WO2020081447A1 - Système d'électrodéposition de substrats conducteurs - Google Patents

Système d'électrodéposition de substrats conducteurs Download PDF

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Publication number
WO2020081447A1
WO2020081447A1 PCT/US2019/056107 US2019056107W WO2020081447A1 WO 2020081447 A1 WO2020081447 A1 WO 2020081447A1 US 2019056107 W US2019056107 W US 2019056107W WO 2020081447 A1 WO2020081447 A1 WO 2020081447A1
Authority
WO
WIPO (PCT)
Prior art keywords
substrate
coating composition
electrocoating
electrodepositable coating
tank
Prior art date
Application number
PCT/US2019/056107
Other languages
English (en)
Inventor
Brent A. Schwartz
Tammy L. HUTCHINSON
Dennis J. Siefer
Judith A. BETHOSKI
Irina G. Schwendeman
Mark L. Follet
Amy E. HARRISON
Original Assignee
Ppg Industries Ohio, Inc.
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 Ppg Industries Ohio, Inc. filed Critical Ppg Industries Ohio, Inc.
Priority to BR112021007150-4A priority Critical patent/BR112021007150A2/pt
Priority to MX2021004316A priority patent/MX2021004316A/es
Priority to EP19797493.4A priority patent/EP3867424A1/fr
Priority to US17/285,640 priority patent/US20210388525A1/en
Priority to KR1020217013624A priority patent/KR20210072056A/ko
Priority to CN201980067955.XA priority patent/CN113260741A/zh
Publication of WO2020081447A1 publication Critical patent/WO2020081447A1/fr

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Classifications

    • C—CHEMISTRY; METALLURGY
    • C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
    • C25D21/00—Processes for servicing or operating cells for electrolytic coating
    • C25D21/16—Regeneration of process solutions
    • C25D21/18—Regeneration of process solutions of electrolytes
    • C—CHEMISTRY; METALLURGY
    • C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
    • C25D13/00—Electrophoretic coating characterised by the process
    • C25D13/22—Servicing or operating apparatus or multistep processes
    • C—CHEMISTRY; METALLURGY
    • C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
    • C25D13/00—Electrophoretic coating characterised by the process
    • C25D13/04—Electrophoretic coating characterised by the process with organic material
    • C—CHEMISTRY; METALLURGY
    • C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
    • C25D13/00—Electrophoretic coating characterised by the process
    • C25D13/12—Electrophoretic coating characterised by the process characterised by the article coated
    • C—CHEMISTRY; METALLURGY
    • C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
    • C25D13/00—Electrophoretic coating characterised by the process
    • C25D13/20—Pretreatment

Definitions

  • the present invention relates to electrocoating systems for electrocoating a substrate.
  • the present invention also relates to a system for coating substrates, methods for coating substrates, and coated substrates.
  • Electrodeposition as a coating application method involves the deposition of a film-forming composition onto a conductive substrate under the influence of an applied electrical potential. Electrodeposition has gained popularity in the coatings industry because it provides higher paint utilization, outstanding corrosion resistance, and low environmental contamination as compared with non-electrophoretic coating methods. However, some conductive substrates are more difficult to coat by electrodeposition because of a number of factors, including the shape and size of the substrate. For example, it may be difficult to coat both the internal and external surfaces of substrates having an open-pocket shape, such as a container, using conventional electrocoat systems. Therefore, an electrocoating system that is capable of coating a wide range of substrates is desired.
  • an electrocoating system for electrocoating a substrate, the system comprising a tank configured to hold an electrodepositable coating composition; at least one pump in fluid communication with the tank, at least one return conduit connecting the tank with an inlet of the pump, at least one recirculating pipe comprising a first end in fluid communication with an outlet of the pump and a second end having at least one aperture, and the at least one recirculating pipe comprising at least one external electrode positioned at least partially outside of the tank, wherein: the substrate has a first surface and a second surface; the pump is configured to receive the electrodepositable coating
  • Also disclosed herein is a method for coating a substrate comprising electrophoretically applying a coating deposited from an electrodepositable coating composition to at least a portion of the substrate using the electrocoating system of the present invention.
