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EP0337217B1 - Detergent containing a storage-stable bleach - Google Patents

Detergent containing a storage-stable bleach Download PDF

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Publication number
EP0337217B1
EP0337217B1 EP89105743A EP89105743A EP0337217B1 EP 0337217 B1 EP0337217 B1 EP 0337217B1 EP 89105743 A EP89105743 A EP 89105743A EP 89105743 A EP89105743 A EP 89105743A EP 0337217 B1 EP0337217 B1 EP 0337217B1
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EP
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Prior art keywords
weight
bleach
detergent
layered silicate
washing
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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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EP89105743A
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German (de)
French (fr)
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EP0337217A2 (en
EP0337217A3 (en
Inventor
Franz-Josef Dr. Dany
Werner Gohla
Günther Dr. Schimmel
Hans Peter Dr. Rieck
Ingrid Czeslik
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Clariant Produkte Deutschland GmbH
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Clariant GmbH
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Publication of EP0337217A3 publication Critical patent/EP0337217A3/en
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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
    • C11D3/395—Bleaching 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
    • C11D3/02—Inorganic compounds ; Elemental compounds
    • C11D3/12—Water-insoluble compounds
    • C11D3/124—Silicon containing, e.g. silica, silex, quartz or glass beads
    • C11D3/1246—Silicates, e.g. diatomaceous earth
    • C11D3/1253—Layer silicates, e.g. talcum, kaolin, clay, bentonite, smectite, montmorillonite, hectorite or attapulgite
    • C11D3/1273—Crystalline layered silicates of type NaMeSixO2x+1YH2O
    • 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
    • C11D3/3902—Organic or inorganic per-compounds combined with specific additives
    • C11D3/3905—Bleach activators or bleach catalysts
    • C11D3/3907—Organic compounds
    • C11D3/3917—Nitrogen-containing compounds

Definitions

  • TAED tetraacetylethylenediamine
  • Modern detergents therefore consist of a combination of Detergents as detergent substances, bleaches and the Detergent strengthening additives, the so-called builders, the remove the hardness of the wash liquor on the one hand and on the other hand Prevent deposits of inorganic salts on the laundry and thereby for a "soft grip" of the laundry after Ensure the washing process.
  • Polymeric phosphates are considered to be excellent builders, in particular Sodium tripolyphosphate. Because of the risk of eutrophication of the rivers and lakes due to the phosphate content in domestic wastewater the use of zeolites was proposed as a builder.
  • DE-34 16 669 A1 has therefore proposed that Detergent additionally 1 to 20 wt .-% crystalline layered silicate or add alkali silicate. This could make a "softer Handle "of the laundry can also be achieved when as a builder Zeolites are used; the storage stability of the detergent however, was not affected by this.
  • EP-A-0 263 520 describes a detergent which, in addition to the usual constituents, contains 0 to 5% by weight of a quaternary ammonium compound and 1 to 30% by weight of a plasticizer system consisting of 10 to 90% by weight of an alkylamine and 90 to 10% by weight of a crystalline sheet silicate of the formula Me 2 Si x O 2x + 1 .yH 2 O, in which Me contains an alkali metal or H, x is a number less than 7 and y is a number less than 7x.
  • EP-A-0 028 432 describes a detergent composition which contains, inter alia, sodium tripolyphosphate, insoluble silicates, TAED, alkylbenzyl sulfonates, ethoxylated C 15 alcohols, sodium perborate tetrahydrate, brighteners and sodium sulfate.
  • EP-A-0 634 484 describes packaged granules Detergent compositions where packaging determined Has water vapor permeability values.
  • the invention thus relates to a detergent of the type described above Kind, which is characterized in that it the bleach is sodium percarbonate and the amount of bleaching agent is such that 0.5 to 4 wt .-%, in particular 1.0 to 2.5% by weight of washing-active oxygen in the detergent available.
  • alkylbenzenesulfonates can act as a detergent, alkali salts of alkylbenzenesulfonates, higher Alkyl sulfonates and / or higher fatty alcohol polyethoxylate sulfates, especially with alkyl residues with an average of 10 contain up to 18 carbon atoms in the alkyl group.
  • carboxymethyl cellulose it can be used as a washing aid, carboxymethyl cellulose, carboxymethyl starch and / or methyl cellulose in amounts of up to 10 % By weight.
  • Crystalline layered silicates can according to the DE-34 13 571 A1 can be produced.
  • the determination of the wash-active oxygen (AVOX) of the bleach and the detergent was carried out according to Dr. (. NaBO 3 4H 2 O) E. Heinerth, surfactants, 2 (1965) 180.
  • the investigated sodium perborate tetrahydrate had a AVOX number of from 10% by weight; the sodium perborate monohydrate (NaBO 3 .H 2 O) had an AVOX number of 15% by weight; the sodium percarbonate (2 Na 2 CO 3 .3H 2 O 2 ) had an AVOX number of 13.5% by weight.
  • the washing power (bleaching effect) of the detergent was determined as Whiteness of the test fabrics (WFK polyester / cotton with Tea soiling, order code 20 G) determined according to DIN 44983.
  • the storage tests were carried out according to the following forced test conditions:
  • the detergent to be examined was stored in a climatic cabinet at a relative humidity of 70% at a temperature of 37 ° C.
  • the detergent was packed in a wax box.
  • the water vapor permeability of the packaging was 0.4 g / m 2 ⁇ h.
  • Table 1 shows the detergent formulations tested listed.
  • Table 2 shows the degradation values of the bleaching agent in Depends on the time after the forced storage test conditions compiled.
  • two were commercially available Detergent based on zeolite and sodium tripolyphosphate included in Table 2.
  • the bleach breakdown, especially sodium percarbonate is present of zeolite very large.
  • Table 3 lists the test results according to DIN 44983 for the different detergent formulations which were determined in accordance with equation I. It can be seen from the test values that the bleaching action is increased when crystalline layered silicate is used as the builder instead of zeolite. In the presence of TAED there is a synergistic increase in the washing power (bleaching effect) of the detergent.

