EP1153669B1 - Verfahren für Mehrschichtbeschichtung - Google Patents

Verfahren für Mehrschichtbeschichtung Download PDF

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Publication number
EP1153669B1
EP1153669B1 EP20000109836 EP00109836A EP1153669B1 EP 1153669 B1 EP1153669 B1 EP 1153669B1 EP 20000109836 EP20000109836 EP 20000109836 EP 00109836 A EP00109836 A EP 00109836A EP 1153669 B1 EP1153669 B1 EP 1153669B1
Authority
EP
European Patent Office
Prior art keywords
coating
clearcoat
basecoat
functionality
epoxy
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.)
Expired - Lifetime
Application number
EP20000109836
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English (en)
French (fr)
Other versions
EP1153669A1 (de
Inventor
Rodney Briggs
Gregory Menovcik
Josef Rademacher
Cynthia Stants
Michele L. Stauffer
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BASF Corp
Original Assignee
BASF Corp
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 BASF Corp filed Critical BASF Corp
Priority to EP20000109836 priority Critical patent/EP1153669B1/de
Priority to DE2000633787 priority patent/DE60033787T2/de
Priority to ES00109836T priority patent/ES2283254T3/es
Publication of EP1153669A1 publication Critical patent/EP1153669A1/de
Application granted granted Critical
Publication of EP1153669B1 publication Critical patent/EP1153669B1/de
Anticipated expiration legal-status Critical
Expired - Lifetime legal-status Critical Current

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Classifications

    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B05—SPRAYING OR ATOMISING IN GENERAL; APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
    • B05D—PROCESSES FOR APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
    • B05D7/00—Processes, other than flocking, specially adapted for applying liquids or other fluent materials to particular surfaces or for applying particular liquids or other fluent materials
    • B05D7/50—Multilayers
    • B05D7/52—Two layers
    • B05D7/54—No clear coat specified
    • B05D7/546—No clear coat specified each layer being cured, at least partially, separately
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B05—SPRAYING OR ATOMISING IN GENERAL; APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
    • B05D—PROCESSES FOR APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
    • B05D5/00—Processes for applying liquids or other fluent materials to surfaces to obtain special surface effects, finishes or structures
    • B05D5/06—Processes for applying liquids or other fluent materials to surfaces to obtain special surface effects, finishes or structures to obtain multicolour or other optical effects
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B05—SPRAYING OR ATOMISING IN GENERAL; APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
    • B05D—PROCESSES FOR APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
    • B05D7/00—Processes, other than flocking, specially adapted for applying liquids or other fluent materials to particular surfaces or for applying particular liquids or other fluent materials
    • B05D7/50—Multilayers
    • B05D7/56—Three layers or more
    • B05D7/57—Three layers or more the last layer being a clear coat
    • B05D7/577—Three layers or more the last layer being a clear coat some layers being coated "wet-on-wet", the others not