  • a system for coating a substrate comprising the electrocoating system of the present invention, and further comprising a pretreatment system for pretreating the substrate prior to processing the substrate in the electrocoating system; a primer system for applying a primer to the substrate prior to processing the substrate in the electrocoating system; and/or a topcoat system for applying a topcoat coating to the substrate after processing the substrate in the electrocoating system.
  • Figure 1 is an illustration of an electrocoating system with a recirculating pipe comprising an external electrode and extending into the tank, according to the present invention.
  • Figure 2 is an illustration of an electrocoating system of Figure 1 with an insulating part extending out of the tank the length of the recirculating pipe to the pump.
  • Figure 3 is an illustration of an electrocoating system of Figure 1 without internal electrodes.
  • the present invention is directed to an electrocoating system for electrocoating a substrate.
  • the present specification also discloses systems for coating a substrate, methods for coating substrates, substrates coated in accordance with one or more of the methods described herein, and/or through the use of one or more the systems described herein.
  • the present invention is directed to an electrocoating system 10 for electrocoating a substrate, the system comprising a tank 100 configured to hold an electrodepositable coating composition; at least one pump 200 in fluid communication with the tank 100, at least one return conduit 210 connecting the tank 100 to an inlet of the pump 200, at least one recirculating pipe 300 comprising a first end 310 in fluid
  • the at least one recirculating pipe 300 comprising at least one external electrode 400 positioned at least partially outside of the tank 100, wherein the substrate has a first surface and a second surface;
  • the return conduit 210 is configured to connect the tank 100 to an inlet of the pump 200;
  • the pump 200 is configured to receive the electrodepositable coating composition 600 from the return conduit 210 and deliver the electrodepositable coating composition 600 into the tank 100 through the recirculating pipe 300;
  • the external electrode 400 is configured to provide an electric charge to the electrodepositable coating composition 600;
  • the recirculating pipe 300 is configured to extend into the interior of the tank 100 and position the aperture 330 of the second end 320 to deliver at least a portion of the electrically charged electrodepositable coating composition 600 to the first surface of the substrate.
  • the tank 100 is configured to hold an electrodepositable coating composition.
  • the tank 100 may comprise any material known in the art.
  • the tank 100 may comprise plastic, metal having an insulating liner such as metal having an internal plastic liner, or metal having an insulating coating.
  • the tank 100 may comprise any geometric shape.
  • the tank 100 may be generally rectangular or generally round or spherical.
  • the tank 100 may comprise a base portion 110 and at least one side wall 120 extending up from the base portion 110 to form a cavity within which the electrodepositable coating composition 600 may be held.
  • the tank 100 is also configured to contain, at least partially, a substrate 500 for electrocoating.
  • the substrate 500 may be a grounded electrical conductor and may generally be substantially configured of a conductive substance, such as, for example, a metallic substance.
  • the substrate 500 serves as a counter-electrode in electrical
  • the substrate 500 may comprise any cross-sectional shape, or multiple cross-sectional shapes if the substrate 500 does not have a uniform cross-sectional shape.
  • the substrate may comprise any dimensions.
  • the substrate 500 may comprise an open-polygon cross-sectional shape, such as an open-pocket cross-sectional shape.
  • the cross-sectional shape may comprise a generally rectangular or a generally round cross-sectional shape.
  • the substrate may comprise a first surface 510 and a second surface 520.
  • the first surface 510 may comprise an internal surface of the substrate 500
  • the second surface 520 may comprise an external surface of the substrate 500.
  • the first surface 510 may comprise the internal surface of the substrate 500
  • the second surface 520 may comprise the external surface of the substrate 500.
  • the substrate 500 may comprise a container, such as, for example, an intermodal container.
  • the substrate 500 may have an external length of 8 feet (2.44 m), 10 feet (3.05 m), 20 feet (6.10 m), 40 feet (12.19 m), 45 feet (13.72 m) or 53 feet (16.15 m); an external width of 7 feet (2.13 m) or 8 feet (2.44 m); and an external height of 7.5 feet (2.29 m), 8.5 feet (2.59 m) or 9.5 feet (2.90 m).
  • the substrate 500 may have a length of at least 8 feet (2.44 m), such as at least 10 feet (3.05 m), such as at least 20 feet (6.10 m), such as at least 40 feet (12.19 m), such as at least 45 feet (13.72 m) or such as at least 53 feet (16.15 m).
  • the first surface 510 of the substrate 500 may have a surface area that varies based on the length of the substrate 500.
