EP0337217A2 - Detergent containing a storage-stable bleach - Google Patents

Detergent containing a storage-stable bleach Download PDF

Info

Publication number
EP0337217A2
EP0337217A2 EP89105743A EP89105743A EP0337217A2 EP 0337217 A2 EP0337217 A2 EP 0337217A2 EP 89105743 A EP89105743 A EP 89105743A EP 89105743 A EP89105743 A EP 89105743A EP 0337217 A2 EP0337217 A2 EP 0337217A2
Authority
EP
European Patent Office
Prior art keywords
weight
mixed
detergent
layered silicate
crystalline layered
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.)
Granted
Application number
EP89105743A
Other languages
German (de)
French (fr)
Other versions
EP0337217A3 (en
EP0337217B1 (en
Inventor
Franz-Josef Dr. Dany
Werner Gohla
Günther Dr. Schimmel
Hans Peter Dr. Rieck
Ingrid Czeslik
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Clariant Produkte Deutschland GmbH
Original Assignee
Hoechst AG
Priority date (The priority date 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 date listed.)
Filing date
Publication date
Application filed by Hoechst AG filed Critical Hoechst AG
Publication of EP0337217A2 publication Critical patent/EP0337217A2/en
Publication of EP0337217A3 publication Critical patent/EP0337217A3/en
Application granted granted Critical
Publication of EP0337217B1 publication Critical patent/EP0337217B1/en
Anticipated expiration legal-status Critical
Expired - Lifetime legal-status Critical Current

Links

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

  • the present invention relates to a detergent with a storage-stabilized bleaching system and 2 to 20% by weight of detergents and customary washing auxiliaries, including fillers, in particular a household detergent for coarse, white and colored laundry, as used in automatic washing machines.
  • the detergent Due to the increasing spread of household washing machines, the detergent has to be adapted to the changed washing conditions.
  • Modern detergents therefore consist of a combination of detergents as washing-active substances, bleaching agents and additives that increase washing power, the so-called builders, which on the one hand remove the hardness of the washing liquor and on the other hand prevent deposits of inorganic salts on the laundry and thereby ensure a "soft touch" Provide laundry 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 due to the phosphate content in the domestic wastewater, the use of zeolites was proposed as a builder.
  • the invention has for its object to provide a detergent with a storage-stabilized bleaching system, which exerts an increased bleaching action on the laundry and maintains the "soft handle" in the laundry.
  • a detergent with a storage-stabilized bleaching agent is obtained if it as a builder contains 10 to 50% by weight, in particular 20 to 35% by weight, of crystalline sheet silicate and 1 to 5% by weight, in particular 2.0 to 3.0% by weight.
  • TAED tetraacetylethylene diamine
  • AVOX washing-active oxygen
  • the crystalline sheet silicates used in the preparation of the detergent according to the invention can be prepared in accordance with DE-34 13 571 A1.
  • the determination of the wash-active oxygen (AVOX) of the bleach and the detergent was carried out according to the instructions of Dr. E. Heinerth, Tenside 2 (1965) 180.
  • the sodium perborate tetrahydrate (NaBO3. 4 H2O) examined had an AVOX number of 10% by weight; the sodium perborate monohydrate (NaBO3. H2O) had an AVOX number of 15% by weight "; the sodium percarbonate (2 Na2CO3. 3 H2O2) had an AVOX number of 13.5% by weight.
  • the washing power (bleaching effect) of the detergent was determined as the whiteness of the test fabrics (WFK polyester / cotton with tea soiling, order code 20 G) according to DIN 44983.
  • the storage tests were carried out according to the following forced test conditions:
  • the detergent to be investigated 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 / m2. H.
  • Table 2 shows the degradation values of the bleaching agent as a function of time after the forced storage test conditions.
  • the bleach degradation, especially sodium percarbonate, is very large in the presence of zeolite.
  • 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.

Landscapes

  • 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)

Abstract

The detergent contains a storage-stabilised bleaching system and 2 to 20 % by weight of detergents and customary detergent auxiliaries, including fillers, plus, as builder, 10 to 50 % by weight of crystalline sheet silicate, and 1 to 5 % by weight of tetraacetylethylenediamine (TAED) and a bleach, where the amount of bleach is such that the detergent contains 0.5 to 4 % by weight of active oxygen (AVOX).

