EP0322564A2 - Stable detergents containing optical brighteners - Google Patents
Stable detergents containing optical brighteners Download PDFInfo
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- EP0322564A2 EP0322564A2 EP88119486A EP88119486A EP0322564A2 EP 0322564 A2 EP0322564 A2 EP 0322564A2 EP 88119486 A EP88119486 A EP 88119486A EP 88119486 A EP88119486 A EP 88119486A EP 0322564 A2 EP0322564 A2 EP 0322564A2
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- European Patent Office
- Prior art keywords
- formula
- hydrogen
- compound
- optical brightener
- halogen
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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
- C11D3/39—Organic or inorganic per-compounds
- C11D3/3942—Inorganic per-compounds
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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
- C11D3/39—Organic or inorganic per-compounds
- C11D3/3945—Organic per-compounds
-
- 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 application relates to storage-stable detergents which, in addition to at least one peracid or its salts, contain at least one specific optical brightener of the stilbene type, and to their use for washing textiles.
- M in formula (I) is, for example, alkaline earth metal such as magnesium or calcium, but preferably alkali metal such as lithium, sodium, potassium and optionally substituted ammonium such as ammonium, mono-, di- or triethanol-ammonium, mono-, di- or tripropanol -ammonium or tri- or tetramethyl-ammonium.
- alkaline earth metal such as magnesium or calcium
- alkali metal such as lithium, sodium, potassium
- ammonium such as ammonium, mono-, di- or triethanol-ammonium, mono-, di- or tripropanol -ammonium or tri- or tetramethyl-ammonium.
- optical brighteners of the formulas I to V are known and can be prepared by known methods.
- the peracids or their salts are organic or inorganic compounds described in the literature or on the market, which bleach textiles at temperatures from 20 ° C.
- Diperoxydodecanedioic acid (DPDDA) can be used as the organic peracid.
- the amount of organic peracid to be used is preferably 0.5% to 10%, in particular 1% to 5%.
- very effective, inorganic peracids such as persulfate and / or percarbonate can also be used.
- the amount of these inorganic peracids is preferably 1% to 30%, in particular 10% to 20%, based on the total detergent weight. If appropriate and advantageously, they are used in combination with small amounts of catalytically active bivalent metal salts, as are described in US Pat. Nos. 4,655,782 and 4,655,953.
- Metal salts and copper and / or manganese are preferably used.
- the peracids are added to the detergent by dry mixing e.g. with the help of automatic screw dosing systems and / or fluidized bed mixers.
- the detergents are dry detergents of conventional compositions.
- they contain, for example, anionic, nonionic, amphoteric and / or cationic surfactants, builders such as, for example, pentasodium tripolyphosphate or substitute products such as phosphonates, polycarboxylates, acrylic-maleic copolymers, zeolites, nitrilotriacetate, ethylenediaminotetraacetate , Dirt suspending agents such as sodium carboxymethyl cellulose, salts for adjusting the pH such as alkali or alkaline earth silicates, foam regulators such as soap, salts for adjusting the spray drying and granulate properties such as sodium sulfate, perfumes, and optionally antistatic and softening agents, enzymes, photo bleaching agents, pigments and / or shading agents.
- these components should be stable with respect to the bleaching system used.
- a granulate A is produced by drying and granulating a slurry consisting of approx. 1 part water and 1 part detergent of the following composition: 84 g Linear dodecylbenzenesulfonate 31 g Tallow alcohol-tetradecane-ethylene glycol ether (14 AeO) 37 g Na soap (mainly from behenic acid and C14-C20) 458 g Na tripolyphosphate 79 g Na silicate 20 g Mg silicate 12 g Carboxymethyl cellulose 2 g Ethylenediamine tetraacetate 222 g Na sulfate 1 g optical brighteners (FWA) according to the formula (II) - (V).
- FWA optical brighteners
- the peracid B (15 g DPDDA) is homogeneously mixed into 500 g of this granulate A, which has a residual moisture of Rest5% after drying.