  • the first surface 510 of the substrate 500 may have a surface area of at least 285 ft 2 (26.48 m 2 ), such as at least 340 ft 2 (31.59 m 2 ), such as at least 600 ft 2 (55.74 m 2 ), such as at least 1, 145 ft 2 (106.37 m 2 ), such as at least 1,275 ft 2 (118.45 m 2 ), such as at least 1,490 ft 2 (138.43 m 2 ).
  • the first surface 510 of the substrate 500 may have a surface area of 285 ft 2 (26.48 m 2 ) to 1,890 ft 2 (175.59 m 2 ) or larger. With respect to a container, the surface area may vary depending upon the length of the substrate 500.
  • the first surface 510 of an 8 foot substrate 500 may have a surface area of 285 ft 2 (26.48 m 2 ) to 400 ft 2 (37.16 m 2 ), the first surface 510 of a 10 foot substrate 500 may have a surface area of 340 ft 2 (31.59 m 2 ) to 460 ft 2 (42.74 m 2 ), the first surface 510 of a 20 foot substrate 500 may have a surface area of 600 ft 2 (55.74 m 2 ) to 795 ft 2 (73.86 m 2 ), the first surface 510 of a 40 foot substrate 500 may have a surface area of 1,145 ft 2 (106.37 m 2 ) to 1,460 ft 2 (135.64 m 2 ), the first surface 510 of a 45 foot substrate 500 may have a surface area of 1,275 ft 2 (118.45 m 2 ) to 1,620 ft 2 (150.50 m 2 ), and the first surface 510 of
  • the second surface 520 of the substrate 500 may have a surface area that varies based on the length of the substrate 500.
  • the second surface 520 of the substrate 500 may have a surface area of at least such as at least 330 ft 2 (30.66 m 2 ), 380 ft 2 (35.30 m 2 ), such as at least 675 ft 2 (62.71 m 2 ), such as at least 1,250 ft 2 (116.13 m 2 ), such as at least 1,390 ft 2 (129.14 m 2 ), such as at least 1,630 ft 2 (151.43 m 2 ).
  • the second surface 520 of the substrate 500 may have a surface area of 330 ft 2 (30.66 m 2 ) to 1,750 ft 2 (162.58 m 2 ) or larger. With respect to a container, the surface area may vary depending upon the length of the substrate 500.
  • the second surface 520 of an 8 foot substrate 500 may have a surface area of 330 ft 2 (30.66 m 2 ) to 440 ft 2 (40.88 m 2 ), the second surface 520 of a 10 foot substrate 500 may have a surface area of 380 ft 2 (35.30 m 2 ) to 520 ft 2 (48.31 m 2 ), the second surface 520 of a 20 foot substrate 500 may have a surface area of 675 ft 2 (62.71 m 2 ) to 865 ft 2 (80.36 m 2 ), the second surface 520 of a 40 foot substrate 500 may have a surface area of 1250 ft 2 (116.13 m 2 ) to 1,575 ft 2 (146.32 m 2 ), the second surface 520 of a 45 foot substrate 500 may have a surface area of 1,390 ft 2 (129.14 m 2 ) to 1,750 ft 2 (162.58 m 2 ), and the second surface 520
  • the substrate may have a cross-sectional area of at least 40 m 2 , such as at least
  • the substrate may have a cross-sectional area of 40 m 2 to 100 m 2 , such as 45 m 2 to 85 m 2 , such as 50 m 2 to 80 m 2 .
  • the term“cross-sectional area” with respect to the substrate refers to the largest cross-sectional area of the substrate as measured perpendicular to the longest axis of the substrate. With respect to a container shaped substrate, the cross-sectional area will be the width multiplied by the height.
  • the substrate may comprise any conductive substrate.
  • the substrate may comprise a metal, metal alloy, and/or materials that have been metallized, such as nickel-plated plastic.
  • substrates may comprise non-metal conductive materials including composite materials such as, for example, materials comprising carbon fibers or conductive carbon.
  • the metal or metal alloy may comprise, for example, cold rolled steel, hot rolled steel, steel coated with zinc metal, zinc compounds or zinc alloys, such as electrogalvanized steel, hot-dipped galvanized steel, galvanealed steel, nickel-plated steel, and steel plated with zinc alloy.
  • the substrate may comprise an aluminum alloy.
