+

WO2018236993A1 - Revêtement en aluminium - Google Patents

Revêtement en aluminium Download PDF

Info

Publication number
WO2018236993A1
WO2018236993A1 PCT/US2018/038487 US2018038487W WO2018236993A1 WO 2018236993 A1 WO2018236993 A1 WO 2018236993A1 US 2018038487 W US2018038487 W US 2018038487W WO 2018236993 A1 WO2018236993 A1 WO 2018236993A1
Authority
WO
WIPO (PCT)
Prior art keywords
coating
maleimide
benzoxazine
acid
adhesive
Prior art date
Application number
PCT/US2018/038487
Other languages
English (en)
Inventor
James Biron Williams
Tarek Agag
Original Assignee
Lord Corporation
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 Lord Corporation filed Critical Lord Corporation
Publication of WO2018236993A1 publication Critical patent/WO2018236993A1/fr

Links

Classifications

    • 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
    • C09D5/00—Coating compositions, e.g. paints, varnishes or lacquers, characterised by their physical nature or the effects produced; Filling pastes
    • C09D5/002—Priming paints
    • 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
    • C09D171/00—Coating compositions based on polyethers obtained by reactions forming an ether link in the main chain; Coating compositions based on derivatives of such polymers
    • 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
    • C09D5/00—Coating compositions, e.g. paints, varnishes or lacquers, characterised by their physical nature or the effects produced; Filling pastes
    • C09D5/08—Anti-corrosive paints
    • 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
    • C08G2650/00—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule
    • C08G2650/28—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule characterised by the polymer type
    • C08G2650/56—Polyhydroxyethers, e.g. phenoxy resins

