EP0321715B1 - Stable detergents containing optical brighteners - Google Patents
Stable detergents containing optical brighteners Download PDFInfo
- Publication number
- EP0321715B1 EP0321715B1 EP88119487A EP88119487A EP0321715B1 EP 0321715 B1 EP0321715 B1 EP 0321715B1 EP 88119487 A EP88119487 A EP 88119487A EP 88119487 A EP88119487 A EP 88119487A EP 0321715 B1 EP0321715 B1 EP 0321715B1
- Authority
- EP
- European Patent Office
- Prior art keywords
- salts
- fluorescent whitening
- peracids
- peracid
- detergent according
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Expired - Lifetime
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Classifications
-
- C—CHEMISTRY; METALLURGY
- C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
- C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
- C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
- C11D3/40—Dyes ; Pigments
- C11D3/42—Brightening agents ; Blueing agents
-
- 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
-
- 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
Definitions
- the present invention relates to storage-stable detergents which, in addition to at least diperoxydodecanedioic acid or its salts, contain at least one specific optical brightener of the bis-benzofuranyl type, and to the production and use thereof 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.
- the detergents contain brighteners of the formula
- These optical brighteners of the formula I and II are known and can be prepared by known methods (DE-OS-2 238 734).
- the peracids or their salts are organic or inorganic compounds which have been described in the literature or are on the market and which preferably bleach textiles even at temperatures from 20 ° C.
- Diperoxydodecanedioic acid (DPDDA) is necessary as an organic peracid.
- the amount of organic peracid to be used is preferably 0.5% to 10%, in particular 1% to 5%. But it can also be very effective, inorganic peracids such as persulfate and / or percarbonate are used.
- the amount of inorganic peracids is preferably 1% to 20%, in particular 10% to 20%, based on the total weight of the detergent and, if appropriate, and advantageously in combination with small amounts of catalytic bivalent metal salts, as described in US Pat. No. 4,655,782 and U.S. 4,655,953.
- Metal salts of copper and / or manganese are preferably used.
- the peracids are mainly added to the detergent by mixing the components e.g. with the help of 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 e.g. Pentasodium tripolyphosphate or substitute products such as phosphonates, polycarboxylates, acrylic-maleic copolymers, zeolites, nitrilotriacetate, ethylenediaminotetraacetic acid, soil suspending agents such as e.g. Sodium carboxymethyl cellulose, salts for adjusting the pH such as e.g.
- Alkali or alkaline earth silicates foam regulators such as Soap
- salts to adjust the spray drying and granulate properties such as Sodium sulfate, perfumes, and optionally antistatic and softening agents, enzymes, photobleaches, 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 20g magnesium silicate 12 g carboxymethyl cellulose 2 g ethylenediamine tetraacetate 222 g Na sulfate 1 g optical brightener (FWA) according to the formula (I) - (II).
- FWA optical brightener
- the peracid B (15 g DPDDA) is mixed homogeneously into 500 g of this granulate A, which has a residual moisture of ⁇ 5% after drying.
- the FWA determination mentioned above is carried out as follows: The washing powder is homogenized well by grinding and 1 g of it is mixed with 200 ml Solvent consisting of 9 parts of dimethyl sulfoxide and 1 part of water is added, and the mixture is 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 absorbance is proportional to the FWA concentration. The reproducibility of the results is approx. ⁇ 1% if the test conditions are observed exactly the same.
- Example According to the conditions described above, the percentage FWA loss is determined. 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)
- Wood Science & Technology (AREA)
- Organic Chemistry (AREA)
- Inorganic Chemistry (AREA)
- Detergent Compositions (AREA)
Description
Die vorliegende Erfindung betrifft lagerstabile Waschmittel, die neben mindestens Diperoxydodecandisäure oder deren Salze mindestens einen spezifischen optischen Aufheller vom Bis-benzofuranyl-Typ enthalten, sowie deren Herstellung und Verwendung zum Waschen von Textilien.The present invention relates to storage-stable detergents which, in addition to at least diperoxydodecanedioic acid or its salts, contain at least one specific optical brightener of the bis-benzofuranyl type, and to the production and use thereof 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 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 produced by auxiliary agents such as 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 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 schon bei Temperaturen 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 included. On the one hand, these new bleaching agents show excellent bleaching effects even at temperatures from 20 ° C, on the other hand they destroy the usual optical brighteners contained in detergents.
Es wurde nun gefunden, dass spezielle Bis-benzofuranyl-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 Bis-benzofuranyl-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 bis-benzofuranyl compounds surprisingly have excellent stability in detergents which contain such strong bleaches. Under average storage conditions and even under more stringent conditions (temperatures above 30 ° C and air humidity above 60%), these special bis-benzofuranyl brighteners in detergents are completely stable over several months or are broken down to an extent that is not disturbing in practice.