- Samples of the detergent W thus obtained are: - On the one hand to check the initial value, determined immediately by extraction and spectrophotometric extinction measurement for the FWA content, (theoretically: 0.1% FWA based on the weight of the granulate A) - On the other hand stored in commercial washing powder-compatible cardboard packages, ie with a coating, under selected and controlled temperature and humidity conditions for certain periods of time. After storage, the FWA content of each detergent is determined immediately. The difference from the initial value, expressed as a percentage, is a measure of the stability of the FWA against the corresponding bleach in the washing powder.
- the washing powder is homogenized well by grinding and 1 g of it is mixed with 200 ml of solvent consisting of 9 parts of dimethyl sulfoxide and 1 part of water and stirred at room temperature for 30 minutes. Then it is centrifuged for 30 minutes. A sample of the clear solution thus obtained is transferred with a pipette into a 1 cm quartz cuvette and its absorbance in the UV range is measured at the absorption maximum against a standard solution of the respective FWA. The extinction is proportional to the FWA concentration. The reproducibility of the results is approx. ⁇ 1% if the test conditions are observed exactly the same.
- the percentage FWA loss is determined according to the conditions described above. Storage is in a closed package, at 20 to 25 ° C. After 6 months the FWA loss is:
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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)
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- Inorganic Chemistry (AREA)
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Abstract
Description
Die Anmeldung betrifft lagerstabile Waschmittel, die neben mindestens einer Persäure oder deren Salze mindestens einen spezifischen optischen Aufheller vom Stilben-Typ enthalten, sowie deren Verwendung zum Waschen von Textilien.The application relates to storage-stable detergents which, in addition to at least one peracid or its salts, contain at least one specific optical brightener of the stilbene type, and to their use for washing textiles.
Begründet durch den gestiegenen Anteil an Kunstfasern bzw. Mischfasern in den heute hergestellten Textilien, dem Wunsch, bunte Wäsche nicht mehr separat zu waschen sowie aus Energie-Sparmassnahmen wird in vielen Ländern die Wäsche nicht mehr bei 90°C-95°C oder beim Kochen sondern bei tieferen Temperaturen gewaschen. Dies führte dazu, dass die bislang meistens in Waschmitteln enthaltenen, als Bleichmittel wirkenden, Perborate durch Hilfsmittel wie z.B. Tetraacetylethylendiamin (TAED) aktiviert werden mussten, um akzeptable Bleicheffekte auch bei Waschtemperaturen von 60-80°C zu erlangen. Bei noch tieferen Waschtemperaturen liefern auch die Perborat/Aktivator-Systeme keine befriedigenden Ergebnisse mehr.Founded by the increased proportion of synthetic fibers or mixed fibers in the textiles manufactured today, the desire to no longer wash colored laundry separately, and energy-saving measures, laundry is no longer at 90 ° C-95 ° C or in cooking in many countries but washed at lower temperatures. This has led to the fact that the perborates, which have hitherto mostly been used in detergents and act as bleaching agents, are caused by auxiliaries such as e.g. Tetraacetylethylenediamine (TAED) had to be activated in order to achieve acceptable bleaching effects even at washing temperatures of 60-80 ° C. At even lower washing temperatures, the perborate / activator systems also no longer provide satisfactory results.
Seit einiger Zeit werden daher Waschmittel beschrieben (DE-OS-27 56 583, EP-A-145 438, GB-2 141 754, GB-2 141 755, US-4 028 263, GB-59 272), die stärkere Bleichmittel wie z.B. Persäuren enthalten. Diese neuen Bleichmittel zeigen einerseits zwar hervorragende Bleicheffekte bei Temperaturen schon ab 20°C, andererseits zerstören sie aber die üblichen in Waschmitteln enthaltenen optischen Aufheller.Detergents have therefore been described for some time (DE-OS-27 56 583, EP-A-145 438, GB-2 141 754, GB-2 141 755, US-4 028 263, GB-59 272), the stronger bleach such as peracids. On the one hand, these new bleaching agents show excellent bleaching effects at temperatures as low as 20 ° C, but on the other hand they destroy the usual optical brighteners contained in detergents.
