EP0906407A1 - Produit de rin age pour lave-vaisselle, faiblement alcalin, contenant du mgda - Google Patents

Produit de rin age pour lave-vaisselle, faiblement alcalin, contenant du mgda

Info

Publication number
EP0906407A1
EP0906407A1 EP97928266A EP97928266A EP0906407A1 EP 0906407 A1 EP0906407 A1 EP 0906407A1 EP 97928266 A EP97928266 A EP 97928266A EP 97928266 A EP97928266 A EP 97928266A EP 0906407 A1 EP0906407 A1 EP 0906407A1
Authority
EP
European Patent Office
Prior art keywords
mgda
acid
agents
residues
salts
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
EP97928266A
Other languages
German (de)
English (en)
Other versions
EP0906407B1 (fr
Inventor
Guido Wäschenbach
Paul William Robinson
Laurence Geret
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.)
Reckitt Benckiser NV
Original Assignee
Benckiser NV
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
Family has litigation
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Application filed by Benckiser NV filed Critical Benckiser NV
Priority to EP01105118A priority Critical patent/EP1113070B1/fr
Publication of EP0906407A1 publication Critical patent/EP0906407A1/fr
Application granted granted Critical
Publication of EP0906407B1 publication Critical patent/EP0906407B1/fr
Anticipated expiration legal-status Critical
Revoked 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
    • C11D3/16—Organic compounds
    • C11D3/26—Organic compounds containing nitrogen
    • C11D3/33—Amino carboxylic acids
    • 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
    • C11D3/3947—Liquid compositions
    • 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
    • C11D7/00—Compositions of detergents based essentially on non-surface-active compounds
    • C11D7/22—Organic compounds
    • C11D7/32—Organic compounds containing nitrogen
    • C11D7/3245—Aminoacids
    • 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
    • C11D7/00—Compositions of detergents based essentially on non-surface-active compounds
    • C11D7/22—Organic compounds
    • C11D7/32—Organic compounds containing nitrogen
    • C11D7/3281—Heterocyclic compounds