Definitions

  • the invention relates to coating compositions provided to enhance corrosion resistance of metallic substrates and act as a primer for subsequent adhesive bonding.
  • the coating compositions of the invention are particularly well suited for aluminum substrates as a replacement for conventional wash primers.
  • Bonding of aluminum substrates can be achieved with a number of structural adhesives, typically epoxy based.
  • the aluminum substrates are typically treated with chemistries that improve the adhesion of the structural adhesives and provide resistance to under-bond corrosion that otherwise compromises bond integrity.
  • wash primers often fail to provide acceptable under-bond corrosion resistance, particularly on high strength aluminum alloys such as 7075 -T6, as well as other 7- and 8- thousand series aluminums. Additionally, operation of the baths used to deposit wash primers on aluminum substrates requires careful control of bath chemistries.
  • a coating comprising a film former, a thermosetting resin mixture comprising at least two of a triazine, a benzoxazine, or a maleimide, and a crosslinker.
  • the maleimide comprises a bismaleimide
  • the film former comprises a phenoxy resin based on bisphenol A, and/or a methacrylic acid grafted phenoxy resin.
  • the coating further comprises at least one of a corrosion inhibitor or an adhesion promoter, and the corrosion inhibitor preferably comprises a triazole or phosphate, and the adhesion promoter preferably comprises a ureidosilane.
  • the crosslinker comprises trifluoromethane sulfonic acid, acid catalyst, diphenyl phosphate / 1 -methylimidazole, or tetrol.
  • the acid catalyst comprises at least one of a covalently blocked dinonylnaphthalenesulfonic acid (DN SA) catalyst or an amine neutralized dinonylnaphthalenesulfonic acid (DN DSA) catalyst.
  • DN SA covalently blocked dinonylnaphthalenesulfonic acid
  • DN DSA amine neutralized dinonylnaphthalenesulfonic acid
  • the thermosetting resin mixture comprises a triazine, a benzoxazine, and a maleimide and the ratio of benzoxazine to maleimide is about 1 : 1. And in another embodiment of the present invention, the ratio of triazine to benzoxazine is 2: 1.
  • thermosetting coating compositions of embodiments of the present invention offer exceptional compatibility with a broad array of structural adhesives, particularly including epoxy formulations. In their cured form, they are very thermally stable and provide excellent adhesion to both the aluminum substrates and the structural adhesives.
  • One embodiment of the present invention discloses a system that utilizes a multiple-catalyst approach to facilitate the proper cure of the coating in combination with corrosion inhibitors that further improve under-bond corrosion resistance.
  • Aluminum coatings improves the adhesion of the structural adhesives, provides under-bond corrosion resistance, and serves as a primer for topcoat applications.
  • the coating may find application opportunities in automotive light-weighting and product assembly.
  • the aluminum coating may be applied prior to parts forming operations as a coil coating or after parts forming is completed.
  • Use as a primer prior to the application of hem flange adhesives and sealants, such as may be used in truck bed assemblies, enables the use of higher grade aluminum alloys than may be used with existing wash primer technologies due to limitations in under-bond corrosion resistance.
  • the aluminum coating composition comprises a film former, a thermosetting resin mixture, a crosslinker, and a carrier fluid.
  • the film former comprises a monomer or pre-polymer.
  • the film former is provided to produce a contiguous film on a substrate that offers a physical barrier to ingress and impedance to electrolytic solutions that otherwise facilitate corrosion.
  • the film former comprises a phenoxy resin, preferably a bis-A based phenoxy resin, and most preferably a methacrylic acid-grafted phenoxy resin.
  • the film former is chosen to provide synergy with benzoxazine resin (i.e. through formation of a monolithic layer wherein the benzoxazine enhances the adhesion of the composite), compatibility with epoxy-based structural adhesives (i.e.
  • Solvent-soluble phenoxy resins are known in the art from a number of producers, however particularly suitable examples of phenoxy resins for solvent-based adhesives include the solid PKHH grade sold by Phenoxy Associates or PKHS-40, which is a PKHH grade pre- dissolved in methylethyl ketone (MEK). Likewise, aqueous phenoxy resins are also available from this same supplier under the PKHW grade.
  • thermosetting resin mixture employed in the present invention combines at least two thermosetting resins.
  • Preferred thermosetting resins comprise rigid, heavily crosslinked polymeric materials with higher mechanical strength and higher heat resistance than common thermoplastics.
  • the thermosetting resin mixture comprises at least two of a triazine resin, a benzoxazine resin, and a maleimide resin.
  • Triazine resins promote thermal stability, corrosion resistance, ligand bonding to metals including copper, and have established use in automotive primers and coil coatings.
  • Preferred triazine resins comprise melamine formaldehyde resins.
  • Benzoxazine reins are known to have excellent adhesion to aluminum, are compatible with phenoxy resin (same backbone), and have high thermal and mechanical properties.
  • Maleimides and particularly bismaleimides are known to be synergistic with benzoxazine, improve the cure rate, and may reduce the need for catalysts.
  • the adhesive further comprises a maleimide compound.
  • Maleimide containing adhesives of this embodiment are particularly useful for bonding peroxide cured adhesives.
  • the maleimide compound comprises any compound containing at least two maleimide groups.
  • the maleimide groups may be attached to one another or may be joined to and separated by an intervening divalent radical such as alkylene, cyclo-alkylene, epoxydimethylene, phenylene (all 3 isomers), 2,6-dimethylene-4- alkylphenol, or sulfonyl.