Es wurde nun gefunden, dass spezielle Stilben-Verbindungen überraschenderweise eine ausgezeichnete Stabilität in Waschmitteln aufweisen, die solche starken Bleichmittel enthalten. Unter durchschnittlichen Lagerbedingungen und sogar unter verschärften Bedingungen (Temperaturen über 30°C und Luftfeuchtigkeit über 60 %) sind diese speziellen Stilben-Aufheller im Waschmittel über mehrere Monate vollständig stabil oder werden höchstens in einem für die Praxis nicht störenden Mass abgebaut.It has now been found that special stilbene compounds surprisingly have excellent stability in detergents which contain such strong bleaches. Under average storage conditions and even under tougher conditions (temperatures above 30 ° C and humidity above 60%), these special stilbene brighteners in the detergent are completely stable over several months or are broken down to a degree that is not disturbing in practice.
Gegenstand der Anmeldung sind somit lagerstabile Waschmittel enthaltend 0,5 bis 30 % einer anorganischen Persäure oder Diperoxydodecandisäure als organische Persäure oder deren Salze oder Mischungen von Persäuren oder deren Salze sowie 0,03 % bis 0,5 % eines optischen Aufhellers oder eine Mischung von optischen Aufhellern, der Formel (I)
A = Wasserstoff, -SO₃M, Halogen, Phenyl oder Phenylpyrazolyl-1;
B = Benzofuranyl-2 falls A Wasserstoff ist,
2-(Stilbenyl-4)-oxadiazolyl-5 falls A Halogen ist,
Phenylpyrazolyl-1 falls A Phenylpyrazolyl-1 ist,
Benzoxazolyl-2 falls A -SO₃M oder Phenyl ist,
Naphthoxazolyl-2 falls A Wasserstoff ist;
R₁, R₂ = unabhängig voneinander Wasserstoff, Halogen, C₁-C₄-Alkyl oder C₁-C₄-Alkoxy;
M = Wasserstoff oder ein Aequivalent eines nicht chromophoren Kations und
n = Null bis 2 bedeuten, wobei die Verbindung der Formel (I) jedoch mindestens eine -SO₃M Gruppe enthält.The application thus relates to storage-stable detergents containing 0.5 to 30% of an inorganic peracid or diperoxydodecanedioic acid as organic peracid or their salts or mixtures of peracids or their salts and 0.03% to 0.5% of an optical brightener or a mixture of optical Brightener, the formula (I)
A = hydrogen, -SO₃M, halogen, phenyl or phenylpyrazolyl-1;
B = benzofuranyl-2 if A is hydrogen,
2- (stilbenyl-4) -oxadiazolyl-5 if A is halogen,
Phenylpyrazolyl-1 if A is phenylpyrazolyl-1,
Benzoxazolyl-2 if A is -SO₃M or phenyl,
Naphthoxazolyl-2 if A is hydrogen;
R₁, R₂ = independently of one another hydrogen, halogen, C₁-C₄-alkyl or C₁-C₄-alkoxy;
M = hydrogen or an equivalent of a non-chromophoric cation and
n = zero to 2, but the compound of the formula (I) contains at least one -SO₃M group.
M in Formel (I) steht beispielsweise für Erdalkalimetall wie Magnesium oder Calcium, vorzugsweise jedoch Alkalimetall, wie Lithium, Natrium, Kalium und gegebenenfalls substituiertes Ammonium, wie Ammonium, Mono-, Di- oder Triethanol-ammonium, Mono-, Di- oder Tripropanol-ammonium oder Tri- oder Tetramethyl-ammonium.M in formula (I) is, for example, alkaline earth metal such as magnesium or calcium, but preferably alkali metal such as lithium, sodium, potassium and optionally substituted ammonium such as ammonium, mono-, di- or triethanol-ammonium, mono-, di- or tripropanol -ammonium or tri- or tetramethyl-ammonium.
