EP1918418B1 - Verfahren zur Beschichtung eines Substrats - Google Patents

Verfahren zur Beschichtung eines Substrats Download PDF

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Publication number
EP1918418B1
EP1918418B1 EP06022490A EP06022490A EP1918418B1 EP 1918418 B1 EP1918418 B1 EP 1918418B1 EP 06022490 A EP06022490 A EP 06022490A EP 06022490 A EP06022490 A EP 06022490A EP 1918418 B1 EP1918418 B1 EP 1918418B1
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European Patent Office
Prior art keywords
inorganic
coating
substrate
component
organic
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English (en)
French (fr)
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EP1918418A1 (de
Inventor
Wu Li
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Tata Steel UK Ltd
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Tata Steel UK Ltd
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Priority to AT06022490T priority Critical patent/ATE496152T1/de
Priority to DE602006019740T priority patent/DE602006019740D1/de
Priority to ES06022490T priority patent/ES2359930T3/es
Priority to EP06022490A priority patent/EP1918418B1/de
Publication of EP1918418A1 publication Critical patent/EP1918418A1/de
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Classifications

    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C18/00—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating
    • C23C18/02—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating by thermal decomposition
    • C23C18/12—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating by thermal decomposition characterised by the deposition of inorganic material other than metallic material
    • C23C18/125—Process of deposition of the inorganic material
    • C23C18/1262—Process of deposition of the inorganic material involving particles, e.g. carbon nanotubes [CNT], flakes
    • C23C18/127—Preformed particles
    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C18/00—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating
    • C23C18/02—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating by thermal decomposition
    • C23C18/12—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating by thermal decomposition characterised by the deposition of inorganic material other than metallic material
    • C23C18/1204—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating by thermal decomposition characterised by the deposition of inorganic material other than metallic material inorganic material, e.g. non-oxide and non-metallic such as sulfides, nitrides based compounds
    • C23C18/122—Inorganic polymers, e.g. silanes, polysilazanes, polysiloxanes
    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C18/00—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating
    • C23C18/02—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating by thermal decomposition
    • C23C18/12—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating by thermal decomposition characterised by the deposition of inorganic material other than metallic material
    • C23C18/125—Process of deposition of the inorganic material
    • C23C18/1254—Sol or sol-gel processing