Definitions

  • the invention relates to a method for a multilayer coating providing intercoat adhesion between a powder primer coating layer and a clearcoat layer.
  • a multilayer coating provides a decorative or a protective coating on a substrate.
  • the multilayer coating on a substrate employs at least two coating layers which may be any combination of electrocoat, primer, filler, pigmented basecoat, and clearcoat coating layers.
  • the multilayer coating may be obtained by first applying a powder primer to a bare or electrocoated substrate. Over the primer layer, other coatings such as the basecoat and clearcoat may be applied. In some instances, a basecoat is applied over the primer and then a clearcoat layer of a coating is applied over the basecoat. Where a two color coating is desired, different approaches may be taken.
  • one color basecoat may be applied to part of a primer-coated substrate, then a clearcoat is applied to the entire substrate, followed by application of a different color basecoat to the remainder of the substrate, and finally a clearcoat layer being applied over all.
  • one primer-coated area may be painted with basecoat, followed by application of the clearcoat, and curing of both layers together or sequentially. The area is then covered to protect it from a second color. Subsequently, a second primer-coated area is coated with a different color basecoat, then coated with clearcoat, and the layers are cured together or sequentially.
  • the present invention is directed to a method for forming a multilayer coating promoting intercoat adhesion.
  • the present invention is further directed to a method for forming a multilayer coating, promoting intercoat adhesion between a primer layer and a clearcoat layer in direct contact with each other.
  • a method for obtaining a cured multi-layer coating which promotes intercoat adhesion comprising the steps of:
  • the present invention provides a method for forming a multilayer coating which promotes intercoat adhesion.
  • the method is particularly useful in a multilayer coating utilizing a powder primer comprising a polyester resin and an epoxy functional crosslinking agent and a clearcoat composition comprising a hydroxy functional acrylic resin and a crosslinking agent reactive with the hydroxy functionality.
  • the invention is useful for promoting intercoat adhesion between the primer and basecoat or the primer and clearcoat layers that directly contact each other.
  • the polyester resin of the invention has a carboxyl functionality of less than two. It is undesirable that the polyester have a carboxyl functionality of greater than 2, as coatings containing such polyesters demonstrate less desirable appearance and adhesion.
  • Such polyester resins are obtained by a condensation reaction between a polyol component and a poly-functional acid component or its anhydride. Excess poly-functional acid is used so that an acid-functional polyester is formed.
  • the polyester resin has an acid number of 30 to 38 mg KOH/g.
  • the polyester resin also preferably has a Tg of 50 to 60°C.
  • the viscosity of the polyester, as measured at 200°C, is preferably from 4500 to 5500 mPas.
  • the poly-functional acid or anhydride compound used to form the polyester may be alkyl, alkylene, aralkylene, or aromatic compounds.
  • Dicarboxylic acids and anhydrides are preferred. However, acids or anhydrides with higher functionality may also be used. If tri-functional compounds or compounds of higher functionality are used, these may be used in mixture with mono-functional carboxylic acids or anhydrides of monocarboxylic acids, such as versatic acid, fatty acids, or neodecanoic acid.
  • acid or anhydride functional compounds suitable for forming the polyester groups or anhydrides of such compounds include phthalic acid, phthalic anhydride, isophthalic acid, terephthalic acid, hexahydrophthalic acid, tetrachlorophthalic anhydride, hexahydrophthalic anhydride, pyromellitic anhydride, succinic acid, azeleic acid, adipic acid, 1,4-cyclohexanedicarboxylic acid, citric acid, and trimellitic anhydride.
  • the polyol component used to make the polyester resin also has a hydroxyl functionality of at least 2.0.
  • the polyol component may contain mono-, di-, and tri-functional alcohols, as well as alcohols of higher functionality. Diols are preferred as the polyol component. Alcohols with higher functionality may be used where some branching of the polyester is desired, and mixtures of diols and triols are also preferred as the polyol component. Highly branched polyesters are not desired due to undesirable effects on the coating, such as decreased flow and undesirable effects on the cured film, such as diminished chip resistance and smoothness.
  • useful polyols are ethylene glycol, diethylene glycol, triethylene glycol, propylene glycol, dipropylene glycol, butylene glycol, glycerine, trimethylolpropane, trimethylolethane, pentaerythritol, neopentyl glycol, 2,2,4-trimethyl-1,3-pentanediol, 1,6-hexanediol, 1,4-cyclohexane dimethanol, hydrogenated bisphenol A, and hydoxyalkylated bisphenols.