Insbesondere enthalten die Waschmittel als Aufheller Verbindungen der Formeln
und/oder
and or
All diese optischen Aufheller der Formel I bis V sind bekannt und können nach bekannten Methoden hergestellt werden.All of these optical brighteners of the formulas I to V are known and can be prepared by known methods.
Bei den Persäuren bzw. deren Salzen handelt es sich um der Literatur beschriebene oder auf dem Markt befindliche organische oder anorganische Verbindungen, die Textilien schon bei Temperaturen ab 20°C bleichen. Als organische Persäure kommt Diperoxydodecandisäure (DPDDA) in Frage. Die einzusetzende Menge an organischer Persäure liegt vorzugsweise bei 0,5 % bis 10 %, insbesondere 1 % bis 5 %. Es können aber auch sehr wirksame, anorganische Persäuren wie Persulfat und/oder Percarbonat eingesetzt werden. Die Menge dieser anorganischen Persäuren liegt vorzugsweise bei 1 % bis 30 %, insbesondere 10 % bis 20 %, bezogen auf das gesamte Waschmittelgewicht. Gegebenenfalls und vorteilhaft werden sie in Kombination mit kleinen Mengen katalytisch wirkender bivalenter Metall-Salze, wie sie in der US-4 655 782 und US-4 655 953 beschrieben werden verwendet. Bevorzugt werden Metallsalze und Kupfer und/oder Mangan eingesetzt.The peracids or their salts are organic or inorganic compounds described in the literature or on the market, which bleach textiles at temperatures from 20 ° C. Diperoxydodecanedioic acid (DPDDA) can be used as the organic peracid. The amount of organic peracid to be used is preferably 0.5% to 10%, in particular 1% to 5%. However, very effective, inorganic peracids such as persulfate and / or percarbonate can also be used. The amount of these inorganic peracids is preferably 1% to 30%, in particular 10% to 20%, based on the total detergent weight. If appropriate and advantageously, they are used in combination with small amounts of catalytically active bivalent metal salts, as are described in US Pat. Nos. 4,655,782 and 4,655,953. Metal salts and copper and / or manganese are preferably used.
Selbstverständlich können auch Mischungen der organischen und anorganischen Persäuren bzw. -Salze oder nur Mischungen der anorganischen Persäuren eingesetzt werden.Mixtures of organic and inorganic peracids or salts or only mixtures of inorganic peracids can of course also be used.
Die Zugabe der Persäuren in das Waschmittel erfolgt durch trockenes Mischen z.B. mit Hilfe von automatischen Schnecken-Dosier-Systemen und/oder Wirbelschicht-Mischern.The peracids are added to the detergent by dry mixing e.g. with the help of automatic screw dosing systems and / or fluidized bed mixers.
Bei den Waschmitteln handelt es sich um trockene Waschmittel üblicher Zusammensetzungen. In der Regel enthalten sie neben der erfindungsgemässen Kombination aus Persäure und Aufheller, beispielsweise anionische, nicht-ionogene, amphotere und/oder kationische Tenside, Builder wie z.B. Pentanatriumtripolyphosphat oder Ersatzprodukte wie Phosphonate, Polycarboxylate, Acryl-Malein-Copolymere, Zeolithe, Nitrilotriacetat, Ethylendiaminotetraessigsäure, Schmutzsuspendiermittel wie z.B. Natriumcarboxymethylcellulose, Salze zur Einstellung des pH-Werts wie z.B. Alkali- oder Erdalkalisilikate, Schaum-Regulatoren wie z.B. Seife, Salze zur Einstellung der Sprühtrocknungs- und Granulat-Eigenschaften wie z.B. Natriumsulfat, Parfums, sowie gegebenenfalls antistatische und weichmachende Mittel, Enzyme, Photobleichmittel, Pigmente und/oder Nuancierungsmittel, Selbstverständlich sollen diese Bestandteile gegenüber dem eingesetzten Bleichsystem stabil sein.The detergents are dry detergents of conventional compositions. As a rule, in addition to the combination of peracid and brightener according to the invention, they contain, for example, anionic, nonionic, amphoteric and / or cationic surfactants, builders such as, for example, pentasodium tripolyphosphate or substitute products such as phosphonates, polycarboxylates, acrylic-maleic copolymers, zeolites, nitrilotriacetate, ethylenediaminotetraacetate , Dirt suspending agents such as sodium carboxymethyl cellulose, salts for adjusting the pH such as alkali or alkaline earth silicates, foam regulators such as soap, salts for adjusting the spray drying and granulate properties such as sodium sulfate, perfumes, and optionally antistatic and softening agents, enzymes, photo bleaching agents, pigments and / or shading agents. Of course, these components should be stable with respect to the bleaching system used.
