EP0337219B1 - Storage stabilized detergent with increased bleaching effect - Google Patents

Storage stabilized detergent with increased bleaching effect Download PDF

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Publication number
EP0337219B1
EP0337219B1 EP89105745A EP89105745A EP0337219B1 EP 0337219 B1 EP0337219 B1 EP 0337219B1 EP 89105745 A EP89105745 A EP 89105745A EP 89105745 A EP89105745 A EP 89105745A EP 0337219 B1 EP0337219 B1 EP 0337219B1
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Prior art keywords
weight
detergent
layered silicate
washing
mixed
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EP89105745A
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German (de)
French (fr)
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EP0337219A3 (en
EP0337219A2 (en
Inventor
Franz-Josef Dr. Dany
Werner Dr. 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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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
    • C11D3/39—Organic or inorganic per-compounds
    • C11D3/3902—Organic or inorganic per-compounds combined with specific additives
    • C11D3/3937—Stabilising 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

Definitions

  • Modern detergents therefore consist of a combination of detergents as wash-active Substances, bleaching agents and additives that increase washing power, the so-called builders, which on the one hand remove the hardness of the wash liquor and on the other hand deposits of inorganic Prevent salting on the laundry and thereby for a "soft grip" of the laundry care after washing.
  • Polymeric phosphates in particular sodium tripolyphosphate, are considered to be excellent builders. Because of the risk of eutrophication of the rivers and lakes by the phosphate content in the domestic Sewage has been suggested to use zeolites as a builder.
  • 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 granular detergent compositions where the packaging has certain water vapor permeability values.
  • the invention is therefore based on the object of providing a detergent which is improved Has storage stability and an increased bleaching effect as well as the "soft" in the laundry Grip 'maintained.
  • a detergent of the type mentioned at the outset characterized in that that the bleach is sodium percarbonate and the amount of Bleaching agent is such that 0.5 to 4% by weight, in particular 1.0 to 2.5% by weight, is more active in washing There is oxygen in the detergent.
  • the crystalline sheet silicates used in the preparation of the detergent according to the invention can be prepared according to DE-34 13 571 A1. Although all of the crystalline sheet silicates listed in DE-34 13 571 A1 can be used in the detergent according to the invention, it has been shown that ⁇ -Na 2 Si 2 O 5 should be given preference if there is an increased bleaching effect in the Washing process arrives.
  • the determination of the wash-active oxygen (AVOX) of the bleach and the detergent was carried out according to Dr. E. Heinerth, Tenside 2 (1965) 180.
  • the sodium perborate tetrahydrate (NaBO 3 .4H 2 O) investigated had an AVOX number of 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 staining, 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 bleach in Depends on the time after the forced storage test conditions compiled.
  • 2 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.
  • the detergent formulations were in accordance with DIN 44983 2 and 4 tested and calculated according to equation I.
  • the washing power (bleaching effect) of the detergent 2 was 30.0%; that of the detergent according to the invention was 4 36.5%.

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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 Erfindung betrifft ein lagerstabiles Waschmittel, enthaltend 10 bis 50 Gew.-% kristallines Natriumschichtsilikat der Formel NaMSi2O5, in der M = Na oder H ist, 2 bis 20 Gew.-% Detergentien und übliche Waschhilfsstoffe einschließlich Füllstoffe sowie ein Bleichmittel, wie es in Waschautomaten verwendet wird.The invention relates to a storage-stable detergent containing 10 to 50% by weight of crystalline layered sodium silicate of the formula NaMSi 2 O 5 , in which M = Na or H, 2 to 20% by weight of detergents and customary washing aids including fillers and a bleaching agent, 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 has to be changed Washing conditions can be adjusted.

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 wash-active Substances, bleaching agents and additives that increase washing power, the so-called builders, which on the one hand remove the hardness of the wash liquor and on the other hand deposits of inorganic Prevent salting on the laundry and thereby for a "soft grip" of the laundry care after washing.

