334372A1 (en) | 1989-09-27 |
| JPH01271497A (en) | 1989-10-30 |
| ES2053843T3 (en) | 1994-08-01 |
| US4940555A (en) | 1990-07-10 |
| AU621094B2 (en) | 1992-03-05 |
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