Definitions

  • the present invention relates to the field of abrasion-resistant coatings for coil substrates and method for producing coated coil products, in particular, but not exclusively, abrasion-resistant organic-inorganic coatings for coil substrates.
  • Scratch and abrasion resistant coatings have been successfully developed and commercially exploited to protect the surface of transparent plastics from abrasion.
  • an acidic dispersion of colloidal silica and hydroxylated silsesquioxane has been used in an alcohol-water medium to coat substrates such as acrylic lenses to provide an abrasion-resistant coating.
  • a coil or strip product manufactured in drawing processes requires a coating to be sufficiently flexible to withstand winding operations and have adequate abrasion resistant so as to endure a production environment in which the surface of the coil could be damaged and consequently its properties impaired to intolerant levels.
  • the object of this invention is to create a multi-functional coating that can be applied in a single pass utilising existing coating technology.
  • the flexibility of the coating can be achieved by the use of organic materials while the hardness of inorganic materials can improve mechanical properties.
  • An object of this invention is to combine inorganic and organic components into one material to provide an organic-inorganic hybrid material.
  • the properties can be varied continuously from soft and flexible to brittle and hard materials and thus enable the 'tailoring' of certain properties to form an optimum coating.
  • Such multifunctional coatings described in the invention of this patent can be realised by using the sol-gel process, wherein inorganic material can be synthesized in organic media at temperatures at which organic compounds are thermally stable.
  • the sol-gel process starts with a colloidal dispersion, or sol, from the hydrolysis and condensation reactions of metal alkoxides such as silicone, aluminium or titanium metal alkoxides.
  • metal alkoxides such as silicone, aluminium or titanium metal alkoxides.
  • the sol may be transformed into a rigid gel, which could be shaped into different forms such as films, monoliths, or fibres.
  • sol-gel coatings for coil-coating applications has previously been avoided due to their long curing times and poor flexibility caused by the build up of intrinsic coating stresses and rigidity of inorganic content. With this development of the coatings of this invention, it has been seen that the final product combines the hardness associated with harder co-laminated products with a similar flexibility to DA polyesters.
  • the invention addresses the disadvantages and deficiencies of organic or inorganic protective coatings alone, and provides an abrasion-resistant flexible coating for a variety of substrates.
  • the hybrid coating composition has one inorganic compound of hydrolysed glycidoxyalkyltrialkoxysilane, an organic compound selected from the group consisting of modified diamine, and a curing agent. It is preferred that the inorganic compound is alkylsilane with an epoxy group.
  • the composition is coated to the primed non-primed metal substrate and then thermal cured to constitute an abrasion resistant but flexible coating film.
  • the flexibility of the hybrid coating is controlled by the molar ratio between the organic and inorganic compound.
  • the inorganic component is selected from a group comprising hydrolysed silanes, and the organic component is selected from a group comprising modified di-amines.
  • preparing the inorganic component and the organic component includes weighing the appropriate fractions of each components.
  • the step of combining the inorganic and the organic components includes mechanical stirring preferably magnetic stirring of the components.
  • the step of applying the combined inorganic and organic components over the substrate is achieved by draw bar coating the components as a film having a pre-determined thickness.
  • the step of preparing the inorganic component is undertaken by hydrolysing glycidoxyalkyltrialkoxysilane (GPS) alone.
  • GPS glycidoxyalkyltrialkoxysilane
  • step of hydrolysing GPS is undertaken in combination with other silanes.
  • the step of hydrolysing GPS is undertaken in combination with colloidal silica nanoparticles.
  • the step of preparing the organic component includes endcapping ethanolamine to a bisphenol A diglyoxygl ether compound to produce a modified amine.
  • Typical difunctional amines are ethanolamine, propylamine and ethylamine, cyclohexanamine etc.
  • Typical difunctional diglycidyl ethers are bisphenol A diglycidyl ether.
  • the molar ratio of the ethanolamine (diamine) to a bisphenol A diglyoxygl ether (diglycidyl ether) compound is from 2:1 to 2:1.6
  • the molar ratio of the ethanolamine (diamine) to a bisphenol A diglyoxygl ether (diglycidyl ether) compound is 2:1.1.
  • the step of exposing the inorganic and organic components is undertaken at a predetermined temperature ranging from 80°C to 280°C, for a period typically around 30 seconds to 30 minutes, preferably hot air or current or IR lamp is used to heat the substrate.
  • the step of exposing the inorganic and organic components leads to a metal peak temperature of between 160° C to 234° C.
  • method can be applied for coating a strip product.
  • method can be applied for coating a coil product.
  • the combined inorganic and organic components are applied using the draw bar method
  • organic/inorganic hybrid coatings relating to this invention are provided for in the context of a two-pack system produced by sol-gel processing, both of which will be described hereunder with reference the drawings indicated above.
  • the hybrid coating are to be applied to primed or unprimed steel strips.
  • Substrates that can have improved abrasion resistance using the above coatings in accordance with this invention include a variety of plastic substrates, including polycarbonate and acrylic, and non-plastic substrates.
  • the abrasion resistant hybrid coating composition comprises an inorganic component ("Component A”) and an organic component (“Component B”) and each can be prepared in the following manner. Preparation of the inorganic component is undertaken by hydrolysing glycidoxyalkyltrialkoxysilane alkylalkoxysilane (GPS) alone, or in combination with other silane or colloidal silica nanoparticles.
  • Component A inorganic component
  • Component B organic component
  • Preparation of the inorganic component is undertaken by hydrolysing glycidoxyalkyltrialkoxysilane alkylalkoxysilane (GPS) alone, or in combination with other silane or colloidal silica nanoparticles.