Dank der erfindungsgemässen Kombination ist es möglich, Waschmittel anzubieten, die dem üblichen Standard wie z.B. punkto Waschkraft, Fleckenentfernung, Erfrischung des Aussehens der gewaschenen Artikel entsprechen, auch wenn bei Temperaturen von 20°C-60°C gewaschen wird. Vorteilhafterweise können somit Buntwäsche und Weisswäsche unabhängig von der Faser zusammen gewaschen werden.Thanks to the combination according to the invention, it is possible to offer detergents which meet the usual standard, e.g. in terms of washing power, stain removal, refreshment of the appearance of the washed items, even when washing at temperatures of 20 ° C-60 ° C. Colored laundry and white laundry can thus advantageously be washed together regardless of the fiber.
Die nachfolgenden Beispiele erläutern die Erfindung, ohne sie darauf zu beschränken. Prozent-Angaben sind Gewichtsprozente.The following examples illustrate the invention without restricting it. Percentages are percentages by weight.
Die Waschmittel der folgenden Beispiele werden nach dem üblichen Verfahren, in zwei Stufen hergestellt:
Zuerst wird ein Granulat A durch Trocknung und Granulierung eines Slurry bestehend aus ca. 1 Teil Wasser und 1 Teil Waschmittel folgender Zusammensetzung hergestellt:
First, a granulate A is produced by drying and granulating a slurry consisting of approx. 1 part water and 1 part detergent of the following composition:
Zu 500 g dieses Granulats A, das nach der Trocknung eine Restfeuchte von ∼5 % aufweist, wird die Persäure B (15 g DPDDA) im trockenen Zustand homogen zugemischt.The peracid B (15 g DPDDA) is homogeneously mixed into 500 g of this granulate A, which has a residual moisture of Rest5% after drying.
Proben des so erhaltenen Waschmittels W (Granulat A + Persäure B) werden:
- einerseits zur Kontrolle des Ausgangswertes, sofort durch Extraktion und spektrophotometrische Extinktions-Messung auf den Gehalt an FWA bestimmt, (theoretisch: 0.1 % FWA bezogen auf das Gewicht des Granulats A)
- andererseits in Handels-Waschpulver gerechten Karton-Paketen, d.h. mit Beschichtung, unter ausgewählten und kontrollierten Temperatur- und Luftfeuchtigkeits-Bedingungen während bestimmten Zeit-Perioden gelagert. Nach der Lagerung wird von jedem Waschmittel sofort der Gehalt an FWA bestimmt. Der Unterschied zum Ausgangswert, in Prozent ausgedrückt, ist ein Mass für die Stabilität des FWA gegenüber dem entsprechenden Bleichmittel im Waschpulver.Samples of the detergent W thus obtained (granules A + peracid B) are:
- On the one hand to check the initial value, determined immediately by extraction and spectrophotometric extinction measurement for the FWA content, (theoretically: 0.1% FWA based on the weight of the granulate A)
- On the other hand stored in commercial washing powder-compatible cardboard packages, ie with a coating, under selected and controlled temperature and humidity conditions for certain periods of time. After storage, the FWA content of each detergent is determined immediately. The difference from the initial value, expressed as a percentage, is a measure of the stability of the FWA against the corresponding bleach in the washing powder.