Definitions

  • the invention relates to machine dishwashing detergents of low alkalinity which contain methylglycinediacetic acid (MGDA) or a salt thereof and which preferably have a reduced bleaching agent content.
  • MGDA methylglycinediacetic acid
  • US-A 3,673,098 discloses non-bleaching caustic compositions based on KOH and nitrilotriacetic acid (NTA).
  • Fr-A 1 590 416 likewise discloses caustic compositions without bleaching agents, which are based on alkali metal hydroxides, pyrophosphates and NTA. Such agents were later formulated without caustic alkalis and the performance loss was compensated for by the addition of chlorine bleach, as exemplified in US-A-3,826,748. These non-caustic alkalis still had a high pH greater than 11.
  • EP-A-530 635 discloses acidic to mildly alkaline compositions (pH 5-9) which contain no complexing agents and are based on builders, enzymes and optionally oxygen bleaching.
  • DE-A-3 833 047 discloses acidic compositions (pH 2-6) with hydrolases and builders or complexing agents.
  • the examples disclose compositions with a high NTA or EDTA content (up to 30%). While these compositions can e.g. Eliminate tea residues well, their effect on milk residues is measured on a scale from 0 to 10, but always below 5.
  • DE-A-3 829 847 and DE-A-4 036 995 disclose the use of other biodegradable complexing agents, such as ß-alaninediacetic acid (ß-ADA) and isoserinediacetic acid (ISDA), in cleaning agents. If these documents contain application examples for machine dishwashing detergents, it is machine dishwashing - 3 -
  • ß-ADA ß-alaninediacetic acid
  • ISDA isoserinediacetic acid
  • detergents which have a pH of more than 10.5 in approximately 0.5% aqueous solution.
  • these compounds have a significantly less complex effect than NTA and can only replace them in an insufficient way in the finished agent.
  • DE-A-4 319 935 discloses the use of MGDA in dishwasher detergents without giving an example.
  • MGDA methylglycinediacetic acid
  • MGDA MGDA in laundry detergents
  • MGDA is said to have a better effect, in particular in the case of blood-soiled laundry, than phosphonates and, in the case of tea-soiled laundry, has approximately the same action as phosphonates.
  • MGDA in a dishwashing detergent similar to NTA, shows very good deposit inhibition on glass, metal and porcelain, whereby a dishwashing detergent is disclosed which has a solution in solution provides pH of more than 10.5. It is also suggested to use MGDA for dairy cleaning in very alkaline conditions.
  • a dishwashing detergent is said to have excellent cleaning performance for dishes which are contaminated by both milk and tea residues.
  • This object is achieved by a machine dishwashing detergent which contains methylglycinediacetic acid or its salts as a complexing agent and is characterized in that it does not exceed a pH of 10.4 in approximately 0.5% aqueous solution.
  • Milk residues consist of a mixture of denatured proteins (casein), fats, sugars and mineral deposits and consist of around 70% calcium phosphate (Ca3 (PO _ *.) 2).
  • Complexing agents therefore have a significant influence on the removal of milk residues because they dissolve calcium phosphates by complexing the calcium ions.
  • Tea residues are also based, among other things, on Ca deposits that arise when tea is brewed with hard water.
  • tea residues usually place different requirements on a machine dishwashing liquid than Milk residues, which can already be seen from the fact that the detergent disclosed in DE-A 3 833 047 removes tea residues satisfactorily in the acidic range (pH 2-6), but cannot convince with milk residues.
  • the ability (based on the weight of the complexing agent) to complex calcium ions at a certain pH value depends on the stability constant of the calcium complex (pKc) r, the acidic character of the complexing agent (PK3) and its molecular weight.
  • MGDA was also used only in dishwashing detergents which have a pH of more than 10.4 in approximately 0.5% aqueous solution.
  • dishwashing detergents which contain MGDA and which provide an approximately 0.5% aqueous solution with a pH of up to 10.4 can better remove both tea residues and milk residues and have an overall better dishwashing result as a dishwashing detergent that contains a complexing agent like the common NTA instead of MGDA.
  • the dishwashing detergent according to the invention can be liquid or powder and can also be in the form of a single-layer or multilayer tablet. Appropriate dosage forms and methods of obtaining them are known to the person skilled in the art.
  • the dishwasher detergents according to the invention preferably contain one or more enzymes such as, for example, amylase, protease, lipase or cellulase.
  • amylase such as, for example, amylase, protease, lipase or cellulase.
  • protease such as, for example, amylase, protease, lipase or cellulase.
  • the best cleaning results were achieved by the combined use of amylase and protease.
  • These enzymes can be used particularly effectively in the pH ranges described here; For example, the temperature-stable amylase Termamyl (Novo) achieves the optimum of its spectrum of activity at pH 7-8.
  • the enzymes come in Granular form or in solution with commercial concentrations or activities for use, wherein the content of enzymes can be 0.5-6, preferably 1-4% by weight.
  • Suitable builders are, for example, homo- and copolymeric polycarboxylic acids and their partially or completely neutralized salts, monomeric polycarboxylic acids and hydroxycarboxylic acids and their salts, carbonates, bicarbonates, borates, phosphates, silicates, aluminosilicates and mixtures of such substances.
  • Preferred salts of the above compounds are the ammonium and / or alkali salts, i.e. the lithium,
  • Sodium, potassium and rubidium salts and particularly preferably the sodium salt are particularly preferably the sodium salt.
  • Suitable polycarboxylic acids are acyclic, alicyclic, heterocyclic and aromatic carboxylic acids, these containing at least two carboxy groups which are each separated from one another by preferably no more than two carbon atoms.