  • Non limiting examples of aluminum alloys include the 1XXX, 2XXX, 3XXX, 4XXX, 5XXX, 6XXX, or 7XXX series as well as clad aluminum alloys and cast aluminum alloys.
  • the substrate may comprise a magnesium alloy.
  • the substrate used in the present invention may also comprise other suitable non-ferrous metals such as titanium or copper, as well as alloys of these materials.
  • the electrocoating system 10 also comprises a return conduit 210 that connects the tank 100 to the pump 200.
  • the return conduit 210 is configured to recycle the electrodepositable coating composition 600 from the tank 100 to the pump 200.
  • the return conduit 210 may comprise any combination of pipes, hoses, valves, and any other fluid conveying devices configured to perform the purposes stated herein.
  • the pump 200 is in fluid communication with the tank 100.
  • the pump 200 is configured to receive the electrodepositable coating composition 600 from the return conduit 210 and deliver the electrodepositable coating composition 600 into the tank 100 through a recirculating pipe 300.
  • the recirculating pipe 300 comprises a first end 310 in fluid communication with an outlet of the pump 200 and a second end 320 having at least one aperture 330.
  • the recirculating pipe 300 is configured to extend into the interior of the tank 100, immersed in the electrodepositable coating
  • the return conduit 210, pump 200, and recirculating pipe 300 may be directly coupled to form at least one continuous and uninterrupted loop for constrained flow of the
  • the pump 200 is configured to deliver the electrodepositable coating composition 600 into the tank 100 through the recirculating pipe 300 at a flow rate and pressure appropriate for electrocoating a substrate 500, as described herein.
  • the pump may deliver the electrodepositable coating composition 600 to the tank 100 at a pressure from about 1 psi to about 50 psi, such as from about 15 psi to about 40 psi, and at a flow rate from about 0.1 liters per second to about 65.0 liters per second.
  • the pump 200 may comprise, for example, a centrifugal pump. It is contemplated, however, that any pump 200 configured to perform the purposes stated herein may be utilized in the electrocoating system 10 of the present invention.
  • the external electrode 400 is positioned outside of the tank 100.
  • the external electrode 400 is configured to provide an electric charge to the electrodepositable coating composition 600 delivered by the pump 200 into the tank 100 through the recirculating pipe 300.
  • the external electrode 400 provides the electric charge to the electrodepositable coating composition 600 prior to its delivery into the tank 100 for electrocoating.
  • the pump 200 generally delivers the electrodepositable coating composition 600 past the external electrode 400 through the recirculating pipe 300 and into the tank 100 at a flow rate appropriate for the external electrode 400 to sufficiently electrically charge the electrodepositable coating composition 600.
  • This flow rate of the electrodepositable coating composition 600 delivered past the external electrode 400 may vary depending upon a volume of the electrodepositable coating composition 600 delivered by the pump 200 relative to the surface area of the external electrode 400. For example, it is contemplated that as a volume of the electrodepositable coating composition 600 increases, a slower flow rate of the electrodepositable coating composition 600 may be provided to increase a contact time between the electrodepositable coating composition 600 and the external electrode 400 and enable the external electrode 400 to sufficiently electrically charge the electrodepositable coating composition 600. Likewise, it is contemplated that an increase in the surface area of the external electrode 400 requires less contact time with the external electrode 400 in order to sufficiently electrically charge the electrodepositable coating composition 600.
  • the external electrode 400 may be configured in any variety of cross- sectional shapes, such as, for example, tubular, flat plate, C-shape, fanned, or annular, and may comprise, for example, a conductive pipe or pipe section, such as a metal pipe.
  • the external electrode 400 may have an internal surface configured to contact the electrodepositable coating composition 600, and the electrocoating system 10 may be configured such that the ratio of a total combined surface area of an external surface of the external electrode(s) 400 to a surface area of the first surface 510 of the substrate 500 is from 1 :7 to 1 : 1, such as 1 :6 to 1 :2, such as 1 :5 to 1 :3, such as about 1 :4.
  • At least a portion of the recirculating pipe 300 comprises the external electrode, and the portion of the recirculating pipe 300 comprising the external electrode 400 is located at least partially or completely outside of the tank 100.