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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)
  • Crystallography & Structural Chemistry (AREA)
  • Detergent Compositions (AREA)

Description

Die vorliegende Erfindung betrifft ein Waschmittel mit lagerstabilisiertem Bleichsystem, enthaltend 10 bis 50 Gew.-% kristallines Natriumschichtsilikat der Formel NaMSixO2x+1 · y H2O, worin x = 1,9 bis 4,0, M = Na oder H, y = 0 bis 20 bedeutet, 1 bis 5 Gew.-% Tetraacetylethylendiamin (TAED) sowie 2 bis 20 Gew.-% Detergentien und üblichen Waschhilfsstoffe, einschließlich Füllstoffe sowie ein Bleichmittel, insbesondere ein Haushaltswaschmittel für Grob-, Weiß- und Buntwäsche, wie es in Waschautomaten verwendet wird.The present invention relates to a detergent with a storage-stabilized bleaching system containing 10 to 50% by weight of crystalline layered sodium silicate of the formula NaMSi x O 2x + 1 .yH 2 O, where x = 1.9 to 4.0, M = Na or H , y = 0 to 20 means 1 to 5% by weight of tetraacetylethylenediamine (TAED) and 2 to 20% by weight of detergents and customary washing aids, including fillers and a bleach, in particular a household detergent for rough, white and colored laundry, as used in washing machines.

Durch die zunehmende Verbreitung von Haushaltswaschautomaten muß das Waschmittel den geänderten Waschbedingungen angepaßt werden.Due to the increasing spread of household washing machines the detergent can be adapted to the changed washing conditions.

Moderne Waschmittel bestehen deshalb aus einer Kombination von Detergentien als waschaktive Substanzen, Bleichmitteln und die Waschkraft verstärkenden Zusätzen, den sogenannten Buildern, die einerseits die Härte der Waschlauge beseitigen und andererseits Ablagerungen von anorganischen Salzen auf dem Waschgut verhindern und dadurch für einen "weichen Griff" des Waschgutes nach dem Waschvorgang sorgen.Modern detergents therefore consist of a combination of Detergents as detergent substances, bleaches and the Detergent strengthening additives, the so-called builders, the remove the hardness of the wash liquor on the one hand and on the other hand Prevent deposits of inorganic salts on the laundry and thereby for a "soft grip" of the laundry after Ensure the washing process.