Description

Die vorliegende Erfindung betrifft ein Waschmittel mit la­gerstabilisiertem Bleichsystem sowie 2 bis 20 Gew% Deter­gentien und üblichen Waschhilfsstoffen, einschließlich Füllstoffen, 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 and 2 to 20% by weight of detergents and customary washing auxiliaries, including fillers, in particular a household detergent for coarse, white and colored laundry, as used in automatic 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 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 washing-active substances, bleaching agents and additives that increase washing power, the so-called builders, which on the one hand remove the hardness of the washing liquor and on the other hand prevent deposits of inorganic salts on the laundry and thereby ensure a "soft touch" Provide laundry 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 due to the phosphate content in the 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 items to be washed lose the desired "soft feel" in the course of several washes. In addition, during the storage period, which lies between the production and the consumption of the detergent, the detergent by decomposing the bleach partially lost 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 ein "weicher Griff" des Waschgutes auch dann er­reicht werden, wenn als Builder Zeolithe verwendet werden; 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% by weight of crystalline layered silicate or alkali silicate to the detergent. As a result, a "soft grip" of the laundry could be achieved even if zeolites are used as builders; however, the storage stability of the detergent was not affected by this.

Der Erfindung liegt die Aufgabe zugrunde, ein Waschmittel mit lagerstabilisiertem Bleichsystem bereitzustellen, das eine verstärkte Bleichwirkung auf das Waschgut ausübt und im Waschgut den "weichen Griff" aufrechterhält.The invention has for its object to provide a detergent with a storage-stabilized bleaching system, which exerts an increased bleaching action on the laundry and maintains the "soft handle" in the laundry.

Überraschenderweise wurde gefunden, daß ein Waschmittel mit lagerstabilisiertem Bleichmittel erhalten wird, wenn es als Builder 10 bis 50 Gew%, insbesondere 20 bis 35 Gew%, kri­stallines Schichtsilikat sowie 1 bis 5 Gew%, insbesondere 2,0 bis 3,0 Gew%, Tetraacetylethylendiamin (TAED) und ein Bleichmittel enthält, wobei die Bleichmittelmenge so bemes­sen ist, daß 0,5 bis 4 Gew%, insbesondere 1,0 bis 2,5 Gew%, waschaktiver Sauerstoff (AVOX) im Waschmittel vorliegt.Surprisingly, it has been found that a detergent with a storage-stabilized bleaching agent is obtained if it as a builder contains 10 to 50% by weight, in particular 20 to 35% by weight, of crystalline sheet silicate and 1 to 5% by weight, in particular 2.0 to 3.0% by weight. Contains tetraacetylethylene diamine (TAED) and a bleaching agent, the amount of bleaching agent being such that 0.5 to 4% by weight, in particular 1.0 to 2.5% by weight, of washing-active oxygen (AVOX) is present in the detergent.

Besonders bewährt hat sich ein kristallines Schichtsilikat der allgemeinen Formel
Na M SiX O2X+1 . Y H₂O
worin
X = 1,9 bis 4,0,
M = Na oder H,
Y = 0 bis 20
bedeuten. Ganz besonders gute Ergebnisse werden erreicht, wenn das kristalline Schichtsilikat der δ-Modifikation des Na₂Si₂O₅ entspricht.A crystalline layered silicate of the general formula has proven particularly useful
Na M Si X O 2X + 1 . Y H₂O
wherein
X = 1.9 to 4.0,
M = Na or H,
Y = 0 to 20
mean. Particularly good results are achieved if the crystalline layered silicate corresponds to the δ modification of Na₂Si₂O₅.

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) das Bleichmittel Natriumperborat-Tetrahydrat, Natrium­perborat-Monohydrat und/oder Natriumpercarbonat ist;
  • d) es anorganische und/oder organische Phosphate, Borate, Zitrate, Gluconate, Nitrilotriessigsäure und/oder Imino­diacetate als zusätzliche Builder in Mengen von bis zu 20 Gew% enthält;
  • e) es aus Agglomeratteilchen mit einer Teilchengröße im Be­reich von 0,25 bis 2,5 mm besteht und durch einen Sprüh­nebelmischprozeß erhalten wurde;
  • f) es als Detergent Alkalisalze von Alkylbenzolsulfonaten, höheren Alkylsulfonaten und/oder höheren Fettalkoholpo­lyethoxylatsulfaten, insbesondere mit Alkylresten mit durchschnittlich 10 bis 18 C-Atomen in der Alkylgruppe, enthält;
  • g) es als Waschhilfsstoff Carboxymethylcellulose, Carboxy­methylstärke und/oder Methylcellulose in Mengen von bis zu 10 Gew% enthält.
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) the bleaching agent is sodium perborate tetrahydrate, sodium perborate monohydrate and / or sodium percarbonate;
  • d) 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;
  • e) 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;
  • f) it contains, as detergent, alkali metal salts of alkylbenzenesulfonates, higher alkylsulfonates and / or higher fatty alcohol polyethoxylate sulfates, in particular with alkyl radicals with an average of 10 to 18 carbon atoms in the alkyl group;
  • g) it contains carboxymethyl cellulose, carboxymethyl starch and / or methyl cellulose in amounts of up to 10% by weight as washing auxiliary.