  • at least partially or completely outside of the tank 100 means that at least a portion of the external electrode 400 is present outside of the tank 100 and not immersed in the electrodepositable coating composition 600, or that the entire external electrode 400 is located outside of the tank 100 and not immersed in the electrodepositable coating composition 600.
  • at least a portion or all of the recirculating pipe 300 that comprises the external electrode 400 is not immersed in the electrodepositable coating composition 600 held within the tank 100.
  • substantially all of the recirculating pipe 300 may comprise the external electrode 400.
  • the external electrode 400 may comprise at least 50% of the recirculating pipe 300, such as at least 60%, such as at least 75%, such as at least 85%, such as at least 95%, such as 100%.
  • the remainder of the recirculating pipe 300 may comprise a combination of non-conductive and/or conductive materials.
  • the recirculating pipe 300 may comprise any combination of pipes, hoses, valves, and any other fluid conveying devices configured to perform the purposes stated herein.
  • the external electrode 400 may be contained within an insulating part 410.
  • the insulating part 410 may prevent a user of the electrocoating system 10 from being exposed to the electric charge of the external electrode 400 when an electrical potential is applied to the electrocoating system 10.
  • the insulating part 410 may alternatively, or in addition to, be located on the recirculating pipe 300 that extends into the tank 100.
  • the insulating part 410 may comprise, for example, a polyvinyl chloride (PVC) pipe in which the external electrode 400 is contained. It is contemplated, however, that any insulating part 410 configured to perform the purposes stated herein may be utilized according to the
  • a membrane may be used to cover the internal surface of the external electrode 400 so as to remove acid build-up from the electrodepositable coating composition 600 during the process of electrocoating a substrate 500.
  • a membrane may be covered by a membrane to control pH of the electrodepositable coating composition through the removal of acid generated during electrocoating.
  • Membrane covered anodes generally are referred to in the industry as anolyte cells.
  • An external electrode 400 that is substantially membrane-free is one that is membrane-free to an extent that any existing membrane does not interfere, to any significant degree, with the electric charging of the electrodepositable coating composition 600 by the external electrode 400.
  • the external electrode 400 may be completely membrane-free.
  • the external electrode 400 may comprise, for example, a membrane-free 316 type stainless steel pipe.
  • the entirely exposed wall of the channel of the membrane-free metal pipe external electrode 400 combined with the flow of the electrodepositable coating composition 600 through the external electrode 400 may aid in the external electrode 400 providing the electric charge substantially uniform to the electrodepositable coating composition 600 so as to promote substantially equal electric charge distribution throughout the electrodepositable coating composition 600.
  • Substantially equal electric charge distribution throughout the electrodepositable coating composition 600 optimizes the electrocoating of the substrate 500 by providing a substantially uniform attraction of charged molecules of the electrodepositable coating composition 600 to the oppositely charged substrate 500.
  • a greater surface area of the external electrode 400 may be provided to sufficiently electrically charge the electrodepositable coating composition 600 delivered by the pump 200.
  • a minimum surface area of the external electrode 400 per unit volume of electrodepositable coating composition 600 flow may be provided to sufficiently charge the electrodepositable coating composition 600 prior to its delivery to the tank 100 for electrocoating a substrate 500.
  • the surface area of the external electrode 400 may be manipulated by, for example, increasing the length of the external electrode 400 (i.e., increasing the length of the portion of the recirculating pipe 300 that comprises the external electrode 400, or, if the entire recirculating pipe 300 comprises the external electrode 400, increasing the length of the recirculating pipe 300), or changing the cross-sectional shape of the external electrode 400.
  • the second end 320 of the recirculating pipe 300 may comprise a nozzle which comprises the aperture 330.
  • the nozzle may comprise any nozzle known in the art.
  • the second end 320 of the recirculating pipe 300 may comprise a plurality of apertures 330 through which the electrodepositable coating composition 600 may pass.
  • the recirculating pipe may also comprise a plurality of second ends 320.
  • the recirculating pipe may be branched with each branch comprising a second end 320 comprising at least one aperture 330.
  • Each second end 320 of the branched recirculating pipe 300 may be configured to deliver at least a portion of the electrodepositable coating composition 600 electrically charged by the external electrode 400 to different sections of the first surface 510 of the substrate 500.
  • the electrocoating system 10 may comprise a plurality of return conduits 210, pumps 200, and/or recirculating pipes 300.