  • An example of a maleimide compound wherein the maleimide groups are attached to a phenylene radical is m-phenylene bismaleimide and is available as HVA-2 from E.I. Du Pont de Nemours & Co. (Delaware, U. S.A.).
  • the maleimide compound crosslinker may also be an aromatic polymaleimide compound.
  • Aromatic polymaleimides having from about 2 to 100 aromatic nuclei wherein no more than one maleimide group is directly attached to each adjacent aromatic ring are preferred.
  • aromatic polymaleimides are common materials of commerce and are sold under different trade names by different companies, such as BMI-M-20 and BMI-S aromatic polymaleimides supplied by Mitsui Chemicals, Incorporated.
  • the coating comprises a compound that cures the resins and promotes the crosslinking of the constituent materials.
  • These materials are known as crosslinkers, curatives, catalysts, and/or reaction accelerators. These are selected so as to match the crosslinking of the constituent materials with the required cure profiles to best coincide with subsequent bonding and coating processes.
  • the crosslinker comprises at least one of trifluoromethane sulfonic acid, which is an effective catalyst with all resins listed in formulary, acid catalysts such as a covalently blocked dinonylnaphthalenesulfonic acid (DN SA) catalyst (NaCure 1419) or an amine neutralized dinonylnaphthalenesulfonic acid (DN DSA) catalyst (NaCure X49-1 10), which are a potential altemative for triflic acid when maleimide resin is included in the formulation, diphenyl phosphate / 1-methylimidazole, which is synthesized in-house, and tetrol, which crosslinks with resins used and improves adhesion.
  • Additional known crosslinkers such as peroxides and the like may also be employed in embodiments of the present invention.
  • the coating composition optionally comprises one or more additives or modifiers, such as phenol which improves mobility of triazine after vitrification, and reduces crosslink density after first thermal cycle.
  • Another useful modifier is a UV indicator such as Tinopal NFW to aid in film detection upon application to the substrate.
  • an adhesion promoter is selected to facilitate bonding of the coating to aluminum substrates.
  • the adhesion promoter comprises a ureidosilane.
  • the coating composition comprises a corrosion inhibitor.
  • Preferred corrosion inhibitors comprise materials that passivate the metal surface and ion exchange anticorrosive pigments.
  • the corrosion inhibitor comprises a triazole or phosphate corrosion inhibitor, with triazole inhibitors being particularly effective with copper, since copper is a common additive in aluminum alloys.
  • the coating composition is provided in a carrier fluid to promote application and handling characteristics.
  • carrier fluids include: cyclohexanone, methyl ethyl ketone, which is rapid drying; di methyl carbonate, which is a good solvent for benzoxazine and bismaleimide resins and is VOC friendly; glycol ethers such as Dowanol PM which is a tail solvent and solubilizes the Tinopal NFW if used, and combinations of these and other carrier fluids.
  • the carrier fluid comprises water.
  • the coating described in embodiments of the present invention are particularly well suited for use with aluminum and aluminum alloy substrates, however other materials such as steel and copper may be coated.
  • the coating may be used as a metal protectant to protect the metal substrate from corrosion and oxidation, or may be used in conjunction with an adhesive to bond the metal substrate to another substrate.
  • the coating may be brushed, rolled, sprayed, or otherwise applied to the substrate to a desired thickness preferably not to exceed 0.70 mils, and preferably about 0.50 mils.
  • the coating is then dried at about 150°F for 30 minutes, and preferably cured by heating it to about 400°F for 30 minutes. If used as a primer, it is advantageous to dry the primer as above, then apply the adhesive, then complete the bonding/baking operation.
  • Coating Manufacture As will be appreciated by one of skill in the art, some of the components need to be ground to a smaller particle size via bb mill, sandmill, or Kady mill, while other components can be rolled in since they are in solution or already dispersed in water as received.
  • the coatings were prepared according to the formulations below, and applied, bonded, cured as described below.
  • Coating Application Typical application of the prepared adhesive is to spray apply the coating to the aluminum substrate and allow to dry.
  • adhesive bond quality is tested in several manners.
  • One such test measures the lap shear strength. In this test, two substrates are joined together in an overlap fashion, using the coating as a primer and a structural adhesive, with a typical adhesive area of 6.5 cm2. The lap shear specimen is then pulled apart on an Instron®-type machine at 180 degrees and a rate of 50 mm/min and force and failure mode are measured.
  • Another such test is outlined in ASTM D429 Method B.
  • Formula #1 Composition is shown below
  • Example 1 Made in house at LORD Corporation [0036] The formulation in Example 1 demonstrates a coating according to the present invention which comprises two thermosetting resins, atriazine and a benzoxazine. This coating was applied to aluminum substrates and bonded with a structural adhesive demonstrating satisfactory primary adhesion.
  • aqueous adhesive according to the formulation above was applied to 6061T6 aluminum at a coating thickness of 0.50 mils and dried.
  • BetaMate 4601 adhesive available from Dow Automotive
  • the bonded assemblies where cured at 178°C for 30 minutes and tested for primary adhesion by the lap shear test and environmental resistance by exposure to salt spray for 1080 hours, then pulled.
  • a total of 12 assemblies where tested by each method with the results as follows:
  • the coating exhibited excellent properties when used as a primer along with a structural adhesive, and exhibited no degradation in bond strength when exposed to salt spray.