Die bei der Herstellung des erfindungsgemäßen Waschmittels eingesetzten kristallinen Schichtsilikate können gemäß der DE-34 13 571 A1 hergestellt werden.The crystalline sheet silicates used in the preparation of the detergent according to the invention can be prepared in accordance with DE-34 13 571 A1.

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 the instructions of Dr. E. Heinerth, Tenside 2 (1965) 180. The sodium perborate tetrahydrate (NaBO₃. 4 H₂O) examined had an AVOX number of 10% by weight; the sodium perborate monohydrate (NaBO₃. H₂O) had an AVOX number of 15% by weight "; the sodium percarbonate (2 Na₂CO₃. 3 H₂O₂) 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 the whiteness of the test fabrics (WFK polyester / cotton with tea soiling, order code 20 G) 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 washing liquor was determined using the difference method, which is derived from equation I
% WK =% WG g -% WG 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 investigated 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 / m². H.

In der Tabelle 1 sind die getesteten Waschmittelformu­lierungen aufgelistet.The detergent formulations tested are listed in Table 1.

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 Natriumtripolyphos­ phat-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 as a function of time after the forced storage test conditions. In addition, two commercial detergents on zeolite and sodium tripolyphos phat basis included in Table 2. The bleach degradation, especially sodium percarbonate, is very large in the presence of zeolite.

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. TABELLE 1 Waschmittelformulierungen Inhaltsstoffe (Gew%) Beispiel 1 Beispiel 2 *) Beispiel 3 *) Beispiel 4 Beispiel 5 Anionische Tenside 6.5 6.5 6.5 6.5 6.5 Nichtionische Tenside 3.5 3.5 3.5 3.5 3.5 Seife 4.5 4.5 4.5 4.5 4.5 Zeolith A 21.5 - - 21.5 - δ -Na₂Si₂O₅ - 21.5 21.5 - 21.5 Soda 7.5 - - 7.5 - NaBO₃ · H₂O 10.0 10.0 - - - TAED 2.5 2.5 2.5 - - 2 Na₂CO₃ ·3 H₂O₂ - - 18.0 18.0 18.0 Opt. Aufheller 0.2 0.2 0.2 0.2 0.2 Schmutzträger 1.5 1.5 1.5 1.5 1.5 Enzyme 0.3 0.3 0.3 0.3 0.3 Dispergatoren (Polycarboxylate) 4.0 2.0 - 4.0 2.0 Na-Silikat 5.0 - - 5.0 - Stellmittel (Na₂SO₄) auf 100 % *) erfindungsgemäßes Waschmittel TABELLE 2 AVOX-Abbäu Beispiel AVOX-Abbau in % 1 Woche 2 Wochen 3 Wochen 1 14 29 32 2 *) 0 9 11 3 *) 0 5 9 4 33 50 86 5 0 4 8 Handelsware Zeolith-Basis 16 22 37 Handelsware Na₅P₃O₁₀-Basis 0 16 21 *) erfindungsgemäßes Waschmittel TABELLE 3 Bleichmittelwirkung, ermittelt nach Gleichung I Beispiel % Waschkraft 1 37.5 2 *) 43.0 3 *) 42.0 4 31.5 5 38.5 *) erfindungsgemäßes Waschmittel 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. TABLE 1 Detergent formulations Ingredients (% by weight) example 1 Example 2 *) Example 3 *) Example 4 Example 5 Anionic surfactants 6.5 6.5 6.5 6.5 6.5 Nonionic surfactants 3.5 3.5 3.5 3.5 3.5 Soap 4.5 4.5 4.5 4.5 4.5 Zeolite A 21.5 - - 21.5 - δ -Na₂Si₂O₅ - 21.5 21.5 - 21.5 soda 7.5 - - 7.5 - NaBO₃ · H₂O 10.0 10.0 - - - TAED 2.5 2.5 2.5 - - 2 Na₂CO₃ · 3 H₂O₂ - - 18.0 18.0 18.0 Opt. Brightener 0.2 0.2 0.2 0.2 0.2 Dirt carrier 1.5 1.5 1.5 1.5 1.5 Enzymes 0.3 0.3 0.3 0.3 0.3 Dispersants (polycarboxylates) 4.0 2.0 - 4.0 2.0 Na silicate 5.0 - - 5.0 - Adjusting agent (Na₂SO₄) to 100% *) Detergent according to the invention AVOX degradation example AVOX reduction in% 1 week 2 weeks 3 weeks 1 14 29 32 2 *) 0 9 11 3 *) 0 5 9 4th 33 50 86 5 0 4th 8th Merchandise zeolite base 16 22 37 Merchandise Na₅P₃O₁₀ base 0 16 21st *) Detergent according to the invention Bleaching effect, determined according to equation I example % Washing power 1 37.5 2 *) 43.0 3 *) 42.0 4th May 31 5 38.5 *) Detergent according to the invention