Gegenstand der vorliegenden Erfindung sind somit lagerstabile trockene Waschmittel enthaltend eine organische Persäure oder deren Salze oder deren Mischungen mit anderen Persäure oder deren Salze sowie einen optischen Aufheller oder eine Mischung von optischen Aufhellern, dadurch gekennzeichnet, dass sie
- a) 0,5 bis 30 % Diperoxydodecandisäure als organische Persäure oder deren Salze oder 0,5 bis 30% Mischungen aus Diperoxydodecandisäure oder deren Salze mit anderen Persäuren oder deren Salze und
- b) 0,03 % bis 0,5 % eines optischen Aufhellers oder eine Mischung von optischen Aufhellern der Formel (I)
M = Wasserstoff oder ein Aequivalent eines nicht chromophoren Kations und
n = 2 bis 4 bedeutet, enthalten.
- a) 0.5 to 30% diperoxydodecanedioic acid as organic peracid or its salts or 0.5 to 30% mixtures of diperoxydodecanedioic acid or its salts with other peracids or their salts and
- b) 0.03% to 0.5% of an optical brightener or a mixture of optical brighteners of the formula (I)
M = hydrogen or an equivalent of a non-chromophoric cation and
n = 2 to 4 means included.
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 Formel
Diese optischen Aufheller der Formel I und II sind bekannt und können nach bekannten Methoden hergestellt werden (DE-OS-2 238 734).In particular, the detergents contain brighteners of the formula
These optical brighteners of the formula I and II are known and can be prepared by known methods (DE-OS-2 238 734).
Bei den Persäuren bzw. deren Salze handelt es sich um in der Literatur bescriebene oder auf dem Markt befindliche organische oder anorganische Verbindungen die vorzugsweise Textilien schon bei Temperaturen ab 20°C bleichen. Als organische Persäure ist Diperoxydodecandisäure (DPDDA) notwendig. 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 Mengen anorganischer Persäuren liegt vorzugsweise bei 1 % bis 20 %, insbesondere 10 % bis 20 %, bezogen auf das gesamte Waschmittelgewicht und gegebenenfalls sowie vorteilhaft 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. Bevorzugt werden Metallsalze von Kupfer und/oder Mangan verwendet.The peracids or their salts are organic or inorganic compounds which have been described in the literature or are on the market and which preferably bleach textiles even at temperatures from 20 ° C. Diperoxydodecanedioic acid (DPDDA) is necessary as an organic peracid. The amount of organic peracid to be used is preferably 0.5% to 10%, in particular 1% to 5%. But it can also be very effective, inorganic peracids such as persulfate and / or percarbonate are used. The amount of inorganic peracids is preferably 1% to 20%, in particular 10% to 20%, based on the total weight of the detergent and, if appropriate, and advantageously in combination with small amounts of catalytic bivalent metal salts, as described in US Pat. No. 4,655,782 and U.S. 4,655,953. Metal salts of copper and / or manganese are preferably used.
Selbstverständlich können auch Mischungen der organischen und/oder anorganischen Persäuren bzw. -Salzen eingesetzt werden.Mixtures of the organic and / or inorganic peracids or salts can of course also be used.
Die Zugabe der Persäuren in das Waschmittel erfolgt vor allem durch Mischen der Komponenten z.B. mit Hilfe von Schnecken-Dosier-Systemen und/oder Wirbelschicht-Mischern.The peracids are mainly added to the detergent by mixing the components e.g. with the help of 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 e.g. Pentasodium tripolyphosphate or substitute products such as phosphonates, polycarboxylates, acrylic-maleic copolymers, zeolites, nitrilotriacetate, ethylenediaminotetraacetic acid, soil suspending agents such as e.g. Sodium carboxymethyl cellulose, salts for adjusting the pH such as e.g. Alkali or alkaline earth silicates, foam regulators such as Soap, salts to adjust the spray drying and granulate properties such as Sodium sulfate, perfumes, and optionally antistatic and softening agents, enzymes, photobleaches, 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:
84 g Lineares Dodecylbenzolsulfonat
31 g Talgalkohol-tetradecan-äthylenglykoläther (14 AeO)
37 g Na-Seife (vorwiegend aus Behen-Säure und C₁₄-C₂₀)
458 g Na-Tripolyphosphat
79 g Na-Silikat
20g Mg-Silikat
12 g Carboxymethylcellulose
2 g Aethylendiamin-tetraacetat
222 g Na-Sulfat
1 g optische Aufheller (FWA) gemäss der Formel (I)-(II).The detergents of the following examples are produced in two stages by the usual method:
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:
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
20g magnesium silicate
12 g carboxymethyl cellulose
2 g ethylenediamine tetraacetate
222 g Na sulfate
1 g optical brightener (FWA) according to the formula (I) - (II).
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 mixed homogeneously into 500 g of this granulate A, which has a residual moisture of ∼5% 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.
- 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, in commercial washing powder-compatible cardboard packages, ie with a coating, stored 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 in percent, 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:
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 FWA determination mentioned above is carried out as follows:
The washing powder is homogenized well by grinding and 1 g of it is mixed with 200 ml Solvent consisting of 9 parts of dimethyl sulfoxide and 1 part of water is added, and the mixture is 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 absorbance is proportional to the FWA concentration. The reproducibility of the results is approx. ± 1% if the test conditions are observed exactly the same.