Die oben erwähnte FWA-Bestimmung wird wie folgt durchgeführt:The FWA determination mentioned above is carried out as follows:
Das Waschpulver wird durch Mahlen gut homogenisiert und 1 g davon wird mit 200 ml Lösungsmittel, bestehend aus 9 Teilen Dimethylsulfoxid und 1 Teil Wasser versetzt, und bei Raumtemperatur während 30 Minuten gerührt. Dann wird während 30 Minuten zentrifugiert. Von der so erhaltenen, klaren Lösung wird eine Probe mit einer Pipette in eine 1 cm Quarz-Küvette transferiert und deren Extinktion im UV-Bereich, beim Absorptionsmaximum gegen eine Standard-Lösung des jeweiligen FWA gemessen. Die Extinktion ist der FWA-Konzentration proportional. Die Reproduzierbarkeit der Resultate liegt bei ca. ± 1 %, sofern die Test-Bedingungen genau gleich eingehalten werden.The washing powder is homogenized well by grinding and 1 g of it is mixed with 200 ml of solvent consisting of 9 parts of dimethyl sulfoxide and 1 part of water and stirred at room temperature for 30 minutes. Then it is centrifuged for 30 minutes. A sample of the clear solution thus obtained is transferred with a pipette into a 1 cm quartz cuvette and its absorbance in the UV range is measured at the absorption maximum against a standard solution of the respective FWA. The extinction is proportional to the FWA concentration. The reproducibility of the results is approx. ± 1% if the test conditions are observed exactly the same.
Gemäss oben beschriebenen Bedingungen, wird der prozentuale FWA-Verlust bestimmt. Die Lagerung erfolgt in geschlossenem Paket, bei 20 bis 25°C. Nach 6 Monaten beträgt der FWA-Verlust von:
Claims (9)
A = Wasserstoff, -SO₃M, Halogen, Phenyl oder Phenylpyrazolyl-1;
B = Benzofuranyl-2 falls A Wasserstoff ist,
2-(Stilbenyl-4)-oxadiazolyl-5 falls A Halogen ist,
Phenylpyrazolyl-1 falls A Phenylpyrazolyl-1 ist,
Benzoxazolyl-2 falls A-SO₃M oder Phenyl ist,
Naphthoxazolyl-2 falls A Wasserstoff ist;
R₁, R₂ = unabhängig voneinander Wasserstoff, Halogen, C₁-C₄-Alkyl oder C₁-C₄-Alkoxy;
M = Wasserstoff oder ein Aequivalent eines nicht chromophoren Kations und
n = Null bis 2 bedeuten, wobei die Verbindung der Formel (I) jedoch mindestens eine -SO₃M Gruppe enthalten.1. Storage-stable detergents, characterized in that they contain 0.5 to 30% of an inorganic peracid or diperoxydodecanedioic acid as organic peracid, or their salts or mixtures of peracids or their salts, and 0.03% to 0.5% of an optical brightener or a mixture of optical brighteners, of the formula (I)
A = hydrogen, -SO₃M, halogen, phenyl or phenylpyrazolyl-1;
B = benzofuranyl-2 if A is hydrogen,
2- (stilbenyl-4) -oxadiazolyl-5 if A is halogen,
Phenylpyrazolyl-1 if A is phenylpyrazolyl-1,
Benzoxazolyl-2 if A-SO₃M or phenyl,
Naphthoxazolyl-2 if A is hydrogen;
R₁, R₂ = independently of one another hydrogen, halogen, C₁-C₄-alkyl or C₁-C₄-alkoxy;
M = hydrogen or an equivalent of a non-chromophoric cation and
n = zero to 2, but the compound of the formula (I) contains at least one -SO₃M group.