  • the electrocoating system 10 may comprise a plurality of return conduits 210, pumps 200, and/or recirculating pipes 300.
  • electrocoating system 10 may comprise a plurality of recirculating pipes 300 configured to deliver the electrodepositable coating composition 600 charged by the external electrode(s) 400 to different sections of the first surface 510 of the substrate 500.
  • Each recirculating pipe 300 may be fed by a different pump 200, or a pump 200 may pump the electrodepositable coating composition 600 to multiple recirculating pipes 300.
  • each pump 200 may be fed by a return conduit 210, or a return conduit 210 may feed multiple pumps 200.
  • each component i.e., return conduit 210, pump 200, recirculating pipe 300
  • the number of each component may depend upon a variety of factors, including, for example, the length of the substrate 500, the surface area of the first surface 510 of the substrate 500, the resin solids present in the electrodepositable coating composition 600, the charge density of the electrodepositable coating composition 600, the voltage applied during electrocoating of the substrate, the shape of the substrate, among other factors.
  • the return conduits 210, pumps 200, and/or recirculating pipes 300 may be positioned along a length of the tank 100 such that the electrodepositable coating composition 600 is deposited substantially uniform along the length of the substrate 500 to be electrocoated.
  • the return conduits 210, pumps 200, and/or recirculating pipes 300 may be positioned equidistant along a length of the tank 100.
  • the electrodepositable coating composition 600 flowed into the tank 100 through the recirculating pipe 300 may be substantially deposited onto the first surface 510 of the substrate 500 during electrocoating.
  • positioning the recirculating pipe 300 of the electrocoating system 10 inside the tank 100 to provide a flow of electrodepositable coating composition 600 charged by the external electrode 400 to the first surface 510 of the substrate 500 allows for the deposition of a more uniform coating to be applied to the first surface 510 of the substrate 500 in comparison to an electrocoating system that does not include the recirculating pipe 300 and external electrode 400.
  • the electrodepositable coating composition 600 is charged by the external electrode 400 and, if present, the internal electrode 700, and is attracted to, and deposits on, the oppositely charged substrate 500.
  • Equal, or substantially equal, charge distribution throughout the electrically charged fluid provided by the electrocoating system 10 of the present invention enhances the electrocoating process by generally providing a substantially uniform coating thickness of the electrodepositable coating composition 500 deposited on the substrate 500.
  • the electrocoating system 10 optionally may further comprise at least one internal electrode 700 positioned inside the tank 100 to provide additional electric charge to the electrodepositable coating composition 600, as shown in Figures 1 and 2.
  • the internal electrode 700 may comprise any suitable conductive material known in the art.
  • the internal electrode 700 may comprise a pipe electrically coupled with the power source.
  • the internal electrode(s) 700 may be membrane-free, or substantially membrane-free, or substantially covered by a membrane.
  • the electrocoating system 10 may comprise a plurality of internal electrodes 700, and the internal electrodes 700 may be positioned along a length of the tank 100 such that the electrodepositable coating composition 600 is deposited substantially uniform along the length of the substrate 500 to be electrocoated.
  • the internal electrode 700 may be positioned equidistant along a length of the tank 100.
  • the electrocoating system 10 may be configured such that the ratio of a total combined surface area of the internal electrode(s) 700 to the surface area of the second surface 510 of the substrate 500 may be from 1 :7 to 1 : 1, such as 1 :6 to 1 :2, such as 1 :5 to 1 :3, such as 1 :4.
  • the internal electrode 700 does not recirculate or transport the electrodepositable coating composition 600 within the electrocoating system 10.
  • the use of the internal electrode 700 in an electrocoating system will not provide a sufficient charge to the electrodepositable coating composition 600 to enable a uniform deposition of the electrodepositable coating composition 600 over the entire surface of the substrate 500 without the recirculating pipe 300 comprising the external electrode 400 also being present.
  • the internal electrode 700 may provide a sufficient charge to the electrodepositable coating composition 600
  • electrodepositable coating composition 600 to deposit a coating on a surface of the substrate 500 located near the internal electrode 700, such as, for example, the second surface 520 of the substrate 500, but may not provide a sufficient charge to enable deposition on other portions of the substrate, such as, for example, the first surface 510 of the substrate 500.
  • the electrocoating system 10 further comprises at least one power source (not shown) to provide an electrical current to the electrocoating system 10.