  • Polycarboxylates containing two carboxy groups include, for example, water-soluble salts of succinic acid, malonic acid, (ethylenedioxy) diacetic acid, maleic acid, diglycolic acid, tartaric acid, tartronic acid and fumaric acid.
  • Polycarboxylates containing three carboxy groups include, for example, water-soluble citrates. Accordingly, citric acid is suitable as the hydroxycarboxylic acid.
  • one of aspartic acid can also be used
  • the homopolymer of acrylic acid is also suitable as the polycarboxylic acid.
  • borate builders which release borates under the detergent storage conditions or rinsing conditions can also be used as borate builders.
  • Polyphosphates such as tripolyphosphate, pyrophosphate, orthophosphate and the polymeric metaphosphate are suitable as phosphates.
  • Examples include alkali metal tripolyphosphates, sodium, potassium and ammonium pyrophosphate, sodium and potassium orthophosphate and sodium polymetaphosphate, in which the degree of polymerization preferably ranges from 5 to 21.
  • Sodium silicates such as sodium disilicate, sodium metasilicate and crystalline layered silicates are suitable as silicates.
  • Sodium aluminosilicates (zeolites) are also suitable.
  • a builder system from the salt of a hydroxycarboxylic acid or from the mixture of a hydroxycarboxylic acid and the salt of a hydroxycarboxylic acid is particularly preferred. Both the hydroxycarboxylic acid and the salt of Hydroxycarboxylic acid can be replaced in whole or in part by tripolyphosphate, although this is not preferred.
  • the builder system preferably consists of a hydroxypolycarboxylic acid with 2-4 carboxyl groups (or acidic inorganic salts), which can be mixed with its salt to adjust the pH.
  • Citric acid or a mixture of sodium citrate with citric acid is preferably used.
  • suitable for adjusting the required pH according to the invention are e.g. Mixtures with a predominant proportion of citric acid.
  • the water content of liquid dishwashing detergents can be 40-80% by weight.
  • the liquid dishwashing detergents also contain 0.2-5.0% by weight, preferably 0.5-2% by weight, of a thickener.
  • a thickener preferably 0.5-2% by weight
  • Carboxyvinyl polymers e.g. by B. F. Goodrich under the production name "Carbopol” on the market proved to be very usable.
  • Inorganic compounds that have thickening properties in this product composition can also be used. Examples of this are natural or synthetic thickeners based on differently structured silicate structures. Their use is described in various patents, e.g. in US-A-4 933 101 or EP-A2- 0 407 187.
  • nonionic surfactants are suitable as surfactants. These include, for example, water-soluble ethoxylated C.sub.6 g fatty acid alcohols and C.sub.66 mixed ethoxylated / propoxylated fatty acid alcohols and mixtures thereof, and also polyglucosides.
  • Another class of nonionic surfactants includes polyhydroxy fatty acid amides.
  • the machine dishwashing detergent according to the invention can furthermore contain one or more foam control agents. All foam control agents used in this area, such as silicones and paraffin oil, are suitable for this.
  • the foam control agents are preferably contained in the dishwasher detergent according to the invention with less than 5% by weight of the total weight of the detergent.
  • the machine dishwashing detergents according to the invention can preferably contain chlorine-free, active oxygen-releasing bleaching agents such as inorganic perhydrates or organic peracids and their salts as bleaching agents.
  • inorganic perhydrates are perborates, percarbonates and persulfates such as peroxymonopersulfate.
  • the inorganic perhydrates are normally alkali metal salts, such as lithium, sodium, potassium or rubidium salts, in particular the sodium salts.
  • the inorganic perhydrates can be present in the detergent as crystalline solids without further protection. For certain perhydrates, however, it is advantageous to use them as granular compositions which are provided with a coating which gives the granular products better storage stability.
  • the preferred perborate is sodium perborate, which can be present as a monohydrate with the formula NaB ⁇ 2H2 ⁇ 2 or as a tetrahydrate with the formula NaB02H2Ü2 • 3H20.
  • the preferred percarbonate is sodium percarbonate with the formula 2Na2C ⁇ 33H2 ⁇ 2 •
  • the percarbonate is preferably used in a coated form to increase its stability.
  • Organic peracids include all organic peracids conventionally used as bleaching agents, including for example perbenzoic acid and peroxycarboxylic acids such as mono- or diperoxyphthalic acid, 2-0ctydiperoxysuccinic acid, diperoxydodecanedicarboxylic acid, diperoxyazelaic acid and imidoperoxycarboxylic acid and optionally their salts.
  • perbenzoic acid and peroxycarboxylic acids such as mono- or diperoxyphthalic acid, 2-0ctydiperoxysuccinic acid, diperoxydodecanedicarboxylic acid, diperoxyazelaic acid and imidoperoxycarboxylic acid and optionally their salts.
  • the machine dishwashing detergent according to the invention may further contain one or more bleach activators. These are preferably used in detergents for dishwashing operations at temperatures in the range below 60 ° C. in order to achieve a sufficient bleaching effect.
  • N- and 0-acyl compounds such as acylated amines, acylated glycolurils or acylated sugar compounds are particularly suitable.
  • N, N, N ', N'-tetraacetylethylenediamine (TAED), pentaacetylglucose (PAG) and tetraacetylglycoluril (TAGU) are preferred.
  • catalytically active metal complexes and preferably transition metal complexes are also suitable as bleach activators. Most preferred is TAED.
  • the use of bleaching agents can be reduced and the machine dishwashing detergents according to the invention preferably have an oxygen bleaching agent in an amount of less than 1% by weight, based on the active oxygen.
  • the amount of bleach activator used is adjusted accordingly.
  • the machine dishwashing detergents have a large proportion of MGDA, such as 25% or more, preferably 30% or more, in each case based on the free acid, and an oxygen bleaching agent is dispensed with.
  • the machine dishwashing detergent according to the invention may further contain a silver / copper corrosion protection agent.