  • polyester resins are typically formed by heating together the polyol and poly-functional acid components, with or without catalysis, while removing the by-product of water in order to drive the reaction to completion.
  • a small amount of a solvent, such as toluene, may be added in order to remove the water azeotropically. If added, such solvent is preferably removed from the polyester product before powder coating formulation is begun.
  • polyester resins are commercially available as 100% solid materials that can be used in powder coating compositions, such as those sold by Hoechst, Portsmouth, Virginia 23704, under the tradename Alftalat; by EMS-American Grilon, Inc., Sumter, South Carolina 29151, under the tradename Grilesta; and by CIBA-Geigy Corporation, Ardsley, New York 10502, under the tradename Arakote.
  • thermosetting powder coating composition of the invention further includes a crosslinker that is reactive toward the carboxyl groups of the polyester resin.
  • crosslinker examples include epoxy-functional compounds, such as epoxy-functional epoxy resins, epoxy-functional acrylic resins, and triglycidyl isocyanurate; polyoxazolines; and polydioxanes.
  • epoxy-functional epoxy resins include bisphenol A-type epoxy resins, novolac epoxy resins, and alicyclic epoxy resins. Epoxy resins based on bisphenol A are preferred. The epoxy resins preferably have epoxy equivalent weights between 500 and 2000, and more preferably between 600 and 1000. The polyepoxide may be saturated or unsaturated, aliphatic, cycloaliphatic, aromationc or heterocyclic. Examples of suitable polyhydric alcohols include 2,2-bis(4-hydroxyphenyl)propane (BisphenolA); 2,2-bis(4-hydroxy-tert butylphenyl)propane; .
  • 1,1-bis(4-hydroxyphenyl)ethane 1,1-bis(4-hydroxyphenyl)isobutane; 2,2-bis(4-hydroxytertiarybutylphenyl)propane; bis(2-hydroxynapthyl)methane; 1,5-dihydroxynaphththalene; 1,1 -bis(4-hydroxy-3-alkylphenyl)ethane and the like.
  • Solid epoxy resins suitable for use in powder coatings are readily available commercially, such as bisphenol A, for example, from Dow Chemical Co., Midland, Michigan 48674, under the tradename D.E.R.; Araldite,from CIBA-Geigy Corp., Ardsley, New York, 10502 from Shell Chemicals, Yardley , PA under the tradename Epon.
  • the polyester-epoxy coating composition have a ratio of epoxy to carboxy of greater than one, to provide the intercoat adhesion provided by the present invention.
  • the intercoat adhesion provided between the powder layer and additional coating layers improved greatly where the ratio of epoxy to carboxy functionality was greater than an approximately stoichiometric ratio of 1:1, where a variation of ⁇ 2% is considered within stoichiometric proportions.
  • the preferred ratio of carboxy to epoxy functionality in the primer coating composition is 1.0:1.05 to 1.0:1.9, and more preferably between 1.15:1 and 1.7:1. Most preferanbly, the ratio of epoxy to carboxy functionality is between s 1.4:1 to 1.6:1.
  • the excess epoxy functionality is available to react with the reactive functionality of additional coating layers, where such reactive functionality may be hydroxyl, phenol, amino, carboxyl, epoxy or mercaptan.
  • the excess epoxy also improves rheology of the coating composition and may serve to scavenge excess amines from an electrocoating composition, that may migrate to the surface of a cured coating and deleteriously effect the long term durability of the coating.
  • Clearcoat coating compositions according to the present invention may comprise a polyurethane or acrylic based coating cured with melamine or isocyanate.
  • the clearcoat includes a reactive functionality such as hydroxyl, phenol, amino, carboxyl, epoxy or mercaptan.
  • the clearcoat comprises an acrylic resin having hydroxyl functionality.
  • the acrylic resin has a weight average molecular weight of between about 4000-6000, preferably about 4000, a hydroxy equivalent weight of between about 280-350, preferably about 310-330.
  • the crosslinking agent for the clearcoat is selected from the group consisting of melamine, blocked isocyanate and unblocked isocyanate crosslinkers and mixtures thereof.
  • the clearcoat composition comprises a mixture of alkylated melamine and a blocked isocyanate crosslinker.
  • the clearcoat may be waterborne, solvent borne or powder.
  • the clearcoat is solvent borne.
  • the solvent is present in an amount between 30 and 60%, preferably 40-50% by weight.
  • the clearcoat may comprise additional components such as ultraviolet light absorbers, hindered amine light stabilizers, surfactants, stabilizers, fillers, wetting agents, rheology control agents, dispersing agents and adhesion promoters. While the agents are well known in the prior art, the amount used must be controlled to avoid adversely affecting the coating characteristics.
  • Pigmented basecoat compositions useful for purposes of the present invention include any of a number of types well known in the art, and do not require explanation in detail.
  • Polymers known in the art to be useful in basecoat compositions include acrylics, vinyls, polyurethanes, polycarbonates, polyesters, alkyds and polysiloxanes.
  • Preferred polymers include acrylics, vinyls, polyurethanes, polycarbonates, polyesters, alkyds, and polysiloxanes.