Als hervorragende Builder gelten polymere Phosphate, insbesondere Natriumtripolyphosphat. Wegen der Eutrophierungsgefahr der Flüsse und Seen durch den Phosphatgehalt in den häuslichen Abwässern wurde als Builder die Verwendung von Zeolithen vorgeschlagen. Polymeric phosphates are considered to be excellent builders, in particular Sodium tripolyphosphate. Because of the risk of eutrophication of the rivers and lakes due to the phosphate content in domestic wastewater the use of zeolites was proposed as a builder.

Es hat sich gezeigt, daß der Gebrauch von Zeolithen als Builder die Nachteile hat, daß das Waschgut im Verlaufe von mehreren Waschvorgängen den erwünschten "weichen Griff" verliert. Hinzu kommt, daß während der Lagerzeit, die zwischen der Herstellung und dem Verbrauch des Waschmittels liegt, das Waschmittel durch Zersetzung des Bleichmittels teilweise seine Waschkraft einbüßt.It has been shown that the use of zeolites as a builder has the disadvantages that the laundry is in the course of several Washing processes lose the desired "soft feel". In addition that comes during the storage period between manufacture and the consumption of the detergent lies through the detergent Decomposition of the bleaching agent loses some of its washing power.

In der DE-34 16 669 A1 ist deshalb vorgeschlagen worden, dem Waschmittel zusätzlich 1 bis 20 Gew.-% kristallines Schichtsilikat oder Alkalisilikat zuzusetzen. Hierdurch konnte eine "weicher Griff" des Waschgutes auch dann erreicht werden, wenn als Builder Zeolithe verwendet werden; die Lagerstabilität des Waschmittels wurde jedoch hierdurch nicht beeinflußt.DE-34 16 669 A1 has therefore proposed that Detergent additionally 1 to 20 wt .-% crystalline layered silicate or add alkali silicate. This could make a "softer Handle "of the laundry can also be achieved when as a builder Zeolites are used; the storage stability of the detergent however, was not affected by this.

Die EP-A-0 263 520 beschreibt ein Waschmittel, das neben den üblichen Bestandteilen 0 bis 5 Gew.-% einer quarternären Ammoniumverbindung sowie 1 bis 30 Gew.-% eines Weichmachersystems, bestehend aus 10 bis 90 Gew.-% eines Alkylamins und 90 bis 10 Gew.-% eines kristallinen Schichtsilikats der Formel Me2SixO2x+1 · y H2O, in der Me ein Alkalimetall oder H, x eine Zahl kleiner 7 und y eine Zahl kleiner 7x bedeutet, enthält.EP-A-0 263 520 describes a detergent which, in addition to the usual constituents, contains 0 to 5% by weight of a quaternary ammonium compound and 1 to 30% by weight of a plasticizer system consisting of 10 to 90% by weight of an alkylamine and 90 to 10% by weight of a crystalline sheet silicate of the formula Me 2 Si x O 2x + 1 .yH 2 O, in which Me contains an alkali metal or H, x is a number less than 7 and y is a number less than 7x.

Die EP-A-0 028 432 beschreibt eine Waschmittelzusammensetzung, die u.a. Natriumtripolyphosphat, unlösliche Silikate, TAED, Alkylbenzylsulfonate, ethoxylierte C15-Alkohole, Natriumperborat-Tetrahydrat, Aufheller und Natriumsulfat enthält.EP-A-0 028 432 describes a detergent composition which contains, inter alia, sodium tripolyphosphate, insoluble silicates, TAED, alkylbenzyl sulfonates, ethoxylated C 15 alcohols, sodium perborate tetrahydrate, brighteners and sodium sulfate.

Schließlich beschreibt die EP-A-0 634 484 verpackte granulare Waschmittelzusammensetzungen, bei der die Verpackung bestimmte Wasserdampfdurchlässigkeitswerte aufweist. Finally, EP-A-0 634 484 describes packaged granules Detergent compositions where packaging determined Has water vapor permeability values.

Keines der vorgenannten Dokumente beschreibt jedoch ein Waschmittel, welches zugleich bei verstärkter Bleichwirkung und verbesserter Lagerstabilität den "weichen Griff" aufrechterhält.However, none of the aforementioned documents describes a detergent which at the same time with increased bleaching effect and improved Storage stability maintains the "soft grip".