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, in particular sodium tripolyphosphate, are considered to be excellent builders. Because of the risk of eutrophication of the rivers and lakes by the phosphate content in the domestic Sewage has been suggested to use zeolites 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 loses the desired "soft feel" in the course of several washes. In addition that comes during the storage period between the manufacture and consumption of the detergent lies, the detergent partially decomposes its bleaching power loses.

In der DE-34 16 669 Al ist deshalb vorgeschlagen worden, dem Waschmittel zusätzlich 1 bis 20 Gew.-% kristallines Schichtsilikat oder Alkalisilikat zuzusetzen. Hierdurch konnte ein "weicher Griff' des Waschgutes auch dann erreicht werden, wenn als Builder Zeolithe verwendet weren; die Lagerstabilität des Waschmittels wurde jedoch hierdurch nicht beeinflußt.In DE-34 16 669 A1 it has therefore been proposed to add 1 to 20 to the detergent % By weight of crystalline layered silicate or alkali silicate. This allowed a "softer Handles' of the laundry can also be achieved if zeolites are used as builders; however, the storage stability of the detergent was not affected by this.

Die EP-A-0 263 520 beschreibt ein Waschmittel, das neben den üblichen Bestandteilen 0 bis 5 Gew.-% einer quartären Ammoniumverbindung sowie 1 bis 30 Gew.-% eines Weichmachersy stems, bestehend aus 10 bis 90 Gew.-% eines Alkylamins und 90 bis 10 Gew.-% eines kristallinen Schichtsilikats der Formel Me2SixO2x+1 · yH2O, 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 granular detergent compositions where the packaging has certain 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 above-mentioned documents describes a detergent which is also used in an intensified Bleaching effect and improved storage stability maintains the "soft feel".

Der Erfindung liegt daher die Aufgabe zugrunde, ein Waschmittel bereitzustellen, das eine verbesserte Lagerstabilität und eine verstärkte Bleichwirkung hat sowie im Waschgut den "weichen Griff' aufrechterhält.The invention is therefore based on the object of providing a detergent which is improved Has storage stability and an increased bleaching effect as well as the "soft" in the laundry Grip 'maintained.

Diese Aufgabe wird gelöst durch ein Waschmittel der eingangs genannten Art, daduch gekennzeichnet, 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. This object is achieved by a detergent of the type mentioned at the outset, characterized in that that the bleach is sodium percarbonate and the amount of Bleaching agent is such that 0.5 to 4% by weight, in particular 1.0 to 2.5% by weight, is more active in washing There is oxygen in the detergent.

Ganz besonders gute Ergebnisse werden erzielt, wenn das kristalline Schichtsilikat der δ-Modifikation des Na2Si2O5 entspricht.Particularly good results are achieved if the crystalline layered silicate corresponds to the δ modification of Na 2 Si 2 O 5 .

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

  • a) das kristalline Schichtsilikat einen Teilchendurchmesser von 0,01 bis 1000 um, 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 (NTA) 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 0.01 to 1000 μm, in particular of 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 (NTA) 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.

    • Die bei der Herstellung des erfindungsgemäßen Waschmittels eingesetzten kristallinen Schichtsilikate können gemäß der DE-34 13 571 A1 hergestellt werden. Obwohl alle in der DE-34 13 571 A1 aufgeführten kristallinen Schichtsilikate in das erfindungsgemäße Waschmittel eingesetzt werden können, hat es sich gezeigt, daß dem δ-Na2Si2O5 der Vorzug dann zu geben ist, wenn es auf eine erhöhte Bleichwirkung beim Waschvorgang ankommt.The crystalline sheet silicates used in the preparation of the detergent according to the invention can be prepared according to DE-34 13 571 A1. Although all of the crystalline sheet silicates listed in DE-34 13 571 A1 can be used in the detergent according to the invention, it has been shown that δ-Na 2 Si 2 O 5 should be given preference if there is an increased bleaching effect in the Washing process arrives.

    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. E. Heinerth, Tenside 2 (1965) 180. The sodium perborate tetrahydrate (NaBO 3 .4H 2 O) investigated had an AVOX number of 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 staining, 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 2 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 bleach in Depends on the time after the forced storage test conditions compiled. In addition, 2 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.