  • Preferred polymers include acrylics and polyurethanes.
  • Basecoat polymers may be thermoplastic, but are preferably crosslinkable and comprise one or more type of crosslinkable functional groups.
  • Such groups include for example, hydroxy, isocyanate, amine, epoxy, acrylate, vinyl, silane, and acetoacetate groups. These groups may be masked or blocked in such a way so that they are unblocked and available for a crosslinking reaction under the desired curing conditions, generally elevated temperatures.
  • Useful cross-linkable functional groups include hydroxy, epoxy, acid, anhydride, silane, and acetoacetate groups.
  • Preferred crosslinkable functional groups include hydroxyl functional groups and amino functional groups.
  • Basecoat polymers may be self-crosslinkable, or may require a separate cross-linking agent that is reactive with the functional groups of the polymer.
  • the cross-linking agent may be an aminoplast resin, isocyanate crosslinker, blocked isocyanate crosslinker, acid or anhydride cross-linking agent.
  • the basecoat is preferably pigmented and may include organic or inorganic compounds or colored materials, fillers, metallic or other inorganic flake materials such as mica or aluminum flake, and other materials that the art normally names as pigments. Pigments are usually used in the composition in an amount of 1% to 100% based on the total solid weight of components in the coating composition (i.e. a pigment to binder ratio of 0.1 to 1.0.
  • the coating compositions are subject to conditions so as to cure the coating layers.
  • heat-curing is preferred.
  • heat curing is effected by exposing the coated article to elevated temperatures provided primarily by radiative heat sources. Curing temperatures will vary depending on the particular blocking groups used in the crosslinking agents, however they generally range between 285°F (140.5°C) and 385°F (196.1°C).
  • the curing time will vary depending on the particular components used, and physical parameters such as the thickness of the layers, however typical curing times range between 15 to 60 minutes.
  • the various coating layers may be cured simultaneously or sequentially.
  • the primer layer is applied first and cured.
  • the bake window for the powder primers according to the present invention is between 160°C and 191°C (320°F and 375°F) for between 5 and 60 minutes.
  • the clearcoat and basecoat are applied to the primer layer and cured together.
  • a two tone coating may be obtained by applying basecoat over a portion of a primed substrate, followed by application of clearcoat over the entire substrate and simultaneous curing. The part of the substrate not basecoated is then coated with a second color basecoat and the entire substrate is then coated with clearcoat and the coatings are then cured simultaneously.
  • the method of the present invention provides an expanded bake window for the primer coating used in the multilayer coating.
  • the bake window refers to the time and temperature required to achieve 85-90% cure of the powder primer. Cure refers to reaction of the carboxy functional groups on the polyester with epoxy functional groups on the epoxy resin to form ⁇ -hydroxy ether linkages. It is desirable that the primer not be 100% cured, so that epoxy groups remain available to react with functionality on the clearcoat of the multilayer coating. The reaction between functional groups on the primer and clearcoat provides better intercoat adhesion, because there is a chemical bond between the coatings.
  • the bake window is determined in part by the ratio of epoxy groups to carboxyl groups in the powder primer.
  • the ratio is 0.98, and the coating is 85-90% cured at a bake time of 20 minutes at 335°F (168.3°C).
  • the bake window for the control primer coating is at temperatures between 157°C and 168°C (315°F and 335°F) for between 10 and 60 minutes.
  • the bake window for the powder primers according to the present invention is between 160°C and 191°C (320°F and 375°F) for between 5 and 60 minutes.
  • the bake window for the Control (1) is between 12 minutes at 168°C (335° F) and 60 minutes at 157°C (315° F).
  • the bake window is between 5 minutes at 191°C (375°F) and 52 minutes at 176°C (348° F).
  • the intercoat adhesion failure results due to longer bake times at higher temperatures.
  • Electrocoated panels were powder primer coated at a feathered thickness of 25-127 ⁇ m (1 to 5 mils,) and baked at 171°C (340°F) for 20 minutes. Clearcoat was applied at a thickness of about 46 ⁇ m (1.8 mils), followed by curing at 138°C (280 °F), for 20 min. The basecoat was applied at a thickness of about 18 ⁇ m (0.7 mils), with a flash of 5 minutes at 66°C at (150 °F), followed by curing at 138°C (280 °F) for 20 min.
  • the intercoat adhesion between a primer having a ratio of epoxy functionality to carboxy functionality of at least 1.15:1 demonstrates 100% increase in initial adhesion tests conducted according to ASTM test method D3359, in comparison to a primer coating containing epoxy and carboxy functionality in a stoichiometric ratio, where both primers are coated with identical clearcoats and basecoats and baked under identical conditions.