  • GPS glycidoxyalkyltrialkoxysilane alkylalkoxysilane
  • the organic component is a modified amine prepared by endcapping ethanolamine to a bisphenol A diglyoxygl ether compound (difunctional amine to a diglycidyl ether compound) at molar ratio of 2:1.1.
  • Typical difunctional amines are ethanolamine, propylamine and ethylamine, cyclohexanamine etc.
  • Typical difunctional diglycidyl ethers are bisphenol A diglycidyl ether.
  • the molar ratio between the glycidoxyl group from silane and the amino group from modified amine ranges between 1:0.5 and 2:1.
  • the weight ratio between GPS and other silane from 1:0 to 1:1 can be used, but could preferably be extended to 1:2.
  • Hydrolysed silane and silane-silica solution forms component A of the formulation, while an organic component forms component B of the formulation.
  • component A and component B are weighed to the desired amounts and magnetically stirred before being draw bar coated onto the substrate.
  • the substrate may be primed or non-primed steel and should be cleaned with acetone prior to application of the coating.
  • the two components are mixed together just before being coated to the substrate.
  • the coated material is placed in a chamber in which the wet film may be heated in the temperature range from 80°C to 280°C, for a period typically around 30 seconds to 30 minutes.
  • composition of the hybrid 2-pack coating comprising:
  • composition of another hybrid 2-pack coating comprising:
  • a silicate network is formed by the condensation reaction of hydrolysed silane, with the network providing the desired mechanical property of the coating, in particular, the abrasion resistance.
  • Organic component participates in the network formation by the reaction of the glycidoxyl group and amino group.
  • the level of organic (the molar ratio between glycidoxyl group and amino group) in the composition controls the degree of flexibility of the hybrid coating.
  • Measurements to characterise the coating included coating thickness, Taber abrasion resistance testing and T-bend testing.
  • the former giving an indication of the performance of the hybrid coating in an abrasive environment while the latter giving an indication of the flexibility of the hybrid coating.
  • Coating thickness on the substrate can be measured by permascope or borascopy techniques and was determined to lie in the range between 6-10 ⁇ m.
  • the abrasion resistance was undertaken by Taber abrasion testing while the flexibility of the coatings was determined using the T-bend test.
  • Abrasion resistance was measured by ECCA T16 [1999] Taber abrasion testing using CS10 Calibrase wheels and 1000g weights on the abraser arms for 250 cycles.
  • T-bend test the substrate is wrapped around itself to form a "swiss-roll" configuration, the result being quoted in "T” value and represents the minimum bend radii at which point film failure (in the form of cracking or delamination) does not occur.
  • Half T is the equivalent of one thickness of substrate.
  • the physical properties of the first and second experiment coatings are shown in Table 1 below. As an indication of the improvements in abrasion resistance and flexibility of the new coatings, the results are compared with abrasion resistance and flexibility T-bent tests conducted on domestic appliance polyester and co-laminated products. Table 1. Physical Properties Abrasion resistance: Taber Flexibility: T-Bend DA Polyester 19mg 1T Model coating 1 0.7-0.8mg 2T Model coating 2 a) 0.1 mg a) 4T b) 0.9mg b) 2T
  • the first and second experiment coatings above were tested using salt spray tests, which demonstrated that the coatings act as a good physical barrier against corrosion, but will not prevent or slow down the corrosion reaction, as corrosion inhibitors have not been included within the formulation.
  • the inorganic-organic hybrid coating in accordance with the invention combines excellent abrasion resistance with an acceptable flexibility. It can be seen that by altering the mix of the inorganic-organic components, a wide range of properties can be achieved. For example, it may be possible to increase the flexibility of the coating but with a subsequent reduction in the abrasion resistance.
  • the flexibility of the coating is quite important especially where it is applied on substrates such as coils. In particular flexibility of the coating is paramount where the substrate coils are subjected to moderate to aggressive manufacturing environments in which they are tortuously and repetitively wound before being mounted on the end product.
  • the invention clearly demonstrates that two series of two-pack sol-gel hybrid coatings can be produced which have an excellent combination of abrasion resistance, flexibility and fast curing times. Coatings can be cured at a PMT of 160°C, and more significantly, there is no impact on physical properties from over-curing. In the Taber abrasion resistance test, most novel compositions of the coatings of this invention had a mass loss of 0.1-0.9 mg per 250 cycles but coatings with a mass loss as low as 0.3 mg after 500 cycles have been produced. The flexibility is 2T (4T for the harder coatings) in T-bend test and can be better than 16J in reverse impact tests (move this above).
  • modified amine(s) and the proportions described herein are novel in accordance with this invention. Further, the general use and preparation method of the inorganic component (hydrolysed silane) is well known to the skilled addressee in this field and will not be described herein. Traditional multi-functional amine has been used but leads to a hard and rigid coating.
  • the inorganic and organic compounds that forms a hybrid network on the surface of the substrate.
  • the level of organic component controls the flexibility of the coating. If the organic component is taken away, the conventional sol-gel coating will be formed, which is hard and rigid and may not be useful for coating coil or strip products.
  • the molar ratio between the glycidoxyl group from silane and the amino group from modified amine ranges between 1:1 and 2:1.
  • a molar ratio between epoxy and amine group of 1:2 is used at the moment.
  • Anther ratio such as 1:1.5 could also be used.
  • the weight ratio between GPS and other silane from 1:0 to 1:1 has been used, but could be extend to 1:2.
  • the new hybrid coatings have combined the hardness of a co-laminate and the flexibility of DA polyester. Further, salt spray test results have shown that hybrid coatings can act as a physical barrier and can give good corrosion protection to galvanised steel substrates.