Landscapes

  • Chemical & Material Sciences (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Wood Science & Technology (AREA)
  • Organic Chemistry (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Paints Or Removers (AREA)
  • Adhesives Or Adhesive Processes (AREA)

Abstract

L'invention concerne un revêtement contenant un filmogène, un mélange de résine thermodurcissable comprenant au moins deux parmi une triazine, une benzoxazine, ou un maléimide, et un agent de réticulation. Lorsqu'elle est appliquée sur des substrats en aluminium, le revêtement améliore l'adhérence des adhésifs appliqués ultérieurement, fournit une résistance à la corrosion sous-jacente, et sert d'apprêt pour des applications de couche de finition. En particulier, le revêtement permet une liaison robuste de substrats en alliage d'aluminium.
PCT/US2018/038487 2017-06-21 2018-06-20 Revêtement en aluminium WO2018236993A1 (fr)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
US201762522979P 2017-06-21 2017-06-21
US62/522,979 2017-06-21

Publications (1)

Publication Number Publication Date
WO2018236993A1 true WO2018236993A1 (fr) 2018-12-27

Family

ID=62875334

Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/US2018/038487 WO2018236993A1 (fr) 2017-06-21 2018-06-20 Revêtement en aluminium

Country Status (1)

Country Link
WO (1) WO2018236993A1 (fr)

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN110938351A (zh) * 2019-12-17 2020-03-31 江西南方锅炉股份有限公司 一种城市垃圾焚烧发电锅炉防腐涂料的制备方法
CN113235303A (zh) * 2021-06-08 2021-08-10 青岛大学 一种聚苯并噁嗪改性聚苯硫醚材料及其制备方法

Citations (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US5260357A (en) * 1992-04-30 1993-11-09 The Dexter Corporation Corrosion resistant waterbone adhesive primers
US5378740A (en) * 1992-04-30 1995-01-03 The Dexter Corporation Waterborne epoxy derivative composition
WO2010054287A1 (fr) * 2008-11-07 2010-05-14 Lord Corporation Amorce en poudre pour l'adhésion d'un caoutchouc sur du métal
EP2412743A1 (fr) * 2009-03-27 2012-02-01 Hitachi Chemical Company, Ltd. Composition de résine thermodurcissable, et pré-imprégné, film d'isolation sur support, plaque stratifiée, et carte de circuit imprimé obtenus à partir de celle-ci
US20140087152A1 (en) * 2011-05-27 2014-03-27 Ajinomoto Co., Inc. Resin composition
US20140199549A1 (en) * 2011-07-28 2014-07-17 Protavic Korea Co., Ltd. Flexible bismaleimide, benzoxazine, epoxy-anhydride adduct hybrid adhesive
CN104263306A (zh) * 2014-09-26 2015-01-07 四川东材科技集团股份有限公司 一种聚苯醚胶黏剂及其覆铜板的制备方法
US20160297994A1 (en) * 2015-04-10 2016-10-13 Eastman Chemical Company Curable benzoxazine-based phenolic resins and coating compositions thereof