Claims (8)

1. Verfahren zur Herstellung eines Waschmittels mit lager­stabilisiertem Bleichsystem durch Mischen von 2 bis 20 Gew% Detergentien und üblichen Waschhilfsstoffen, ein­schließlich Füllstoffen, dadurch gekennzeichnet, daß zu­sätzlich als Builder 10 bis 50 Gew%, insbesondere 20 bis 35 Gew%, kristallines Schichtsilikat sowie 1 bis 5 Gew%, insbesondere 2,0 bis 3 ,0 Gew%, Tetraacetylethylendiamin (TAED) und ein Bleichmittel eingemischt werden, wobei die Bleichmittelmenge so bemessen wird, daß 0 ,5 bis 4 Gew%, insbesondere 1,0 bis 2,5 Gew%, waschaktiver Sauer­stoff (AVOX) im Waschmittel vorliegt.1. A process for the preparation of a detergent with a storage-stabilized bleaching system by mixing 2 to 20% by weight of detergents and customary washing auxiliaries, including fillers, characterized in that 10 to 50% by weight, in particular 20 to 35% by weight, of crystalline layered silicate and 1 up to 5% by weight, in particular 2.0 to 3.0% by weight, of tetraacetylethylene diamine (TAED) and a bleaching agent are mixed in, the amount of bleaching agent being such that 0.5 to 4% by weight, in particular 1.0 to 2.5 % By weight of active washing oxygen (AVOX) is present in the detergent. 2. Verfahren nach Anspruch 1, dadurch gekennzeichnet, daß ein kristallines Schichtsilikat der allgemeinen Formel
Na M SiX O2x+1 . Y H₂O,
worin
X = 1,9 bis 4,0,
M = Na oder H,
Y = 0 bis 20
bedeuten, eingemischt wird.2. The method according to claim 1, characterized in that a crystalline layered silicate of the general formula
Na M Si X O 2x + 1 . Y H₂O,
wherein
X = 1.9 to 4.0,
M = Na or H,
Y = 0 to 20
mean is mixed in. 3. Verfahren nach Anspruch 1, dadurch gekennzeichnet, daß ein kristallines Schichtsilikat der δ-Modifikation des Na₂Si₂O₅ eingemischt wird.3. The method according to claim 1, characterized in that a crystalline layered silicate of the δ modification of Na₂Si₂O₅ is mixed. 4. Verfahren nach einem der Ansprüche 1 bis 3, dadurch ge­kennzeichnet, daß ein kristallines Schichtsilikat mit Teilchendurchmessern von 0,01 bis 1000 µm, insbesondere von 1 bis 20 µm, eingemischt wird.4. The method according to any one of claims 1 to 3, characterized in that a crystalline layered silicate with particle diameters of 0.01 to 1000 microns, in particular from 1 to 20 microns, is mixed. 5. Verfahren nach einem der Ansprüche 1 bis 4, dadurch ge­kennzeichnet, daß ein kristallines Schichtsilikat mit einer Ionenaustauschkapazität von 400 bis 1200 mmol Na⁺/100 g wasserfreie Substanz eingemischt wird.5. The method according to any one of claims 1 to 4, characterized in that a crystalline layered silicate having an ion exchange capacity of 400 to 1200 mmol Na⁺ / is mixed in 100 g anhydrous substance. 6. Verfahren nach einem der Ansprüche 1 bis 5, dadurch ge­kennzeichnet, daß als Bleichmittel Natriumperborat-Te­trahydrat, Natriumperborat-Monohydrat und/oder Natrium­percarbonat eingemischt wird.6. The method according to any one of claims 1 to 5, characterized in that sodium perborate tetrahydrate, sodium perborate monohydrate and / or sodium percarbonate is mixed in as the bleaching agent. 7. Verfahren nach einem der Ansprüche 1 bis 6, dadurch ge­kennzeichnet, daß anorganische und/oder organische Phos­phate, Borate, Zitrate, Gluconate, Nitrilotriessigsäure und/oder Iminodiacetate als zusätzliche Builder in Mengen von bis zu 20 Gew% eingemischt werden.7. The method according to any one of claims 1 to 6, characterized in that inorganic and / or organic phosphates, borates, citrates, gluconates, nitrilotriacetic acid and / or iminodiacetates are mixed in as additional builders in amounts of up to 20% by weight. 8. Verfahren nach Anspruch 1, dadurch gekennzeichnet, daß die Waschmittelformulierung in einem Sprühnebelmischpro­zeß unter Bildung von Agglomeratteilchen mit einer Teil­chengröße im Bereich von 0,25 bis 2,5 mm verarbeitet wird.8. The method according to claim 1, characterized in that the detergent formulation is processed in a spray mixing process to form agglomerate particles with 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
DE3812556A DE3812556A1 (en) 1988-04-15 1988-04-15 DETERGENT WITH STORAGE-STABILIZED BLEACHING SYSTEM
DE3812556 1988-04-15