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  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Metallurgy (AREA)
  • Physics & Mathematics (AREA)
  • Thermal Sciences (AREA)
  • General Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Mechanical Engineering (AREA)
  • Inorganic Chemistry (AREA)
  • Nanotechnology (AREA)
  • Dispersion Chemistry (AREA)
  • Application Of Or Painting With Fluid Materials (AREA)
  • Paints Or Removers (AREA)
  • Polymers With Sulfur, Phosphorus Or Metals In The Main Chain (AREA)
  • Macromolecular Compounds Obtained By Forming Nitrogen-Containing Linkages In General (AREA)

Claims (16)

  1. Verfahren zum Beschichten eines Substrats, umfassend die folgenden Schritte:
    Vorsehen eines Substrats;
    Herstellen einer anorganischen Komponente, wobei die anorganische Komponente aus einer Gruppe gewählt ist, die hydrolysierte Silane umfasst;
    Herstellen einer organischen Komponente durch Endverkappen eines difunktionellen Amins an einem Diglycidylether unter Erzeugung eines modifizierten Diamins;
    Kombinieren der anorganischen Komponente mit der organischen Komponente vor der Aufbringung der Mischung auf das Substrat;
    Aufbringen der kombinierten anorganischen und organischen Komponenten über dem Substrat;
    Aussetzen der kombinierten anorganischen und organischen Komponenten einer vorbestimmten Temperatur, um eine Reaktion zwischen anorganischen und organischen Komponenten zu bewirken, um so eine Netzwerkstruktur der Beschichtung auf dem Substrat zu erzeugen.
  2. Verfahren gemäß Anspruch 1, wobei die kombinierten anorganischen und organischen Komponenten unter Anwendung einer Sol-Gel-Verarbeitung hergestellt werden.
  3. Verfahren gemäß einem der vorausgehenden Ansprüche, wobei der Schritt des Herstellens der anorganischen Komponente durch Hydrolysieren von Glycidoxyalkyltrialkoxysilan (GPS) allein durchgeführt wird.
  4. Verfahren gemäß einem der vorausgehenden Ansprüche, wobei der Schritt des Hydrolysierens von GPS in Kombination mit anderen Silanen durchgeführt wird.
  5. Verfahren gemäß einem der vorausgehenden Ansprüche, wobei der Schritt des Hydrolysierens von GPS in Kombination mit kolloidalen Silica-Nanopartikeln durchgeführt wird.
  6. Verfahren gemäß einem der vorausgehenden Ansprüche, wobei der Schritt des Herstellens der organischen Komponente das Endverkappen von Ethanolamin an eine Bisphenol-A-diglyoxyl-etherverbindung unter Erzeugung eines modifizierten Amins einschließt.
  7. Verfahren gemäß einem der vorausgehenden Ansprüche, wobei das Molverhältnis von dem Ethanolamin zu einer Bisphenol-A-diglyoxyl-ether- (Diglycidolether) verbindung im Bereich von 2 : 1 bis 2 : 1,6 liegt.
  8. Verfahren gemäß einem der vorausgehenden Ansprüche, wobei das Molverhältnis von dem Ethanolamin zu einer Bisphenol-A-diglyoxyl-ether- (Diglycidolether) verbindung 2 : 1,1 beträgt.
  9. Verfahren gemäß einem der vorausgehenden Ansprüche, wobei die vorbestimmte Temperatur im Bereich von 80°C bis 280°C für eine Zeitspanne typischerweise um etwa 30 Sekunden bis 30 Minuten liegt; vorzugsweise heiße Luft oder Strom oder eine IR-Lampe zum Erwärmen des Substrats zum Einsatz kommt.
  10. Verfahren gemäß einem der vorausgehenden Ansprüche, wobei der Schritt des Exponierens der anorganischen und organischen Komponenten zu einer Metall-Spitzentemperatur zwischen 160°C bis 234°C führt.
  11. Verfahren gemäß einem der vorausgehenden Ansprüche, wobei die kombinierten anorganischen und organischen Komponenten mit Hilfe des Ziehstabverfahrens aufgebracht werden.
  12. Verfahren gemäß einem der vorausgehenden Ansprüche, wobei die Beschichtung eine Beschichtungsdicke von 6 - 10 µm nach dem Aussetzen der kombinierten anorganischen und organischen Komponenten an eine vorbestimmte Temperatur besitzt.
  13. Verfahren gemäß einem der vorausgehenden Ansprüche 1 - 12 zum Beschichten eines Streifenprodukts.
  14. Verfahren gemäß einem der vorausgehenden Ansprüche 1 - 12 zum Beschichten eines Wicklungsprodukts.
  15. Verfahren gemäß Anspruch 13 oder 14, wobei das Produkt auf einen Gegenstand montiert ist.
  16. Beschichtetes Substrat, wobei die Beschichtung eine kombinierte anorganische Komponente und organische Komponente umfasst, wobei die organische Komponente ein difunktionelles Amin, endverkappt an einem Diglycidylether, umfasst.
EP06022490A 2006-10-27 2006-10-27 Verfahren zur Beschichtung eines Substrats Active EP1918418B1 (de)