Applications Claiming Priority (2)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
CH5009/87 | 1987-12-23 | ||
CH500987 | 1987-12-23 |
Publications (3)
Publication Number | Publication Date |
---|---|
EP0322564A2 true EP0322564A2 (en) | 1989-07-05 |
EP0322564A3 EP0322564A3 (en) | 1989-08-30 |
EP0322564B1 EP0322564B1 (en) | 1994-06-15 |
Family
ID=4286370
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
EP88119486A Expired - Lifetime EP0322564B1 (en) | 1987-12-23 | 1988-11-23 | Stable detergents containing optical brighteners |
Country Status (7)
Country | Link |
---|---|
EP (1) | EP0322564B1 (en) |
JP (1) | JP2634453B2 (en) |
AU (1) | AU624587B2 (en) |
BR (1) | BR8806215A (en) |
DE (1) | DE3850234D1 (en) |
ES (1) | ES2054774T3 (en) |
ZA (1) | ZA888793B (en) |
Cited By (7)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
EP0368100A2 (en) * | 1988-10-27 | 1990-05-16 | FMC Corporation | Particulate composition containing bleach and an optical brightener and process for its manufacture |
EP0724012A1 (en) * | 1995-01-27 | 1996-07-31 | The Procter & Gamble Company | Detergent compositions comprising bleaching agent and brightener |
US6566320B1 (en) | 1999-10-19 | 2003-05-20 | The Procter & Gamble Company | Bleaching composition containing chromotropic compound |
US6569826B1 (en) | 1999-10-19 | 2003-05-27 | The Procter & Gamble Company | Radical scavenger |
EP2112218A1 (en) | 2008-04-25 | 2009-10-28 | The Procter and Gamble Company | Colored bleaching composition |
CN104046350A (en) * | 2013-03-15 | 2014-09-17 | 广州熵能创新材料股份有限公司 | Fluorescent microsphere and preparation method and application thereof |
WO2016207691A1 (en) | 2015-06-22 | 2016-12-29 | Fater S.P.A. | Stable bleaching composition |
Families Citing this family (2)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
ES2065329T3 (en) * | 1987-11-26 | 1995-02-16 | Ciba Geigy Ag | DRY, STABLE DETERGENTS CONTAINING OPTICAL BLEACHERS. |
KR100351295B1 (en) * | 2000-03-29 | 2002-09-05 | 김기식 | Hangers of device for cheeking safety of presses |
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CH610478B (en) * | 1974-06-12 | Ciba Geigy Ag | USE OF DISTILBENYL OXADIAZOLES FOR THE OPTICAL LIGHTENING OF TEXTILE ORGANIC MATERIALS. | |
CH612817B (en) * | 1974-06-12 | Ciba Geigy Ag | USE OF STYLE COMPOUNDS FOR THE OPTICAL LIGHTENING OF TEXTILE ORGANIC MATERIALS. | |
US4028263A (en) * | 1973-08-24 | 1977-06-07 | Colgate-Palmolive Company | Bleaching and brightening detergent composition |
CH603733A5 (en) * | 1975-05-02 | 1978-08-31 | Ciba Geigy Ag | Stilbene cpds. used as optical brightening agents |
EP0002746A1 (en) * | 1977-12-19 | 1979-07-11 | Henkel Kommanditgesellschaft auf Aktien | Bleaching agent containing per-compounds and optical brighteners and its application in textile treatment |
EP0214789A2 (en) * | 1985-08-21 | 1987-03-18 | The Clorox Company | Dry peracid based bleaching product |
EP0317979A2 (en) * | 1987-11-26 | 1989-05-31 | Ciba-Geigy Ag | Stable detergents containing optical brighteners |
Family Cites Families (3)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US4177347A (en) * | 1974-06-12 | 1979-12-04 | Ciba-Geigy Corporation | Distilbenyl-oxdiazoles |
DE2525637A1 (en) * | 1974-06-12 | 1976-01-02 | Ciba Geigy Ag | DISTILBENYL OXDIAZOLE |