    Waschergebnisse:Washing results:

    Entsprechend der DIN 44983 wurden die Waschmittelformulierungen 2 und 4 getestet und nach Gleichung I berechnet. Die Waschkraft (Bleichwirkung) des Waschmittels 2 betrug 30,0 %; die des erfindungsgemäßen Waschmittels 4 betrug 36,5 %.The detergent formulations were in accordance with DIN 44983 2 and 4 tested and calculated according to equation I. The washing power (bleaching effect) of the detergent 2 was 30.0%; that of the detergent according to the invention was 4 36.5%.

    Die Griffbeurteilung durch ein Gremium von Experten ergab einen deutlich "weicheren Griff" des Waschgutes, welches mit dem erfindungsgemäßen Waschmittel 4 gewaschen war, gegenüber dem Waschgut, welches mit dem zeolithhaltigen Waschmittel 2 gewaschen war.

    Figure 00060001
    Figure 00070001
    The handle assessment by a panel of experts resulted in a significantly "softer handle" of the laundry, which had been washed with the detergent 4 according to the invention, compared to the laundry, which had been washed with the zeolite-containing detergent 2.
    Figure 00060001
    Figure 00070001

    Claims (6)

    1. A process for the preparation of a storage-stabilized washing agent by mixing 10 to 50% by weight of a crystalline sodium layered silicate of the formula NaMSi2O5, where M is Na or H, 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 m, in particular from 1 to 20 m, 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 (NTA) 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 spray-mist mixing process with the formation of agglomerate particles having a particle size in the range from 0.25 to 2.5 mm.
    EP89105745A 1988-04-15 1989-04-01 Storage stabilized detergent with increased bleaching effect Expired - Lifetime EP0337219B1 (en)

    Applications Claiming Priority (2)

    Application Number Priority Date Filing Date Title
    DE3812555 1988-04-15
    DE3812555A DE3812555A1 (en) 1988-04-15 1988-04-15 STORAGE-STABILIZED DETERGENT WITH REINFORCED WHITENING EFFECT

    Publications (3)

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    EP0337219A2 EP0337219A2 (en) 1989-10-18
    EP0337219A3 EP0337219A3 (en) 1991-04-10
    EP0337219B1 true EP0337219B1 (en) 1999-09-22

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    EP (1) EP0337219B1 (en)
    JP (1) JPH0633419B2 (en)
    KR (1) KR910006072B1 (en)
    CA (1) CA1324306C (en)
    DE (2) DE3812555A1 (en)
    DK (1) DK169725B1 (en)
    ES (1) ES2138953T3 (en)
    FI (1) FI92329C (en)
    NO (1) NO172750C (en)
    SG (1) SG40030A1 (en)

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    DE4134914A1 (en) * 1991-10-23 1993-04-29 Henkel Kgaa DETERGENT AND CLEANING AGENT WITH SELECTED BUILDER SYSTEMS
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    EP0639639B2 (en) * 1993-08-17 2010-07-28 The Procter & Gamble Company Detergent compositions comprising percarbonate bleaching agents
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    Publication number Publication date
    FI891765A0 (en) 1989-04-13
    DE58909857D1 (en) 1999-10-28
    NO891545D0 (en) 1989-04-14
    NO891545L (en) 1989-10-16
    NO172750B (en) 1993-05-24
    ES2138953T3 (en) 2000-02-01
    FI92329C (en) 1994-10-25
    KR900016446A (en) 1990-11-13
    JPH0633419B2 (en) 1994-05-02
    EP0337219A3 (en) 1991-04-10
    DK181789A (en) 1989-10-16
    DE3812555A1 (en) 1989-10-26
    FI92329B (en) 1994-07-15
    NO172750C (en) 1993-09-01
    DK181789D0 (en) 1989-04-14
    JPH01311197A (en) 1989-12-15
    EP0337219A2 (en) 1989-10-18
    CA1324306C (en) 1993-11-16
    FI891765A (en) 1989-10-16
    DK169725B1 (en) 1995-01-23
    KR910006072B1 (en) 1991-08-12
    SG40030A1 (en) 1997-06-14

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