Publications (3)

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

Family

ID=6352059

Family Applications (1)

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

Country Status (10)

Country Link
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)

Cited By (11)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO1992007928A1 (en) * 1990-10-26 1992-05-14 Henkel Kommanditgesellschaft Auf Aktien Builder for detergents
WO1992016608A1 (en) * 1991-03-21 1992-10-01 Henkel Kommanditgesellschaft Auf Aktien Liquid or paste-like washing product
EP0543911A1 (en) † 1990-08-17 1993-06-02 Procter & Gamble Detergent compositions.
WO1993012843A1 (en) * 1992-01-03 1993-07-08 The Procter & Gamble Company Granular percarbonate laundry bleach containing layered silicate stabilizer
WO1994018294A1 (en) * 1993-02-15 1994-08-18 Henkel Kommanditgesellschaft Auf Aktien Surfactant- and builder-containing detergent additive
WO1995016019A1 (en) * 1993-12-10 1995-06-15 The Procter & Gamble Company Stabilization of oxidation-sensitive ingredients in percarbonate detergent compositions
AU667398B2 (en) * 1992-08-01 1996-03-21 Procter & Gamble Company, The Detergent bleach compositions containing layered silicate builder and percarbonate stabilized by EDDS
US5501814A (en) * 1991-10-23 1996-03-26 Henkel Kommanditgesellschaft Auf Aktien Detergents and cleaning preparations containing selected builder systems
GB2294704A (en) * 1994-11-05 1996-05-08 Procter & Gamble Bleaching composition
EP0738777A2 (en) * 1995-04-20 1996-10-23 Kao Corporation Bleaching detergent composition
EP0750661A1 (en) * 1994-03-14 1997-01-02 The Procter & Gamble Company Granular bleaching compositions

Families Citing this family (27)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
GB9113674D0 (en) * 1991-06-25 1991-08-14 Unilever Plc Detergent compositions
GB9216386D0 (en) * 1992-07-31 1992-09-16 Unilever Plc Use of aluminosilicates of the zeolite p type as low temperature calcium binders
AU4777993A (en) * 1992-08-01 1994-03-03 Procter & Gamble Company, The Low gelling detergent compositions and a process for making such compositions
DE4303320C2 (en) * 1993-02-05 1995-12-21 Degussa Detergent composition having improved soil carrying power, process for its preparation and use of a suitable polycarboxylate therefor
GB9307493D0 (en) * 1993-04-08 1993-06-02 Procter & Gamble Detergent compositions
US5378388A (en) * 1993-06-25 1995-01-03 The Procter & Gamble Company Granular detergent compositions containing selected builders in optimum ratios
DE69326833D1 (en) * 1993-07-14 1999-11-25 Procter & Gamble Stabilized detergent compositions
US5792738A (en) * 1993-07-14 1998-08-11 The Procter & Gamble Company Granular laundry detergent compositions containing stabilised percarbonate bleach particles
DE69422100D1 (en) * 1993-08-17 2000-01-20 Procter & Gamble Detergent compositions containing percarbonate bleach
US5705466A (en) * 1993-08-17 1998-01-06 The Procter & Gamble Company High bulk density granular detergents containing a percarbonate bleach and a powdered silicate
DE4327884A1 (en) * 1993-08-19 1995-02-23 Hoechst Ag Process for the preparation of a mixture of sodium silicates and other salts and the use of the mixture
US5773399A (en) * 1993-12-10 1998-06-30 The Procter & Gamble Comapny Stabilization of oxidation-sensitive ingredients in percarbonate detergent compositions
ZA952081B (en) * 1994-03-14 1996-12-12 Procter & Gamble Granular bleaching composition
JPH09511533A (en) * 1994-09-19 1997-11-18 ザ、プロクター、エンド、ギャンブル、カンパニー Granular bleaching composition
GB2294694A (en) * 1994-11-05 1996-05-08 Procter & Gamble Solid detergent composition
GB2294695A (en) * 1994-11-05 1996-05-08 Procter & Gamble A method of washing laundry
KR100350924B1 (en) * 1994-12-06 2002-10-31 제일제당주식회사 Bleach-containing detergent composition having improved bleaching stability
US5663132A (en) * 1995-03-01 1997-09-02 Charvid Limited Liability Company Non-caustic composition comprising peroxygen compound and metasilicate and cleaning methods for using same
US6194367B1 (en) 1995-03-01 2001-02-27 Charvid Limited Liability Co. Non-caustic cleaning composition comprising peroxygen compound and specific silicate and method of making the same in free-flowing, particulate form
US5898024A (en) * 1995-03-01 1999-04-27 Charvid Limited Liability Non-caustic cleaning composition comprising peroxygen compound and specific silicate, and method of making the same in free-flowing, particulate form
US6034048A (en) * 1995-03-01 2000-03-07 Charvid Limited Liability Co. Non-caustic cleaning composition using an alkali salt
JP3008166B2 (en) * 1995-11-02 2000-02-14 花王株式会社 Detergent particles and granular detergent composition
GB2310849A (en) * 1996-03-08 1997-09-10 Procter & Gamble Crystalline layered silicate
ES2210751T3 (en) 1997-06-04 2004-07-01 THE PROCTER & GAMBLE COMPANY PARTICLES OF DETERGENT ENZYMES THAT HAVE A WATER-COVERED CARBOXYLATE BARRIER LAYER AND COMPOSITIONS THAT INCLUDE THE SAME.
DE10242222A1 (en) * 2002-09-12 2004-03-25 Henkel Kgaa Mechanically compacted washing or detergent agents containing neutralizable organic polycarboxylic acids are given improved odor values by having specific non-water-soluble builder content and pH
US20100056404A1 (en) * 2008-08-29 2010-03-04 Micro Pure Solutions, Llc Method for treating hydrogen sulfide-containing fluids
US9484756B2 (en) 2011-08-24 2016-11-01 Getac Technology Corporation Battery having multi-orientation conductions, battery holder having multi-orientation conductions, and battery assembling method

Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0028432A1 (en) * 1979-11-03 1981-05-13 THE PROCTER & GAMBLE COMPANY Granular laundry compositions
EP0263520A2 (en) * 1986-10-08 1988-04-13 Hoechst Aktiengesellschaft Detergents containing softeners
EP0320770A2 (en) * 1987-12-11 1989-06-21 Hoechst Aktiengesellschaft Process for the preparation of crystalline layered sodium silicates

Family Cites Families (13)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
GB8310698D0 (en) * 1983-04-20 1983-05-25 Procter & Gamble Detergent compositions
DD220326A1 (en) * 1983-09-05 1985-03-27 Bitterfeld Chemie WEISSGRADVERSTAERKER
DD220328A1 (en) * 1983-09-05 1985-03-27 Bitterfeld Chemie WASHING AIDS FOR WHITE GRADE AMPLIFICATION
DD220325A1 (en) * 1983-09-05 1985-03-27 Bitterfeld Chemie WASHING TOOLS
GB8328075D0 (en) * 1983-10-20 1983-11-23 Unilever Plc Dishwashing compositions
DE3413571A1 (en) * 1984-04-11 1985-10-24 Hoechst Ag, 6230 Frankfurt USE OF CRYSTALLINE LAYERED SODIUM SILICATES FOR WATER SOFTENING AND METHOD FOR WATER SOFTENING
DE3416669A1 (en) * 1984-05-05 1985-11-07 Hoechst Ag, 6230 Frankfurt SOFTENING DETERGENT
JPS614879A (en) * 1984-06-15 1986-01-10 Atsugi Motor Parts Co Ltd Motor self-cooling type air pump
FR2588262B1 (en) * 1985-10-08 1988-04-29 Atochem POLYAMIDE-IMIDE POWDERS, METHOD OF MANUFACTURE AND USES
DE3604039A1 (en) * 1986-02-08 1987-08-20 Henkel Kgaa TEXTILE DETERGENT AND CLEANING AGENT
GB8609884D0 (en) * 1986-04-23 1986-05-29 Procter & Gamble Softening detergent compositions
DE3702111A1 (en) * 1987-01-24 1988-08-04 Henkel Kgaa POROESE LAYERED SILICATE / SODIUM SULFATE AGGLOMERATE
DE3702067A1 (en) * 1987-01-24 1988-08-04 Henkel Kgaa TEXTILE SOFTENING DETERGENT

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0028432A1 (en) * 1979-11-03 1981-05-13 THE PROCTER & GAMBLE COMPANY Granular laundry compositions
EP0263520A2 (en) * 1986-10-08 1988-04-13 Hoechst Aktiengesellschaft Detergents containing softeners
EP0320770A2 (en) * 1987-12-11 1989-06-21 Hoechst Aktiengesellschaft Process for the preparation of crystalline layered sodium silicates