DE2525683A1 (en) * | 1974-06-12 | 1976-01-02 | Ciba Geigy Ag | SULFOGROUPHIC HETEROCYCLES |
-
1988
- 1988-11-23 ES ES88119486T patent/ES2054774T3/en not_active Expired - Lifetime
- 1988-11-23 EP EP88119486A patent/EP0322564B1/en not_active Expired - Lifetime
- 1988-11-23 DE DE3850234T patent/DE3850234D1/en not_active Expired - Fee Related
- 1988-11-24 JP JP63294819A patent/JP2634453B2/en not_active Expired - Lifetime
- 1988-11-24 ZA ZA888793A patent/ZA888793B/en unknown
- 1988-11-25 AU AU25935/88A patent/AU624587B2/en not_active Ceased
- 1988-11-25 BR BR888806215A patent/BR8806215A/en unknown
Patent Citations (7)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US4028263A (en) * | 1973-08-24 | 1977-06-07 | Colgate-Palmolive Company | Bleaching and brightening detergent composition |
CH610478B (en) * | 1974-06-12 | Ciba Geigy Ag | USE OF DISTILBENYL OXADIAZOLES FOR THE OPTICAL LIGHTENING OF TEXTILE ORGANIC MATERIALS. | |
CH612817B (en) * | 1974-06-12 | Ciba Geigy Ag | USE OF STYLE COMPOUNDS FOR THE OPTICAL LIGHTENING OF TEXTILE ORGANIC MATERIALS. | |
CH603733A5 (en) * | 1975-05-02 | 1978-08-31 | Ciba Geigy Ag | Stilbene cpds. used as optical brightening agents |
EP0002746A1 (en) * | 1977-12-19 | 1979-07-11 | Henkel Kommanditgesellschaft auf Aktien | Bleaching agent containing per-compounds and optical brighteners and its application in textile treatment |
EP0214789A2 (en) * | 1985-08-21 | 1987-03-18 | The Clorox Company | Dry peracid based bleaching product |
EP0317979A2 (en) * | 1987-11-26 | 1989-05-31 | Ciba-Geigy Ag | Stable detergents containing optical brighteners |
Non-Patent Citations (1)
Title |
---|
Ullmann's Encyclopedia of Industrial Chemistry , 5th ed., vol. A8, pp. 360-362 * |
Cited By (8)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
EP0368100A2 (en) * | 1988-10-27 | 1990-05-16 | FMC Corporation | Particulate composition containing bleach and an optical brightener and process for its manufacture |
EP0368100A3 (en) * | 1988-10-27 | 1992-08-26 | FMC Corporation | Particulate composition containing bleach and an optical brightener and process for its manufacture |
EP0724012A1 (en) * | 1995-01-27 | 1996-07-31 | The Procter & Gamble Company | Detergent compositions comprising bleaching agent and brightener |
US6566320B1 (en) | 1999-10-19 | 2003-05-20 | The Procter & Gamble Company | Bleaching composition containing chromotropic compound |
US6569826B1 (en) | 1999-10-19 | 2003-05-27 | The Procter & Gamble Company | Radical scavenger |
EP2112218A1 (en) | 2008-04-25 | 2009-10-28 | The Procter and Gamble Company | Colored bleaching composition |
CN104046350A (en) * | 2013-03-15 | 2014-09-17 | 广州熵能创新材料股份有限公司 | Fluorescent microsphere and preparation method and application thereof |
WO2016207691A1 (en) | 2015-06-22 | 2016-12-29 | Fater S.P.A. | Stable bleaching composition |
Also Published As
Publication number | Publication date |
---|---|
AU624587B2 (en) | 1992-06-18 |
EP0322564A3 (en) | 1989-08-30 |
BR8806215A (en) | 1989-08-15 |
JPH01172497A (en) | 1989-07-07 |
EP0322564B1 (en) | 1994-06-15 |
AU2593588A (en) | 1989-07-06 |
JP2634453B2 (en) | 1997-07-23 |
DE3850234D1 (en) | 1994-07-21 |
ZA888793B (en) | 1989-08-30 |
ES2054774T3 (en) | 1994-08-16 |
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