EP1366101A1 - Vernis-email polyurethanes de type 1k et leur utilisation - Google Patents

Vernis-email polyurethanes de type 1k et leur utilisation

Info

Publication number
EP1366101A1
EP1366101A1 EP02719832A EP02719832A EP1366101A1 EP 1366101 A1 EP1366101 A1 EP 1366101A1 EP 02719832 A EP02719832 A EP 02719832A EP 02719832 A EP02719832 A EP 02719832A EP 1366101 A1 EP1366101 A1 EP 1366101A1
Authority
EP
European Patent Office
Prior art keywords
lacquer
component
esters
clear
pur
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.)
Withdrawn
Application number
EP02719832A
Other languages
German (de)
English (en)
Inventor
Eberhard König
Christoph Gürtler
Frank Kobor
Wolfram Küttner
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.)
Covestro Deutschland AG
Original Assignee
Bayer 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 Bayer AG filed Critical Bayer AG
Publication of EP1366101A1 publication Critical patent/EP1366101A1/fr
Withdrawn legal-status Critical Current

Links

Classifications

    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/08—Processes
    • C08G18/16—Catalysts
    • C08G18/22—Catalysts containing metal compounds
    • C08G18/222—Catalysts containing metal compounds metal compounds not provided for in groups C08G18/225 - C08G18/26
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/70—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the isocyanates or isothiocyanates used
    • C08G18/72—Polyisocyanates or polyisothiocyanates
    • C08G18/77—Polyisocyanates or polyisothiocyanates having heteroatoms in addition to the isocyanate or isothiocyanate nitrogen and oxygen or sulfur
    • C08G18/78—Nitrogen
    • C08G18/79—Nitrogen characterised by the polyisocyanates used, these having groups formed by oligomerisation of isocyanates or isothiocyanates
    • C08G18/791—Nitrogen characterised by the polyisocyanates used, these having groups formed by oligomerisation of isocyanates or isothiocyanates containing isocyanurate groups
    • C08G18/792—Nitrogen characterised by the polyisocyanates used, these having groups formed by oligomerisation of isocyanates or isothiocyanates containing isocyanurate groups formed by oligomerisation of aliphatic and/or cycloaliphatic isocyanates or isothiocyanates
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/70—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the isocyanates or isothiocyanates used
    • C08G18/72—Polyisocyanates or polyisothiocyanates
    • C08G18/80—Masked polyisocyanates
    • C08G18/8061—Masked polyisocyanates masked with compounds having only one group containing active hydrogen
    • C08G18/8093—Compounds containing active methylene groups
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D175/00—Coating compositions based on polyureas or polyurethanes; Coating compositions based on derivatives of such polymers
    • C09D175/04—Polyurethanes
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
    • Y10T428/00—Stock material or miscellaneous articles
    • Y10T428/31504—Composite [nonstructural laminate]
    • Y10T428/31551—Of polyamidoester [polyurethane, polyisocyanate, polycarbamate, etc.]