Cited By (18)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0543911A1 (en) † 1990-08-17 1993-06-02 Procter & Gamble Detergent compositions.
EP0543911B2 (en) † 1990-08-17 2000-11-08 The Procter & Gamble Company Detergent compositions
WO1992007928A1 (en) * 1990-10-26 1992-05-14 Henkel Kommanditgesellschaft Auf Aktien Builder for detergents
TR25381A (en) * 1990-10-26 1993-03-01 Henkel Kgaa STRICTURE MATERIAL FOR WASHING AGENTS.
US5393455A (en) * 1990-10-26 1995-02-28 Henkel Kommanditgesellschaft Auf Aktien Zeolite-based phosphate-free detergent builder composition
WO1992016608A1 (en) * 1991-03-21 1992-10-01 Henkel Kommanditgesellschaft Auf Aktien Liquid or paste-like washing product
US5501814A (en) * 1991-10-23 1996-03-26 Henkel Kommanditgesellschaft Auf Aktien Detergents and cleaning preparations containing selected builder systems
WO1993012843A1 (en) * 1992-01-03 1993-07-08 The Procter & Gamble Company Granular percarbonate laundry bleach containing layered silicate stabilizer
AU667398B2 (en) * 1992-08-01 1996-03-21 Procter & Gamble Company, The Detergent bleach compositions containing layered silicate builder and percarbonate stabilized by EDDS
WO1994018294A1 (en) * 1993-02-15 1994-08-18 Henkel Kommanditgesellschaft Auf Aktien Surfactant- and builder-containing detergent additive
WO1995016019A1 (en) * 1993-12-10 1995-06-15 The Procter & Gamble Company Stabilization of oxidation-sensitive ingredients in percarbonate detergent compositions
CN1080297C (en) * 1993-12-10 2002-03-06 普罗格特-甘布尔公司 Stabilization of oxidation-sensitive ingredients in percarbonate detergent compositions
EP0750661A1 (en) * 1994-03-14 1997-01-02 The Procter & Gamble Company Granular bleaching compositions
EP0750661A4 (en) * 1994-03-14 1998-10-07 Procter & Gamble Granular bleaching compositions
GB2294704A (en) * 1994-11-05 1996-05-08 Procter & Gamble Bleaching composition
EP0738777A2 (en) * 1995-04-20 1996-10-23 Kao Corporation Bleaching detergent composition
EP0738777A3 (en) * 1995-04-20 1998-12-09 Kao Corporation Bleaching detergent composition
US6159919A (en) * 1995-04-20 2000-12-12 Kao Corporation Bleaching detergent composition

Also Published As

Publication number Publication date
DE58909855D1 (en) 1999-10-07
JPH0633420B2 (en) 1994-05-02
KR910006073B1 (en) 1991-08-12
FI91882B (en) 1994-05-13
NO891546L (en) 1989-10-16
CA1311982C (en) 1992-12-29
FI891766A0 (en) 1989-04-13
FI91882C (en) 1994-08-25
US5078895A (en) 1992-01-07
DK181989A (en) 1989-10-16
DK181989D0 (en) 1989-04-14
NO172901C (en) 1993-09-22
DK169287B1 (en) 1994-10-03
ES2137916T3 (en) 2000-01-01
EP0337217A3 (en) 1991-04-10
EP0337217B1 (en) 1999-09-01
FI891766A (en) 1989-10-16
DE3812556A1 (en) 1989-10-26
JPH0297600A (en) 1990-04-10
KR900016447A (en) 1990-11-13
NO172901B (en) 1993-06-14
NO891546D0 (en) 1989-04-14

Similar Documents

Publication Publication Date Title
EP0337217A2 (en) Detergent containing a storage-stable bleach
EP0554287B1 (en) Builder for detergents
DE2902236C2 (en)
EP0525239B1 (en) Process for increasing the bleaching efficiency of an inorganic persalt
DE3717227A1 (en) PHOSPHATE-FREE DETERGENT WITH REDUCED INCRUSTING TENDENCY
DE2215371A1 (en) laundry detergent
EP1199350B1 (en) Use of quaternary polysiloxanes in detergent compositions
EP0337219A2 (en) Storage stabilized detergent with increased bleaching effect
DE4139826A1 (en) WASHING AND CLEANING AGENT
EP0405122A2 (en) Builder for fabric detergent
EP0395970B1 (en) Washing and cleaning compositions
DE69022515T3 (en) Effective bleach compositions for textiles at low temperatures.
EP0574436B1 (en) Detergents
DD220328A1 (en) WASHING AIDS FOR WHITE GRADE AMPLIFICATION
EP0407626A1 (en) Phosphate-free liquid washing and cleaning composition
EP0340590A1 (en) Detergent additive
EP0419970A2 (en) Granular, phosphate free water softening agent
DE2822838A1 (en) DETERGENT AND CLEANING AGENT
DD161180A3 (en) WASHING AND CLEANING AGENT FOR SOLID SURFACES
EP0345490A2 (en) Mixtures of phosphoric acid partial esters, process for their preparation, their use and washing and cleaning agents containing them
EP0640683A2 (en) Inhibitior for chemical damage of textile fibres
DE19523864A1 (en) Washing compsn., giving better soil release - contains surfactant, silicate or zeolite binding calcium and poly:amino acid or anhydride as co-builder, and is free from inorganic sulphate
CH669209A5 (en) FOR WASHING TEXTILES IN WASHING WATER AT A TEMPERATURE OF UP TO 60 C DETERGENT COMPOSITION.
EP0035137A1 (en) Washing and cleaning product
DE19521291A1 (en) laundry detergent