Die Erfindung betrifft somit ein Waschmittel der eingangs beschriebenen Art, welches dadurch gekennzeichnet ist, daß es sich bei dem Bleichmittel um Natriumpercarbonat handelt und die Menge an Bleichmittel so bemessen ist, daß 0,5 bis 4 Gew.-%, insbesondere 1,0 bis 2,5 Gew.-% waschaktiver Sauerstoff im Waschmittel vorliegen.The invention thus relates to a detergent of the type described above Kind, which is characterized in that it the bleach is sodium percarbonate and the amount of bleaching agent is such that 0.5 to 4 wt .-%, in particular 1.0 to 2.5% by weight of washing-active oxygen in the detergent available.

Das erfindungsgemäße Waschmittel kann weiterhin bevorzugt und wahlweise dadurch gekennzeichnet sein, daß

  • a) das kristalline Schichtsilikat einen Teilchendurchmesser von 0,01 bis 1000 µm, insbesondere von 1 bis 20 µm, hat;
  • b) das kristalline Schichtsilikat eine Ionenaustauschkapazität von 400 bis 1200 mmol Na+/100 g wasserfreie Substanz hat;
  • c) es anorganische und/oder organische Phosphate, Borate, Zitrate, Gluconate, Nitrilotriessigsäure und/oder Iminodiacetate als zusätzliche Builder in Mengen von bis zu 20 Gew.-% enthält;
  • d) es aus Agglomeratteilchen mit einer Teilchengröße im Bereich von 0,25 bis 2,5 mm besteht und durch einen Sprühnebelmischprozeß erhalten wurde.
    • The detergent according to the invention can also be preferred and optionally characterized in that
  • a) the crystalline layered silicate has a particle diameter of from 0.01 to 1000 μm, in particular from 1 to 20 μm;
  • b) the crystalline layered silicate has an ion exchange capacity of 400 to 1200 mmol Na + / 100 g of anhydrous substance;
  • c) it contains inorganic and / or organic phosphates, borates, citrates, gluconates, nitrilotriacetic acid and / or iminodiacetates as additional builders in amounts of up to 20% by weight;
  • d) it consists of agglomerate particles with a particle size in the range from 0.25 to 2.5 mm and was obtained by a spray mixing process.

    • Es kann als Detergent Alkalisalze von Alkylbenzolsulfonaten, höheren Alkylsulfonaten und/oder höheren Fettalkoholpolyetehoxylatsulfaten, insbesondere mit Alkylresten mit durchschnittlich 10 bis 18 C-Atomen in der Alkylgruppe enthalten.It can act as a detergent, alkali salts of alkylbenzenesulfonates, higher Alkyl sulfonates and / or higher fatty alcohol polyethoxylate sulfates, especially with alkyl residues with an average of 10 contain up to 18 carbon atoms in the alkyl group.

    Es kann als Waschhilfsstoff Carboxymethylcellulose, Carboxymethylstärke und/oder Methylcellulose in Mengen von bis zu 10 Gew.-% enthalten.It can be used as a washing aid, carboxymethyl cellulose, carboxymethyl starch and / or methyl cellulose in amounts of up to 10 % By weight.

    Die bei der Herstellung des erfindungsgemäßen Waschmittels eingesetzten kristallinen Schichtsilikate können gemäß der DE-34 13 571 A1 hergestellt werden. The used in the manufacture of the detergent according to the invention Crystalline layered silicates can according to the DE-34 13 571 A1 can be produced.

    Die Bestimmung des waschaktiven Sauerstoffs (AVOX) des Bleichmittels als auch des Waschmittels erfolgte nach der Vorschrift von Dr. E. Heinerth, Tenside 2 (1965) 180. Das untersuchte Natriumperborat-Tetrahydrat (NaBO3 . 4 H2O) hatte eine AVOX-Zahl von 10 Gew%; das Natriumperborat-Monohydrat (NaBO3 · H2O) hatte eine AVOX-Zahl von 15 Gew%; das Natriumpercarbonat (2 Na2CO3 · 3 H2O2) hatte eine AVOX-Zahl von 13,5 Gew%.The determination of the wash-active oxygen (AVOX) of the bleach and the detergent was carried out according to Dr. (. NaBO 3 4H 2 O) E. Heinerth, surfactants, 2 (1965) 180. The investigated sodium perborate tetrahydrate had a AVOX number of from 10% by weight; the sodium perborate monohydrate (NaBO 3 .H 2 O) had an AVOX number of 15% by weight; the sodium percarbonate (2 Na 2 CO 3 .3H 2 O 2 ) had an AVOX number of 13.5% by weight.