Definitions

  • the invention relates to IK polyurethane stoving lacquers whose polyisocyanate crosslinking agents are blocked with CH-acidic esters, in particular malonic esters.
  • the stoving varnishes have a low stoving temperature. They are preferably used for painting plastic parts.
  • One-component paints that are stable in storage can be mixed with malonic ester-blocked polyisocyanates and polymeric OH components (polyesters, polyacrylates, etc.). After application, these harden already at a baking temperature of 100 ° C, for example under baking conditions of 30 minutes. at 100 ° C. With other isocyanate blocking agents, e.g. B. butanone oxime, 1,2,4-triazole, diisopropylamine or 3,5-dimethylpyrazole, such a low baking temperature can hardly be achieved.
  • isocyanate blocking agents e.g. B. butanone oxime, 1,2,4-triazole, diisopropylamine or 3,5-dimethylpyrazole
  • thermoplastics for example for automotive parts such as bumpers, hubcaps or moldings, to be painted.
  • polypropylene parts have been coated with an IC lacquer, which therefore requires an even lower baking temperature than 100 ° C.
  • the object of the invention was therefore to find a catalyst with which 1-component PU stoving lacquers based on polyisocyanates which are blocked with CH-acidic esters cure even at stoving temperatures of ⁇ 100 ° C.
  • the invention therefore relates to solvent-based or water-diluted 1K
  • CH-acidic esters especially malonic esters, blocked polyisocyanates
  • Essential to the invention is the presence of a tetravalent organic titanium compound as a catalyst, which can be processed as a one-component PU lacquer mixture consisting of CH-acidic esters, preferably with malonic esters, blocked polyisocyanates and organic polyhydroxyl compounds, even at a stoving temperature of 90 ° C./30 minute gives a sufficiently good cross-linking, with a baking temperature of 85 ° C / 30 min. also seems feasible.
  • the titanium (IV) catalysts to be used according to the invention are added to the paint binder components mentioned, which are present in dissolved form.
  • PUR lacquer binders are stable in storage and can be formulated, for example, for the following lacquer tasks: filler or primer, metal base lacquer, clear lacquer, pigmented top lacquer or water-diluted soft-feel lacquer. If necessary, you can use conventional additives and additives such as pigments,
  • the titanium IV catalysts to be used according to the invention include, for example, tetra-n-butyl orthotitanate, tetraethyl titanate, tetramethyl titanate, titanium tetra (2-ethyl hexanoate), titanium triisopropylate chloride and cyclopentadienyl titanium trichloride and any mixtures of these titanium IV compounds into consideration. Tetra-n-butyl titanate is particularly preferred.
  • the titanium IV catalysts are used in amounts of 0.5-4.0% by weight, preferably 1.5-2.5% by weight, based on the solids content of the paint binder components.
  • the 1-K-PUR stoving enamels according to the invention can be used to coat substrates made from a wide variety of materials, e.g. for coating substrates made of metals, glass, minerals, ceramics, wood, paper, plastics such as polycarbonate, polymethyl methacrylate, polyamides, polypropylene etc.
  • the invention is also explained on the basis of a catalyzed clear lacquer in comparison with other catalysts based on bismuth, tin and zirconium. It is shown that the curing of the non-catalyzed lacquer can be reduced from 100 ° C to at least 90 ° C and in tendency even to 85 ° C by using tetrabutyl titanate. This also makes it possible to paint polypropylene plastic parts with such one-component paints. Examples
  • Desmodur ® W antrimerized, 80% in butyl diglycol acetate (BDGA), 246.0 1.0 NCO content: found 17.1%
  • Tinuvin® 770 DF 2 3.7 -
  • NMP N-methylpyrrolidone
  • Tinuvin® 770 DF, DBP and IB (remaining amount) is added and the mixture is stirred for about 2 hours at 50 ° C.
  • a storage-stable solution of a malonate-blocked polyisocyanate with the characteristics mentioned at the beginning is obtained.
  • b) As reaction partners for the above malonic crosslinker is the OH-containing polyacrylate Desmophen ® A 665 (Bayer AG, 3% OH content, OH equivalent of the delivery form 567 g, 65% in butyl acetate / xylene 3: used 1).
  • the above clear coat is mixed with 1% or 2%, based on the solids content of the binder, ie 0.41 g or 0.82 g per 100 g clear coat, of the respective catalyst. Using a doctor blade, 120 ⁇ m wet films are produced and baked in the oven under the following conditions.
  • Example 3
  • An unpainted mirror housing from Audi was cleaned with standard rinsing solutions and then rinsed with demineralized water and dried.
  • the spray systems listed below were applied by spray application.
  • a Sata spray gun was used.
  • the nozzle diameter was 1.4 mm and a spray pressure of 2.5 bar was used.
  • the 2K PUR filler commercially available from Du Pont (Wuppertal) was applied evenly with a lacquer film thickness of 30 to 40 ⁇ m and then 30 min. dried at 80 ° C.
  • a coloring and effect-giving lacquer system (metallic basecoat, silver, also from Du Pont) was applied with a lacquer film thickness of 12 to 15 ⁇ m and 5 min. dried at 80 ° C.
  • the third and last layer of lacquer was a clear lacquer, as described in Example 2, with the following lacquer composition: Parts by weight
  • Desmophen® A 665 (see Example Ib) 31.2 Baysilone OL 17, 10% in xylene 0.4
  • Tinuvin® 292 10% in xylene 4, 1
  • the clear coat was applied with a coat film thickness of 40-50 ⁇ m and then for 30 minutes. dried at 80 ° C. The result was clear, high-gloss paint film surfaces with good curing and good paint properties.
  • Values come about when a previously burned-in paint film is over-baked and must not be greater than 1.0.
  • TBT Tetra-n-butyl orthotitanate
  • TBT tetrabutyl titanate
  • Lacquer film signals a usable good cross-linking, which is achieved neither by the zero value nor by the differently catalyzed films. Furthermore shows the

Landscapes

  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Wood Science & Technology (AREA)
  • Paints Or Removers (AREA)
  • Polyurethanes Or Polyureas (AREA)