Legal Events

Date Code Title Description
PUAI Public reference made under article 153(3) epc to a published international application that has entered the european phase

Free format text: ORIGINAL CODE: 0009012

AK Designated contracting states

Kind code of ref document: A2

Designated state(s): AT BE CH DE ES FR GB IT LI NL SE

PUAL Search report despatched

Free format text: ORIGINAL CODE: 0009013

17P Request for examination filed

Effective date: 19901221

AK Designated contracting states

Kind code of ref document: A3

Designated state(s): AT BE CH DE ES FR GB IT LI NL SE

17Q First examination report despatched

Effective date: 19940216

RAP1 Party data changed (applicant data changed or rights of an application transferred)

Owner name: CLARIANT GMBH

GRAG Despatch of communication of intention to grant

Free format text: ORIGINAL CODE: EPIDOS AGRA

GRAG Despatch of communication of intention to grant

Free format text: ORIGINAL CODE: EPIDOS AGRA

GRAH Despatch of communication of intention to grant a patent

Free format text: ORIGINAL CODE: EPIDOS IGRA

GRAH Despatch of communication of intention to grant a patent

Free format text: ORIGINAL CODE: EPIDOS IGRA

GRAA (expected) grant

Free format text: ORIGINAL CODE: 0009210

AK Designated contracting states

Kind code of ref document: B1

Designated state(s): BE CH DE ES FR GB IT LI

RBV Designated contracting states (corrected)

Designated state(s): BE CH DE ES FR GB IT LI

REG Reference to a national code

Ref country code: CH

Ref legal event code: EP

REF Corresponds to:

Ref document number: 58909855

Country of ref document: DE

Date of ref document: 19991007

ITF It: translation for a ep patent filed

Owner name: ING. C. GREGORJ S.P.A.

GBT Gb: translation of ep patent filed (gb section 77(6)(a)/1977)

Effective date: 19991124

ET Fr: translation filed
REG Reference to a national code

Ref country code: ES

Ref legal event code: FG2A

Ref document number: 2137916

Country of ref document: ES

Kind code of ref document: T3

PLBE No opposition filed within time limit

Free format text: ORIGINAL CODE: 0009261

STAA Information on the status of an ep patent application or granted ep patent

Free format text: STATUS: NO OPPOSITION FILED WITHIN TIME LIMIT

26N No opposition filed
REG Reference to a national code

Ref country code: GB

Ref legal event code: IF02

PGFP Annual fee paid to national office [announced via postgrant information from national office to epo]

Ref country code: CH

Payment date: 20020222

Year of fee payment: 14

PGFP Annual fee paid to national office [announced via postgrant information from national office to epo]

Ref country code: BE

Payment date: 20020311

Year of fee payment: 14

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: BE

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 20030430

Ref country code: LI

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 20030430

Ref country code: CH

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 20030430

BERE Be: lapsed

Owner name: *CLARIANT G.M.B.H.

Effective date: 20030430

REG Reference to a national code

Ref country code: CH

Ref legal event code: PL

REG Reference to a national code

Ref country code: FR

Ref legal event code: CD

PGFP Annual fee paid to national office [announced via postgrant information from national office to epo]

Ref country code: ES

Payment date: 20070215

Year of fee payment: 19

PGFP Annual fee paid to national office [announced via postgrant information from national office to epo]

Ref country code: DE

Payment date: 20070223

Year of fee payment: 19

PGFP Annual fee paid to national office [announced via postgrant information from national office to epo]

Ref country code: GB

Payment date: 20070416

Year of fee payment: 19

PGFP Annual fee paid to national office [announced via postgrant information from national office to epo]

Ref country code: IT

Payment date: 20070515

Year of fee payment: 19

PGFP Annual fee paid to national office [announced via postgrant information from national office to epo]

Ref country code: FR

Payment date: 20070215

Year of fee payment: 19

GBPC Gb: european patent ceased through non-payment of renewal fee

Effective date: 20080401

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: DE

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 20081101

REG Reference to a national code

Ref country code: FR

Ref legal event code: ST

Effective date: 20081231

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: FR

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 20080430

REG Reference to a national code

Ref country code: ES

Ref legal event code: FD2A

Effective date: 20080402

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: GB

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 20080401

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: ES

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 20080402

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: IT

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 20080401