    Die Waschkraft (Bleichwirkung) des Waschmittels wurde als Weißgrad der Testgewebe (WFK-Polyester/Baumwolle mit Tee-Anschmutzung, Order-Code 20 G) gemäß der DIN 44983 ermittelt.The washing power (bleaching effect) of the detergent was determined as Whiteness of the test fabrics (WFK polyester / cotton with Tea soiling, order code 20 G) determined according to DIN 44983.

    Die Waschkraft (Bleichwirkung) der Waschflotte wurde nach der Differenzmethode ermittelt, die sich aus der Gleichung I % WK = % WGg - % WGb ergibt. Es bedeutet:

  • % WK = % Waschkraft (Bleichwirkung)
  • % WGg = % Weißgrad des gewaschenen Stoffes
  • % WGb = % Weißgrad des ungewaschenen Stoffes.
    • The washing power (bleaching effect) of the wash liquor was determined using the difference method, which is derived from equation I % WK =% WG G -% flat share b results. It means:
  • % WK =% washing power (bleaching effect)
  • % WG g =% whiteness of the washed fabric
  • % WG b =% whiteness of the unwashed fabric.

    • Die Lagerteste wurden nach folgenden forcierten Testbedingungen gemacht:
    Im Klimaschrank wurde das zu untersuchende Waschmittel bei einer relativen Luftfeuchtigkeit von 70 % bei einer Temperatur von 37°C gelagert. Das Waschmittel war dabei in einem Wachs-Karton verpackt. Die Wasserdampfdurchlässigkeit der Verpackung betrug 0,4 g/m2 · h.    The storage tests were carried out according to the following forced test conditions:
    The detergent to be examined was stored in a climatic cabinet at a relative humidity of 70% at a temperature of 37 ° C. The detergent was packed in a wax box. The water vapor permeability of the packaging was 0.4 g / m 2 · h.

    In der Tabelle 1 sind die getesteten Waschmittelformulierungen aufgelistet.Table 1 shows the detergent formulations tested listed.

    In der Tabelle 2 sind die Abbauwerte des Bleichmittels in Abhängigkeit von der Zeit nach den forcierten Lagertestbedingungen zusammengestellt. Zusätzlich wurden zwei handelsübliche Waschmittel auf Zeolith- und Natriumtripolyphosphat-Basis in die Tabelle 2 aufgenommen. Der Bleichmittelabbau, insbesondere von Natriumpercarbonat, ist in Anwesenheit von Zeolith sehr groß.Table 2 shows the degradation values of the bleaching agent in Depends on the time after the forced storage test conditions compiled. In addition, two were commercially available Detergent based on zeolite and sodium tripolyphosphate included in Table 2. The bleach breakdown, especially sodium percarbonate is present of zeolite very large.

    In der Tabelle 3 sind die Versuchsergebnisse entsprechend der DIN 44983 für die verschiedenen Waschmittelformulierungen, die gemäß Gleichung I bestimmt wurden, aufgelistet.
    Aus den Testwerten ist zu entnehmen, daß die Bleichmittelwirkung gesteigert wird, wenn als Builder kristallines Schichtsilikat anstelle von Zeolith eingesetzt wird. In Anwesenheit von TAED erfolgt eine synergistisch gesteigerte Waschkraft (Bleichwirkung) des Waschmittels.    Table 3 lists the test results according to DIN 44983 for the different detergent formulations which were determined in accordance with equation I.
    It can be seen from the test values that the bleaching action is increased when crystalline layered silicate is used as the builder instead of zeolite. In the presence of TAED there is a synergistic increase in the washing power (bleaching effect) of the detergent.

    Die Griffbeurteilung durch ein Gremium von Experten ergab einen deutlich "weicheren Griff" des Waschgutes, welches mit erfindungsgemäßen Waschmitteln gemäß den Beispielen 2 und 3 gewaschen war, gegenüber dem Waschgut, welches mit zeolithhaltigem Waschmittel gemäß den Beispielen 1 und 4 gewaschen war.