  • the power source may optionally include a rectifier.
  • the power source is electrically coupled to the external electrode(s) 400, the substrate 500, and, if present, the internal electrodes 700, with one pole of the power source coupled to the substrate, and the other pole of the power source coupled to the external electrode(s) 400 and, if present, the internal electrode(s) 700, such that the substrate serves as a counter-electrode to the external electrode 400 and, if present, internal electrode 700.
  • the electrodepositable coating composition 600 is a cationic electrodepositable coating composition
  • the substrate 500 serves as the cathode and the external electrode 400 and, if present, internal electrode 700 serve as anodes, with the polarities reversed for an anionic electrodepositable coating composition.
  • the power source provides an electric current to the electrocoating system 10 such that the external electrode 400 and, if present, internal electrode 700, provide an electric charge to the electrodepositable coating composition 600 sufficient for electrocoating purposes.
  • the electric current provided to the power source may be, but is not limited to, about 25 volts to about 600 volts or higher.
  • the voltage provided to the power source may vary according to a volume of the electrodepositable coating composition 600 delivered by the pump 200. For example, a higher voltage may be provided to the external electrode 400 to sufficiently charge an increased volume and/or increased flow rate of the
  • the electrocoating system 10 may also comprise any additional or other electrical circuitry desired or needed to perform the purposes stated herein.
  • the electrodepositable coating composition 600 may comprise any one of
  • Electrodepositable coating composition refers to a composition that is capable of being deposited onto an electrically conductive substrate under the influence of an applied electrical potential.
  • the electrodepositable coating composition 600 may comprise a cationic or anionic electrodepositable coating composition.
  • the electrodepositable coating composition comprises a film-forming binder.
  • the film-forming binder may comprise an ionic salt group-containing film-forming polymer and, optionally, a curing agent.
  • the ionic salt group-containing film forming polymer may comprise a cationic salt group-containing film-forming polymer.
  • the cationic salt group-containing, film-forming polymer may be used in a cationic
  • the term“cationic salt group- containing film-forming polymer” refers to polymers that include at least partially neutralized cationic groups, such as sulfonium groups and/or ammonium groups, that impart a positive charge to the polymer.
  • the term“polymer” encompasses, but is not limited to, oligomers and both homopolymers and copolymers.
  • the cationic salt group-containing film-forming polymer may comprise active hydrogen functional groups.
  • the term“active hydrogen functional groups” refers to those groups that are reactive with isocyanates as determined by the Zerewitinoff test described in the JOURNAL OF THE AMERICAN CHEMICAL SOCIETY, Vol.
  • Cationic salt group- containing film-forming polymers that comprise active hydrogen functional groups may be referred to as active hydrogen-containing, cationic salt group-containing film-forming polymers.
  • the cationic salt groups may be incorporated into the cationic salt group- containing film-forming polymer as follows:
  • the film-forming polymer may be reacted with a cationic salt group former.
  • cationic salt group former is meant a material which is reactive with epoxy groups present and which may be acidified before, during, or after reaction with the epoxy groups on the film-forming polymer to form cationic salt groups.
  • suitable materials include amines such as primary or secondary amines which can be acidified after reaction with the epoxy groups to form amine salt groups, or tertiary amines which can be acidified prior to reaction with the epoxy groups and which after reaction with the epoxy groups form quaternary ammonium salt groups.
  • examples of other cationic salt group formers are sulfides which can be mixed with acid prior to reaction with the epoxy groups and form ternary sulfonium salt groups upon subsequent reaction with the epoxy groups.
  • Suitable active hydrogen-containing, cationic salt group containing film-forming polymers include polyepoxide-amine adducts, such as the adduct of a polyglycidyl ether of a polyphenol, such as Bisphenol A, and primary and/or secondary amines, such as are described in U.S. Patent No. 4,031,050 at col. 3, line 27 to col. 5, line 50, U.S. Patent No. 4,452,963 at col. 5, line 58 to col. 6, line 66, and U.S. Patent No. 6,017,432 at col. 2, line 66 to col. 6, line 26, these portions of which being incorporated herein by reference.
  • a portion of the amine that is reacted with the polyepoxide may be a ketimine of a polyamine, as is described in U.S. Patent No. 4,104,147 at col. 6, line 23 to col. 7, line 23, the cited portion of which being incorporated herein by reference.