Patent Citations (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US5260357A (en) * 1992-04-30 1993-11-09 The Dexter Corporation Corrosion resistant waterbone adhesive primers
US5378740A (en) * 1992-04-30 1995-01-03 The Dexter Corporation Waterborne epoxy derivative composition
WO2010054287A1 (fr) * 2008-11-07 2010-05-14 Lord Corporation Amorce en poudre pour l'adhésion d'un caoutchouc sur du métal
EP2412743A1 (fr) * 2009-03-27 2012-02-01 Hitachi Chemical Company, Ltd. Composition de résine thermodurcissable, et pré-imprégné, film d'isolation sur support, plaque stratifiée, et carte de circuit imprimé obtenus à partir de celle-ci
US20140087152A1 (en) * 2011-05-27 2014-03-27 Ajinomoto Co., Inc. Resin composition
US20140199549A1 (en) * 2011-07-28 2014-07-17 Protavic Korea Co., Ltd. Flexible bismaleimide, benzoxazine, epoxy-anhydride adduct hybrid adhesive
CN104263306A (zh) * 2014-09-26 2015-01-07 四川东材科技集团股份有限公司 一种聚苯醚胶黏剂及其覆铜板的制备方法
US20160297994A1 (en) * 2015-04-10 2016-10-13 Eastman Chemical Company Curable benzoxazine-based phenolic resins and coating compositions thereof

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
DATABASE WPI Week 201527, Derwent World Patents Index; AN 2015-13930R, XP002783667 *

Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN110938351A (zh) * 2019-12-17 2020-03-31 江西南方锅炉股份有限公司 一种城市垃圾焚烧发电锅炉防腐涂料的制备方法
CN113235303A (zh) * 2021-06-08 2021-08-10 青岛大学 一种聚苯并噁嗪改性聚苯硫醚材料及其制备方法
CN113235303B (zh) * 2021-06-08 2023-08-18 青岛大学 一种聚苯并噁嗪改性聚苯硫醚材料及其制备方法

Similar Documents

Publication Publication Date Title
RU2608400C2 (ru) Поверхностная пленка для композитных структур и способ ее изготовления
WO2007146388A1 (fr) Composition de revêtement sous forme de poudre pour le revêtement de tuyauteries
JP2017122227A (ja) 金属表面用インジケータ塗料
JP2011140067A (ja) 鋼板とアルミニウム板との接合構造体の製造方法およびこの製造方法により製造された鋼板とアルミニウム板との接合構造体
WO2018236993A1 (fr) Revêtement en aluminium
US20240270977A1 (en) Multi-component powder coating compositions and methods for heat sensitive substrates
KR20010021811A (ko) 금속 표면 처리제, 금속 표면 처리 방법 및 프리코트 강판
JP6350768B1 (ja) プレコート金属板
JP2009299145A (ja) 金属（水）酸化物被覆金属材料
US20210309881A1 (en) Low application temperature powder coating
JP3233700B2 (ja) 防食塗料組成物
WO2010002648A1 (fr) Compositions filmogènes ayant des propriétés de réflexion de la chaleur
WO2012039217A1 (fr) Composition aqueuse pour couche d'apprêt, procédé de formation d'un revêtement multicouche et article revêtu
JP6386157B1 (ja) プライマー組成物、プライマー塗膜及びその形成方法、並びに塗膜の形成方法
JPS6241549B2 (fr)
JP3787047B2 (ja) 鋼材用防食塗料組成物
JP3471258B2 (ja) 金属材料の粉体塗装方法
JP4765902B2 (ja) 接着性と皮膜密着性に優れた表面処理金属材
JP2005054074A (ja) ステンレス防食用亜鉛含有塗料組成物
JPS63111049A (ja) 金属−ポリプロピレンフイルム積層体
US7166364B2 (en) Polyester conversion coated metal or its alloys
JP4665151B2 (ja) 鋼材用防食塗料組成物およびそれを塗装した鋼材
JP2010006990A (ja) ポリベンゾイミダゾールプライマー組成物
JP2009001648A (ja) プライマー組成物
JPH08109247A (ja) 一液熱硬化型エポキシ樹脂組成物

Legal Events

Date Code Title Description
121 Ep: the epo has been informed by wipo that ep was designated in this application

Ref document number: 18740036

Country of ref document: EP

Kind code of ref document: A1

NENP Non-entry into the national phase

Ref country code: DE

122 Ep: pct application non-entry in european phase

Ref document number: 18740036

Country of ref document: EP

Kind code of ref document: A1

点击 这是indexloc提供的php浏览器服务，不要输入任何密码和下载