    Figure 00070001
    Figure 00080001
    Figure 00090001
    The handle assessment by a panel of experts resulted in a significantly "softer handle" of the laundry which had been washed with detergents according to the invention according to Examples 2 and 3 compared to the laundry which had been washed with zeolite-containing detergent according to Examples 1 and 4.
    Figure 00070001
    Figure 00080001
    Figure 00090001

    Claims (6)

    1. A process for the preparation of a washing agent with a storage-stabilized bleach system by mixing 10 to 50% by weight of a crystalline sodium layered silicate of the formal NaMSixO2x+1 · yH2O, where x = 1.9 to 4.0, M = Na or H, y = 0 to 20, 1 to 5% by weight of tetraacetylethylenediamine (TAED), 2 to 20% by weight of detergents and conventional washing auxiliaries including fillers and a bleach, wherein the bleach is sodium percarbonate and the quantity of bleach is such that 0.5 to 4% by weight, in particular 1.0 to 2.5% by weight of washing-active oxygen are present in the washing agent.
    2. The process as claimed in claim 1, wherein a crystalline layered silicate of the δ-modification of Na2Si2O5 is mixed in.
    3. The process as claimed in claim 1 or 2, wherein a crystalline layered silicate having particle diameters from 0.01 to 1,000 µm in particular from 1 to 20 µm, is mixed in.
    4. The process as claimed in one of claims 1 to 3, wherein a crystalline layered silicate having an ion exchange capacity from 400 to 1,200 mmol of Na+/100 g of dry matter is mixed in.
    5. The process as claimed in one of claims 1 to 4, wherein inorganic and/ or organic phosphates, borates, citrates, gluconates, nitrilotriacetic acid and/or iminodiacetates are mixed in as additional builders in quantities of up to 20% by weight.
    6. The process as claimed in claim 1, wherein the washing agent formulation is processed in a spraymist mixing process with the formation of agglomerate particles having a particle size in the range from 0.25 to 2.5 mm.
    EP89105743A 1988-04-15 1989-04-01 Detergent containing a storage-stable bleach Expired - Lifetime EP0337217B1 (en)

    Applications Claiming Priority (2)

    Application Number Priority Date Filing Date Title
    DE3812556 1988-04-15
    DE3812556A DE3812556A1 (en) 1988-04-15 1988-04-15 DETERGENT WITH STORAGE-STABILIZED BLEACHING SYSTEM

    Publications (3)

    Publication Number Publication Date
    EP0337217A2 EP0337217A2 (en) 1989-10-18
    EP0337217A3 EP0337217A3 (en) 1991-04-10
    EP0337217B1 true EP0337217B1 (en) 1999-09-01

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    Application Number Title Priority Date Filing Date
    EP89105743A Expired - Lifetime EP0337217B1 (en) 1988-04-15 1989-04-01 Detergent containing a storage-stable bleach

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    US (1) US5078895A (en)
    EP (1) EP0337217B1 (en)
    JP (1) JPH0633420B2 (en)
    KR (1) KR910006073B1 (en)
    CA (1) CA1311982C (en)
    DE (2) DE3812556A1 (en)
    DK (1) DK169287B1 (en)
    ES (1) ES2137916T3 (en)
    FI (1) FI91882C (en)
    NO (1) NO172901C (en)

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    DK181989A (en) 1989-10-16
    ES2137916T3 (en) 2000-01-01
    NO891546L (en) 1989-10-16
    NO172901B (en) 1993-06-14
    DE3812556A1 (en) 1989-10-26
    NO891546D0 (en) 1989-04-14
    KR910006073B1 (en) 1991-08-12
    EP0337217A2 (en) 1989-10-18
    NO172901C (en) 1993-09-22
    US5078895A (en) 1992-01-07
    DK181989D0 (en) 1989-04-14
    JPH0297600A (en) 1990-04-10
    FI91882C (en) 1994-08-25
    DE58909855D1 (en) 1999-10-07
    FI91882B (en) 1994-05-13
    FI891766L (en) 1989-10-16
    EP0337217A3 (en) 1991-04-10
    CA1311982C (en) 1992-12-29
    KR900016447A (en) 1990-11-13
    JPH0633420B2 (en) 1994-05-02
    DK169287B1 (en) 1994-10-03
    FI891766A0 (en) 1989-04-13

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