  • a silver / copper corrosion protection agent includes agents that are intended to prevent or reduce the tarnishing of non-ferrous metals, especially silver and copper.
  • Preferred silver / copper anti-corrosion agents are benzotriazole or bis-benzotriazoles and their substituted derivatives.
  • Suitable agents are organic and / or inorganic redox-active substances and paraffin oil.
  • Benzotriazole derivatives are those compounds in which the available substitution sites of the aromatic ring are partially or completely substituted. Suitable substituents are linear or branched C ⁇ _ 20- A lkyj.9jr , groups and hydroxy, thio, phenyl or halogen such as fluorine, chlorine, bromine and iodine. Preferred substituted benzotriazole is tolyltriazole.
  • Suitable bis-benzotriazoles are those in which the benzotriazole groups are each connected in the 6-position by a group X, in which X is a bond, a straight-chain, optionally substituted with one or more C 1-4 alkyl groups, preferably 1-6 carbon atoms, a cycloalkyl radical having at least 5 carbon atoms, a carbonyl group, a sulfuryl group, an oxygen or a sulfur atom.
  • the aromatic rings of the bis-benzotriazoles can be substituted as defined above for the benzotriazole.
  • Suitable organic redox-active substances are, for example, ascorbic acid, indole, methionine, an N-mono- (C 1 -C 4 alkyl) glycine, an N, N-di (C 1 -C 4 alkyl) glycine, 2- Phenylglycine or a coupler and / or developer compound chosen from the group of diaminopyridines, aminohydroxypyridines, dihydroxypyridines, heterocyclic hydrazones, aminohydroxypyrimidines, dihydroxypyrimidines, tetraaminopyrimidines, triaminohydroxypyrimidines, diamino dihydroxypyrimidines, Dihydroxynaphtaline, naphthols, pyrazolones, hydroxyquinolines, aminoquinolines, primary aromatic amines, which have in the ortho, meta or para position a further free or substituted with C ⁇ ⁇ C4-alkyl or C2-C4-hydroxyalkyl groups hydroxy or
  • Suitable inorganic redox-active substances are, for example, metal salts and / or metal complexes selected from the group consisting of manganese, titanium, zirconium, hafnium, vanadium, cobalt and cerium salts and / or complexes, in which the metals are in one of the oxidation stages II, III, IV, V or VI are present.
  • Metal salts and / or metal complexes selected from the group MnSO4, Mn (II) citrate, Mn (II) stearate, Mn (II) acetylacetonate, Mn (II) - [l-hydroxyethane-l, l- diphosphonate], V2O5, V2O4, VO2, Ti0S04, K 2 TiF 6 , K 2 ZrF 6 , C0SO4, Co (N0 3 ) 2 , Ce (N0 3 ) 3 .
  • Suitable paraffin oil are predominantly branched aliphatic hydrocarbons with a number of carbon atoms in the range from 20 to 50.
  • the paraffin oil is preferably selected from predominantly branched chain C25_45 species with a ratio of cyclic to noncyclic hydrocarbons of 1:10 to 2: 1, preferably of 1: 5 to 1: 1.
  • a silver / copper corrosion protection agent is present in the machine dishwashing detergent according to the invention, it is preferably present with 0.01 to 5% by weight, particularly preferably with 0.1 to 2% by weight, of the total weight.
  • MGDA in the dishwasher detergent is sufficiently high, such as 25% or more, preferably 30% or more, in each case based on the free acid, so that bleaching agents can be dispensed with, a Silver / copper anti-corrosion agents can be dispensed with.
  • the machine dishwashing detergents according to the invention are not caustic and therefore do not require any particularly secure packaging. A good washing result can be achieved with a relatively low amount of 15-20 g powder or 20-50 ml liquid cleaner. According to current knowledge, all ingredients are neither toxic nor otherwise harmful to health.
  • the cleaning agents described here are therefore also an environmentally friendly and consumer-friendly alternative to the conventional cleaners with complexing agents that work in the strongly basic area.
  • the methylglycinediacetic acid used according to the invention has the following structural formula:
  • the methylglycinediacetic acid is particularly preferably used as the free acid or as the sodium or potassium salt and is preferably present in the dishwashing detergent in an amount of 3% to 90%, based on the free acid.
  • the amount of MGDA is preferably at least 5%, based on the free acid.
  • an approximately 0.5% aqueous solution of the washing-up liquid has a pH of not more than 10.4.
  • the pH of an approximately 0.5% aqueous solution of the washing-up liquid according to the invention is preferably from more than 6 to 10.4, particularly preferably from 7 to 10.0.
  • dishwashing detergents are made from the following ingredients:
  • MGDA trisodium salt of methylglycinediacetic acid
  • MGDA is not commercially available in its pure form and therefore a 77% solution in water was used. A larger amount of the commercially available product had to be used, as shown in the table. Two values are given in the table for MGDA. The first value indicates the amount in g of the commercial product, and the second value corresponds to the corresponding amount of pure substance (100%).
  • the following example shows that by replacing part of the builder of a machine dishwashing detergent with methylglycinediacetic acid, an excellent washing performance can be achieved at low pH values and, contrary to theoretical expectations, the ability to remove milk residues and tea residues is higher than with other common complexing agents such as NTA.
  • the example illustrates the invention.
  • Liquid dishwashing detergents were prepared with a composition as shown in Table 1 (both in accordance with the invention using MGDA and using the NTA used in the prior art) and their washing performance was determined by means of dishes which were both milk and milk Contained tea residues, determined.
  • DIN Standard No. 44990, Part 2 was essentially followed.
  • a Bosch SMS 5062 dishwasher was used.
  • the water had a hardness of 19 ° dH (3.39 mmol calcium carbonate), the temperature of the water was 65 ° C and 20 ml detergent was used in each case.
  • the results of the wash performance were rated on a scale of 1-5 (5 stands for 100% clean dishes) and are also listed in Table 1.
  • the non-ionic surfactant is . is a common, low-foaming ethoxylated and propoxylated fatty alcohol. Common proteases and amylases are used. Table 1

