EP0322564A2 - Stable detergents containing optical brighteners - Google Patents

Stable detergents containing optical brighteners Download PDF

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Publication number
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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Prior art keywords
formula
hydrogen
compound
optical brightener
halogen
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EP88119486A
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German (de)
French (fr)
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EP0322564A3 (en
EP0322564B1 (en
Inventor
Claude Dr. Eckhardt
Heinz Dr. Hefti
Hans Rudolf Dr. Meyer
Kurt Dr. Weber
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BASF Schweiz AG
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Ciba Geigy AG
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Classifications

    • CCHEMISTRY; METALLURGY
    • C11ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11DDETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D3/00Other compounding ingredients of detergent compositions covered in group C11D1/00
    • C11D3/39Organic or inorganic per-compounds
    • C11D3/3942Inorganic per-compounds
    • CCHEMISTRY; METALLURGY
    • C11ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11DDETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D3/00Other compounding ingredients of detergent compositions covered in group C11D1/00
    • C11D3/39Organic or inorganic per-compounds
    • C11D3/3945Organic per-compounds
    • CCHEMISTRY; METALLURGY
    • C11ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11DDETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D3/00Other compounding ingredients of detergent compositions covered in group C11D1/00
    • C11D3/40Dyes ; Pigments
    • C11D3/42Brightening 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:

Abstract

Detergents which, besides inorganic and/or organic peracids, contain specific stilbene compounds as optical brighteners are stable for several months and show the usual cleaning properties even at washing temperatures of 20-60 DEG C.

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)

Figure imgb0001
worin
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)
Figure imgb0001
wherein
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

Figure imgb0002
mit R = H oder Halogen und M in der oben angegebenen Bedeutung,
Figure imgb0003
mit R₁, R₂ = H, C₁-C₄-Alkyl und R₃ = -SO₃M oder
Figure imgb0004
und M in der oben angegebenen Bedeutung,
Figure imgb0005
mit M in der oben angegebenen Bedeutung,
und/oder
Figure imgb0006
mit M in der oben angegebenen Bedeutung.In particular, the detergents contain compounds of the formulas as brighteners
Figure imgb0002
with R = H or halogen and M in the meaning given above,
Figure imgb0003
with R₁, R₂ = H, C₁-C₄-alkyl and R₃ = -SO₃M or
Figure imgb0004
and M in the meaning given above,
Figure imgb0005
with M in the meaning given above,
and or
Figure imgb0006
with M in the meaning given above.

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.

WaschmittelzubereitungDetergent preparation

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 20 g Mg-Silikat 12 g Carboxymethylcellulose 2 g Aethylendiamin-tetraacetat 222 g Na-Sulfat 1 g optische Aufheller (FWA) gemäss der Formel (II)-(V).
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 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).

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.

LagertestStorage test

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.

Beispiel :For example:

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:

Figure imgb0007
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:
Figure imgb0007

Claims (9)

1. Lagerstabile Waschmittel dadurch gekennzeichnet, dass sie 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)
Figure imgb0008
enthalten, worin
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)
Figure imgb0008
included in what
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.
2. Mittel nach Anspruch 1, das Persäuren oder deren Salze enthält, die bei einer Temperatur ab 20°C Textilmaterial bleichen.2. Composition according to claim 1, which contains peracids or their salts which bleach textile material at a temperature above 20 ° C. 3. Mittel nach Anspruch 2, das als Persäure bzw. -Salz Persulfat und/oder Percarbonat mit Katalysator-Zusatz enthält.3. Composition according to claim 2, which contains persulfate and / or percarbonate with added catalyst as the peracid or salt. 4. Mittel nach Anspruch 1, das als optischen Aufheller eine Verbindung der Formel (II)
Figure imgb0009
mit R = H oder Halogen und M in der in Anspruch 1 angegebenen Bedeutung enthält.
4. Means according to claim 1, the optical brightener, a compound of formula (II)
Figure imgb0009
with R = H or halogen and M in the meaning given in claim 1.
5. Mittel nach Anspruch 1, das als optischen Aufheller eine Verbindung der Formel (III)
Figure imgb0010
mit R₁, R₂ = H, C₁-C₄-Alkyl und R₃ = -SO₃M oder
Figure imgb0011
und M in der in Anspruch 1 angegebenen Bedeutung enthält.
5. Means according to claim 1, which as optical brightener is a compound of formula (III)
Figure imgb0010
with R₁, R₂ = H, C₁-C₄-alkyl and R₃ = -SO₃M or
Figure imgb0011
and M has the meaning given in claim 1.
6. Mittel nach Anspruch 1, das als optischen Aufheller eine Verbindung der Formel (IV)
Figure imgb0012
mit M in der in Anspruch 1 angegebenen Bedeutung enthält.
6. Composition according to claim 1, which as an optical brightener a compound of formula (IV)
Figure imgb0012
with M in the meaning given in claim 1.
7. Mittel nach Anspruch 1, das als optischen Aufheller eine Verbindung der Formel (V)
Figure imgb0013
mit M in der in Anspruch 1 angegebenen Bedeutung enthält.
7. Composition according to claim 1, which as an optical brightener a compound of formula (V)
Figure imgb0013
with M in the meaning given in claim 1.
8. Verwendung der Mittel gemäss den Ansprüchen 1 bis 7 zum Waschen von Textilien bei Temperaturen von 20-60°C.8. Use of the agent according to claims 1 to 7 for washing textiles at temperatures of 20-60 ° C. 9. Herstellung der Mittel gemäss den Ansprüchen 1 bis 7 durch trockenes Mischen mit Hilfe von automatischen Schnecken-Dosier-Systemen und/oder Wirbelschicht-Mischern.9. Preparation of the compositions according to claims 1 to 7 by dry mixing using automatic screw metering systems and / or fluidized bed mixers.
EP88119486A 1987-12-23 1988-11-23 Stable detergents containing optical brighteners Expired - Lifetime EP0322564B1 (en)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
CH5009/87 1987-12-23
CH500987 1987-12-23

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EP0322564A3 EP0322564A3 (en) 1989-08-30
EP0322564B1 EP0322564B1 (en) 1994-06-15

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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)

* Cited by examiner, † Cited by third party
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)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0317979B1 (en) * 1987-11-26 1994-12-07 Ciba-Geigy Ag Stable detergents containing optical brighteners
KR100351295B1 (en) * 2000-03-29 2002-09-05 김기식 Hangers of device for cheeking safety of presses

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CH612817B (en) * 1974-06-12 Ciba Geigy Ag USE OF STYLE COMPOUNDS FOR THE OPTICAL LIGHTENING OF TEXTILE ORGANIC MATERIALS.
CH610478B (en) * 1974-06-12 Ciba Geigy Ag USE OF DISTILBENYL OXADIAZOLES 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
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CH612817B (en) * 1974-06-12 Ciba Geigy Ag USE OF STYLE COMPOUNDS FOR THE OPTICAL LIGHTENING OF TEXTILE ORGANIC MATERIALS.
CH610478B (en) * 1974-06-12 Ciba Geigy Ag USE OF DISTILBENYL OXADIAZOLES 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
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Cited By (8)

* Cited by examiner, † Cited by third party
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
JPH01172497A (en) 1989-07-07
JP2634453B2 (en) 1997-07-23
AU624587B2 (en) 1992-06-18
AU2593588A (en) 1989-07-06
ES2054774T3 (en) 1994-08-16
BR8806215A (en) 1989-08-15
EP0322564A3 (en) 1989-08-30
DE3850234D1 (en) 1994-07-21
ZA888793B (en) 1989-08-30
EP0322564B1 (en) 1994-06-15

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