Abstract

L'invention concerne des vernis-émail polyuréthanes de type 1K, dont des réticulants polyisocyanates, les esters de l'acide CH, en particulier des esters maloniques, sont bloqués. Ces vernis-émail présentent une faible température de cuisson. Ils sont de préférence utilisés pour la peinture de pièces en plastique.
EP02719832A 2001-02-26 2002-02-14 Vernis-email polyurethanes de type 1k et leur utilisation Withdrawn EP1366101A1 (fr)

Applications Claiming Priority (3)

Application Number Priority Date Filing Date Title
DE10109228A DE10109228A1 (de) 2001-02-26 2001-02-26 1K-Polyurethaneinbrennlacke und deren Verwendung
DE10109228 2001-02-26
PCT/EP2002/001536 WO2002068494A1 (fr) 2001-02-26 2002-02-14 Vernis-email polyurethanes de type 1k et leur utilisation

Publications (1)

Publication Number Publication Date
EP1366101A1 true EP1366101A1 (fr) 2003-12-03

Family

ID=7675544

Family Applications (1)

Application Number Title Priority Date Filing Date
EP02719832A Withdrawn EP1366101A1 (fr) 2001-02-26 2002-02-14 Vernis-email polyurethanes de type 1k et leur utilisation

Country Status (11)

Country Link
US (1) US6919417B2 (fr)
EP (1) EP1366101A1 (fr)
JP (1) JP2004528415A (fr)
KR (1) KR20040030510A (fr)
CN (1) CN1494562A (fr)
CA (1) CA2439077A1 (fr)
DE (1) DE10109228A1 (fr)
MX (1) MXPA03007596A (fr)
PL (1) PL363290A1 (fr)
WO (1) WO2002068494A1 (fr)
ZA (1) ZA200306565B (fr)

Families Citing this family (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE10308105A1 (de) * 2003-02-26 2004-09-09 Bayer Aktiengesellschaft Polyurethan-Beschichtungssysteme
DE10336883A1 (de) * 2003-08-08 2005-03-10 Basf Ag Kunststoff, insbesondere Polyurethan enthaltend ein sterisch gehindertes, verestertes Amin
US20050287349A1 (en) * 2004-06-23 2005-12-29 Yu Poli C Method for coating coils
JP5562267B2 (ja) * 2010-02-08 2014-07-30 旭化成ケミカルズ株式会社 ブロックポリイソシアネート組成物及びこれを含む塗料組成物
JP5572567B2 (ja) * 2010-02-08 2014-08-13 旭化成ケミカルズ株式会社 ブロックポリイソシアネート組成物を製造する方法
EP2535364B1 (fr) * 2010-02-08 2015-01-21 Asahi Kasei Chemicals Corporation Composition de polyisocyanate séquencé et composition de revêtement la contenant
JP5562271B2 (ja) * 2010-06-04 2014-07-30 旭化成ケミカルズ株式会社 ブロックポリイソシアネート組成物の製造方法

Family Cites Families (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE3046409A1 (de) * 1980-12-10 1982-07-15 Bayer Ag, 5090 Leverkusen Beschichtungsmittel und ein verfahren zur herstellung von ueberzuegen
JPS5924771A (ja) * 1982-08-02 1984-02-08 Semedain Kk 一液型室温硬化性シ−ラント組成物
US4727099A (en) * 1986-08-15 1988-02-23 E. I. Du Pont De Nemours And Company Coating composition containing a reactive urethane component, a hydroxyl containing acrylic polymer having pendent ester groups and a metallic alkylate catalyst
US4727100A (en) * 1986-08-15 1988-02-23 E. I. Du Pont De Nemours And Company Coating composition containing a reactive urethane component an acrylic fatty acid drying oil resin and a metallic alkylate
CA2138525C (fr) * 1993-04-29 2002-09-17 Michihiro Ishiguro Composition de polyurethane thermoplastique
US6103849A (en) * 1994-06-27 2000-08-15 Bayer Corporation Storage stable, heat curable polyurethane compositions
DE19813352A1 (de) * 1998-03-26 1999-09-30 Bayer Ag Malonesterblockierte Polyisocyanate mit Formaldehyd gegen Thermovergilbung

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
See references of WO02068494A1 *

Also Published As

Publication number Publication date
MXPA03007596A (es) 2003-12-11
KR20040030510A (ko) 2004-04-09
PL363290A1 (en) 2004-11-15
US6919417B2 (en) 2005-07-19
WO2002068494A1 (fr) 2002-09-06
ZA200306565B (en) 2004-08-23
CN1494562A (zh) 2004-05-05
CA2439077A1 (fr) 2002-09-06
DE10109228A1 (de) 2002-09-05
US20030055158A1 (en) 2003-03-20
JP2004528415A (ja) 2004-09-16

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