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  • Chemical & Material Sciences (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Oil, Petroleum & Natural Gas (AREA)
  • Wood Science & Technology (AREA)
  • Organic Chemistry (AREA)
  • Inorganic Chemistry (AREA)
  • Detergent Compositions (AREA)
EP97928266A 1996-06-21 1997-06-20 PRODUIT DE RINçAGE POUR LAVE-VAISSELLE, FAIBLEMENT ALCALIN, CONTENANT DU MGDA Revoked EP0906407B1 (fr)

Priority Applications (1)

Application Number Priority Date Filing Date Title
EP01105118A EP1113070B1 (fr) 1996-06-21 1997-06-20 Composition de lavage automatique de la vaisselle à basse alkalinité contenant du MGDA

Applications Claiming Priority (3)

Application Number Priority Date Filing Date Title
DE19624839 1996-06-21
DE19624839 1996-06-21
PCT/EP1997/003256 WO1997049792A1 (fr) 1996-06-21 1997-06-20 Produit de rinçage pour lave-vaisselle, faiblement alcalin, contenant du mgda

Related Child Applications (1)

Application Number Title Priority Date Filing Date
EP01105118A Division EP1113070B1 (fr) 1996-06-21 1997-06-20 Composition de lavage automatique de la vaisselle à basse alkalinité contenant du MGDA

Publications (2)

Publication Number Publication Date
EP0906407A1 true EP0906407A1 (fr) 1999-04-07
EP0906407B1 EP0906407B1 (fr) 2001-09-05

Family

ID=7797614

Family Applications (2)

Application Number Title Priority Date Filing Date
EP97928266A Revoked EP0906407B1 (fr) 1996-06-21 1997-06-20 PRODUIT DE RINçAGE POUR LAVE-VAISSELLE, FAIBLEMENT ALCALIN, CONTENANT DU MGDA
EP01105118A Revoked EP1113070B1 (fr) 1996-06-21 1997-06-20 Composition de lavage automatique de la vaisselle à basse alkalinité contenant du MGDA

Family Applications After (1)

Application Number Title Priority Date Filing Date
EP01105118A Revoked EP1113070B1 (fr) 1996-06-21 1997-06-20 Composition de lavage automatique de la vaisselle à basse alkalinité contenant du MGDA

Country Status (6)

Country Link
EP (2) EP0906407B1 (fr)
AT (2) ATE389709T1 (fr)
CA (1) CA2258218A1 (fr)
DE (2) DE59704543D1 (fr)
ES (2) ES2160355T3 (fr)
WO (1) WO1997049792A1 (fr)

Cited By (2)

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WO2020053316A1 (fr) 2018-09-12 2020-03-19 Claro Products Gmbh Agent de protection de l'argent

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WO2020053316A1 (fr) 2018-09-12 2020-03-19 Claro Products Gmbh Agent de protection de l'argent

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Publication number Publication date
EP1113070A2 (fr) 2001-07-04
CA2258218A1 (fr) 1997-12-31
ES2160355T3 (es) 2001-11-01
DE59704543D1 (de) 2001-10-11
ATE205250T1 (de) 2001-09-15
ES2300287T3 (es) 2008-06-16
WO1997049792A1 (fr) 1997-12-31
EP1113070A3 (fr) 2002-01-02
EP1113070B1 (fr) 2008-03-19
EP0906407B1 (fr) 2001-09-05
ATE389709T1 (de) 2008-04-15
DE59712930D1 (de) 2008-04-30

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