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  • Life Sciences & Earth Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Wood Science & Technology (AREA)
  • Application Of Or Painting With Fluid Materials (AREA)
  • Paints Or Removers (AREA)

Claims (12)

  1. Verfahren zur Herstellung eines gehärteten mehrschichtigen Überzugs, der Zwischenschichthaftung bereitstellt, bei dem man:
    a) auf ein Substrat eine Pulverlackzusammensetzung, die
    i) ein Polyesterharz mit einer Carboxylfunktionalität von weniger als zwei und
    ii) eine epoxidfunktionelle Verbindung, die mit der Carboxylfunktionalität von (i) umgesetzt werden kann,
    enthält, wobei das Verhältnis von Epoxidgruppen zu Carboxylgruppen zwischen 1,05:1 und 1,9:1 liegt, aufbringt,
    b) den Pulverlack härtet,
    c) danach direkt auf die gesamte Pulverlackschicht oder einen Teil davon mindestens eine zusätzliche Beschichtungszusammensetzung, die
    i) ein Harz mit reaktiver Funktionalität aus der Gruppe bestehend aus Hydroxyl-, Phenol-, Amino-, Carboxyl-, Epoxid- oder Mercaptanfunktionalität und
    ii) ein Vernetzerharz, das gegenüber der reaktiven Funktionalität der Komponente (c)(i) reaktiv ist, enthält, aufbringt und
    d) die zusätzliche(n) Beschichtungszusammensetzung(en) härtet.
  2. Verfahren nach Anspruch 1, bei dem der Pulverlack ein Verhältnis von Epoxidfunktionalität zu Carboxylfunktionalität zwischen 1,15:1 und 1,5:1 aufweist.
  3. Verfahren nach Anspruch 1, bei dem der Pulverlack ein Verhältnis von Epoxidfunktionalität zu Carboxylfunktionalität zwischen 1,4:1 und 1,6:1 aufweist.
  4. Verfahren nach Anspruch 1, bei dem es sich bei der zusätzlichen Beschichtungszusammensetzung um eine Klarlackzusammensetzung handelt, die ein hydroxyfunktionelles Acrylharz und einen Vernetzer aus der Gruppe bestehend aus Aminoplastvernetzern und blockierten und unblockierten Isocyanatvernetzern und Mischungen davon enthält.
  5. Verfahren nach Anspruch 4, bei dem die Klarlackzusammensetzung eine Mischung aus Melamin-Aminoplastvernetzer und einem blockierten Isocyanatvernetzer enthält.
  6. Verfahren nach Anspruch 4, bei dem man ferner über der Klarlackschicht eine oder mehrere Basislackzusammensetzungen aufbringt.
  7. Verfahren nach Anspruch 1, bei dem man ferner über einem Teil des Pulverlacks (a) eine Basislackzusammensetzung auf das Substrat aufbringt, wobei ein Teil des Pulverlacks basislackfrei bleibt, und dann sowohl über der mit Basislack versehenen Schicht als auch über dem basislackfreien Pulverlack Klarlack aufbringt.
  8. Verfahren nach Anspruch 7, bei dem man ferner über der Pulverlackschicht und der Klarlackschicht einen zweiten Basislack anderer Farbe aufbringt, wodurch man einen Zweiton-Farbeffekt erzielt.
  9. Verfahren nach Anspruch 1, bei dem man
    a) die Pulvergrundierlackzusammensetzung in einer Dicke zwischen 25,4 und 127 µm (1 und 5 Millizoll) aufbringt,
    b) die Pulvergrundierbeschichtung bei einer Temperatur zwischen 160°C (320°F) und 190,5°C (375°F) über einen Zeitraum zwischen 5 und 60 Minuten härtet,
    c) auf die erste Lackschicht (Pulvergrundierlack) eine Basislackschicht und eine Klarlackschicht aufbringt, wobei der Klarlack
    i) ein hydroxyfunktionelles Acrylharz und
    ii) einen Vernetzer, der aus der Gruppe bestehend aus Aminoplast und blockiertem und unblockiertem Isocyanat stammt und gegenüber den Hydroxylgruppen des Acrylharzes reaktiv ist,
    enthält,
    d) die Basislackzusammensetzung und die Klarlackzusammensetzung nacheinander bei einer Temperatur zwischen 126,6°C (260°F) bis 154,4°C (310°F) über einen Zeitraum von 10-25 Minuten härtet.
  10. Verfahren nach Anspruch 9, bei dem die Zwischenschichthaftung zwischen einer Grundierung mit einem Verhältnis von Epoxidfunktionalität zu Carboxylfunktionalität von mindestens 1,15:1 bei Anfangshaftungsprüfungen gemäß ASTM-Prüfmethode D3359 im Vergleich zu einer Grundierung, die Epoxid- und Carboxylfunktionalität in stöchiometrischem Verhältnis enthält, bei Beschichtung beider Grundierungen mit identischen Klarlacken und Brennen unter identischen Bedingungen eine Zunahme von 100% zeigt.
  11. Verfahren nach Anspruch 9, bei dem man ferner über der Grundierung auf einem Teil des Substrats einen Basislack aufbringt und danach auf das gesamte Substrat einen Klarlack aufbringt, wobei ein Teil des beschichteten Substrats eine Grundierungsschicht und eine Klarlackschicht ohne Basislack aufweist.
  12. Verfahren nach Anspruch 9, bei dem man ferner über der Grundierungsschicht und der Klarlackschicht in dem Bereich ohne Basislack einen Basislack anderer Farbe aufbringt, wodurch man einen Zweiton-Farbeffekt erzielt.
EP20000109836 2000-05-10 2000-05-10 Verfahren für Mehrschichtbeschichtung Expired - Lifetime EP1153669B1 (de)