Beispiel: 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 (6)
- A storage-stable dry detergent comprising an organic peracid or salts thereof or mixtures thereof with other peracids or salts thereof, and a fluorescent whitening agent or a mixture of fluorescent whitening agents, which containsa) 0.5 to 30% of diperoxydodecanedioic acid as organic peracid or salts thereof or 0.5 to 30% of mixtures of diperoxydodecanedioic acid or salts thereof with other peracids or salts thereof andb) 0.03% to 0.5% of a fluorescent whitening agent or a mixture of fluorescent whitening agents of the formula (I)
- A detergent according to claim 1, which contains peracids or salts thereof which bleach textile material at a temperature from 20°C.
- A detergent according to claim 2, which contains, as a further peracid or peracid salt, a persulfate and/or a percarbonate with the addition of a catalyst.
- A detergent according to claim 1, which contains, as the fluorescent whitening agent, a compound of the formula (II)
- The use of a detergent according to claims 1 to 4, for washing textiles at temperatures of 20-60°C.
- The preparation of a detergent according to claims 1 to 4 by mixing the components with the aid of screw metering systems and/or fluidized bed mixers.
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CH502787 | 1987-12-23 | ||
| CH5027/87 | 1987-12-23 |
Publications (3)
| Publication Number | Publication Date |
|---|---|
| EP0321715A2 EP0321715A2 (en) | 1989-06-28 |
| EP0321715A3 EP0321715A3 (en) | 1989-08-09 |
| EP0321715B1 true EP0321715B1 (en) | 1994-06-15 |
Family
ID=4286688
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| EP88119487A Expired - Lifetime EP0321715B1 (en) | 1987-12-23 | 1988-11-23 | Stable detergents containing optical brighteners |
Country Status (8)
| Country | Link |
|---|---|
| EP (1) | EP0321715B1 (en) |
| JP (1) | JPH02138398A (en) |
| AU (1) | AU624094B2 (en) |
| BR (1) | BR8806216A (en) |
| DE (1) | DE3850232D1 (en) |
| ES (1) | ES2054775T3 (en) |
| MX (1) | MX169371B (en) |
| ZA (1) | ZA888794B (en) |
Families Citing this family (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| ES2065328T3 (en) * | 1987-11-26 | 1995-02-16 | Ciba Geigy Ag | STABLE DETERGENTS CONTAINING OPTIC BLEACHES. |
| GB8824108D0 (en) * | 1988-10-14 | 1988-11-23 | Unilever Plc | Bleaching & detergent compositions |
| US4970019A (en) * | 1988-10-27 | 1990-11-13 | Fmc Corporation | Particulate composition containing bleach and optical brightener and process for its manufacture |
| EP0394998B1 (en) * | 1989-04-28 | 1996-03-27 | Ciba-Geigy Ag | Liquid detergent |
| US5279772A (en) * | 1989-04-28 | 1994-01-18 | Ciba-Geigy Corporation | Liquid detergents containing specifically disulfonated dibenzofuranyl-biphenyls as flourescent whitening agents |
| MX9207050A (en) * | 1991-12-19 | 1993-06-01 | Ciba Geigy Ag | STABLE BLEACH DISPERSION DURING STORAGE |
Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP0317978A2 (en) * | 1987-11-26 | 1989-05-31 | Ciba-Geigy Ag | Stable detergents containing optical brighteners |
Family Cites Families (4)
| 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 |
| JPS529270B2 (en) * | 1973-06-14 | 1977-03-15 | ||
| ES2001074A6 (en) * | 1985-08-21 | 1988-04-16 | Clorox Co | Dry peracid based bleaching product. |
| GB8824108D0 (en) * | 1988-10-14 | 1988-11-23 | Unilever Plc | Bleaching & detergent compositions |
-
1988
- 1988-11-23 ES ES88119487T patent/ES2054775T3/en not_active Expired - Lifetime
- 1988-11-23 EP EP88119487A patent/EP0321715B1/en not_active Expired - Lifetime
- 1988-11-23 DE DE3850232T patent/DE3850232D1/en not_active Expired - Fee Related
- 1988-11-24 MX MX013913A patent/MX169371B/en unknown
- 1988-11-24 JP JP63294820A patent/JPH02138398A/en active Pending
- 1988-11-24 ZA ZA888794A patent/ZA888794B/en unknown
- 1988-11-25 BR BR888806216A patent/BR8806216A/en unknown
- 1988-11-25 AU AU25932/88A patent/AU624094B2/en not_active Ceased
Patent Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP0317978A2 (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, pppp. 360-362 * |
Also Published As
| Publication number | Publication date |
|---|---|
| AU624094B2 (en) | 1992-06-04 |
| ES2054775T3 (en) | 1994-08-16 |
| BR8806216A (en) | 1989-08-15 |
| ZA888794B (en) | 1989-08-30 |
| EP0321715A3 (en) | 1989-08-09 |
| EP0321715A2 (en) | 1989-06-28 |
| JPH02138398A (en) | 1990-05-28 |
| MX169371B (en) | 1993-06-30 |
| DE3850232D1 (en) | 1994-07-21 |
| AU2593288A (en) | 1989-07-06 |
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