Priority Applications (4)

Application Number Priority Date Filing Date Title
AT06022490T ATE496152T1 (de) 2006-10-27 2006-10-27 Verfahren zur beschichtung eines substrats
DE602006019740T DE602006019740D1 (de) 2006-10-27 2006-10-27 Verfahren zur Beschichtung eines Substrats
ES06022490T ES2359930T3 (es) 2006-10-27 2006-10-27 Método para el recubrimiento de un substrato.
EP06022490A EP1918418B1 (de) 2006-10-27 2006-10-27 Verfahren zur Beschichtung eines Substrats

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
EP06022490A EP1918418B1 (de) 2006-10-27 2006-10-27 Verfahren zur Beschichtung eines Substrats

Publications (2)

Publication Number Publication Date
EP1918418A1 EP1918418A1 (de) 2008-05-07
EP1918418B1 true EP1918418B1 (de) 2011-01-19

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EP06022490A Active EP1918418B1 (de) 2006-10-27 2006-10-27 Verfahren zur Beschichtung eines Substrats

Country Status (4)

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EP (1) EP1918418B1 (de)
AT (1) ATE496152T1 (de)
DE (1) DE602006019740D1 (de)
ES (1) ES2359930T3 (de)

Family Cites Families (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4299746A (en) * 1978-11-30 1981-11-10 General Electric Company Silicone resin coating composition
AU2002220566B8 (en) * 2000-09-25 2007-09-13 Chemetall Gmbh Method for pretreating and coating metal surfaces, prior to forming, with a paint-like coating and use of substrates so coated
ATE553163T1 (de) * 2003-02-25 2012-04-15 Chemetall Gmbh Verfahren zur beschichtung von metallischen oberflächen mit einem gemisch enthaltend mindestens zwei silane
DE10320765A1 (de) * 2003-05-09 2004-11-25 Degussa Ag Mittel zur Beschichtung von Metallen zum Schutz vor Korrosion

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Publication number Publication date
ATE496152T1 (de) 2011-02-15
DE602006019740D1 (de) 2011-03-03
ES2359930T3 (es) 2011-05-30
EP1918418A1 (de) 2008-05-07

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