Priority Applications (3)

Application Number Priority Date Filing Date Title
EP20000109836 EP1153669B1 (de) 2000-05-10 2000-05-10 Verfahren für Mehrschichtbeschichtung
DE2000633787 DE60033787T2 (de) 2000-05-10 2000-05-10 Verfahren für Mehrschichtbeschichtung
ES00109836T ES2283254T3 (es) 2000-05-10 2000-05-10 Procedimiento de revestimiento multicapa.

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
EP20000109836 EP1153669B1 (de) 2000-05-10 2000-05-10 Verfahren für Mehrschichtbeschichtung

Publications (2)

Publication Number Publication Date
EP1153669A1 EP1153669A1 (de) 2001-11-14
EP1153669B1 true EP1153669B1 (de) 2007-03-07

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ES (1) ES2283254T3 (de)

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Publication number Priority date Publication date Assignee Title
CN108588703A (zh) * 2012-03-21 2018-09-28 Swimc有限公司 双涂层单一固化粉末涂料
US9751107B2 (en) 2012-03-21 2017-09-05 Valspar Sourcing, Inc. Two-coat single cure powder coating
CN104962181A (zh) * 2015-06-30 2015-10-07 安徽华辉塑业科技有限公司 一种聚酯丙烯酸粉末涂料

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US5252399A (en) * 1991-12-20 1993-10-12 Hitachi Metal Ltd. Aluminum member provided with weather-resistant coat
DE19735540C1 (de) * 1997-08-16 1999-04-01 Basf Coatings Ag Mit einem Mehrschichtüberzug versehenes Substrat und Verfahren zu dessen Herstellung

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DE60033787D1 (de) 2007-04-19
EP1153669A1 (de) 2001-11-14
DE60033787T2 (de) 2007-11-08
ES2283254T3 (es) 2007-11-01

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