  • ungelled polyepoxide-polyoxyalkylenepolyamine resins such as are described in U.S. Patent No. 4,432,850 at col. 2, line 60 to col. 5, line 58, the cited portion of which being incorporated herein by reference.
  • cationic acrylic resins such as those described in U.S. Patent No. 3,455,806 at col. 2, line 18 to col. 3, line 61 and 3,928,157 at col. 2, line 29 to col. 3, line 21, these portions of both of which are incorporated herein by reference, may be used.
  • the cationic salt group-containing film-forming polymer may comprise a quaternary ammonium salt group-containing resin.
  • a“quaternary ammonium salt group” refers to group comprising a quaternary ammonium cation of the formula NR 4 + , wherein each R group is independently an alkyl or aryl group, and a counter anion.
  • these resins are those which are formed from reacting an organic polyepoxide with a tertiary amine acid salt. Such resins are described in U.S. Patent No. 3,962,165 at col. 2, line 3 to col. 11, line 7; 3,975,346 at col. 1, line 62 to col. 17, line 25 and 4,001,156 at col. 1, line 37 to col. 16, line 7, these portions of which being incorporated herein by reference.
  • Suitable cationic resins include ternary sulfonium salt group-containing resins, such as those described in U.S. Patent. No. 3,793,278 at col. 1, line 32 to col. 5, line 20, this portion of which being incorporated herein by reference. Also, cationic resins which cure via a transesterification mechanism, such as described in European Patent Application No. 12463B1 at pg. 2, line 1 to pg. 6, line 25, this portion of which being incorporated herein by reference, may also be employed.
  • Other suitable cationic salt group-containing film-forming polymers include those that may form photodegradation resistant electrodepositable coating compositions.
  • Such polymers include the polymers comprising cationic amine salt groups which are derived from pendant and/or terminal amino groups that are disclosed in U.S. Patent Application Publication No. 2003/0054193 Al at paragraphs [0064] to [0088], this portion of which being incorporated herein by reference.
  • active hydrogen-containing, cationic salt group-containing resins derived from a polyglycidyl ether of a polyhydric phenol that is essentially free of aliphatic carbon atoms to which are bonded more than one aromatic group, which are described in U.S. Patent Application Publication No. 2003/0054193 Al at paragraphs [0096] to [0123], this portion of which being incorporated herein by reference.
  • the active hydrogen-containing, cationic salt group-containing film-forming polymer may be made cationic and water dispersible by at least partial neutralization with an acid.
  • Suitable acids include organic and inorganic acids.
  • suitable organic acids include formic acid, acetic acid, methanesulfonic acid, and lactic acid.
  • suitable inorganic acids include phosphoric acid and sulfamic acid.
  • sulfamic acid is meant sulfamic acid itself or derivatives thereof such as those having the formula:
  • R is hydrogen or an alkyl group having 1 to 4 carbon atoms. Mixtures of the above- mentioned acids also may be used in the present invention.
  • the extent of neutralization of the cationic salt group-containing film-forming polymer may vary with the particular polymer involved. However, sufficient acid should be used to sufficiently neutralize the cationic salt-group containing film-forming polymer such that the cationic salt-group containing film-forming polymer may be dispersed in an aqueous dispersing medium. For example, the amount of acid used may provide at least 20% of all of the total theoretical neutralization. Excess acid may also be used beyond the amount required for 100% total theoretical neutralization. For example, the amount of acid used to neutralize the cationic salt group-containing film-forming polymer may be 30.l% based on the total amines in the active hydrogen-containing, cationic salt group-containing film-forming polymer.
  • the amount of acid used to neutralize the active hydrogen-containing, cationic salt group-containing film-forming polymer may be £ 100% based on the total amines in the active hydrogen-containing, cationic salt group-containing film-forming polymer.
  • the total amount of acid used to neutralize the cationic salt group-containing film forming polymer may range between any combination of values, which were recited in the preceding sentences, inclusive of the recited values.
  • the total amount of acid used to neutralize the active hydrogen-containing, cationic salt group-containing film forming polymer may be 20%, 35%, 50%, 60%, or 80% based on the total amines in the cationic salt group-containing film-forming polymer.
  • the cationic salt group-containing film-forming polymer may be present in the cationic electrodepositable coating composition in an amount of at least 40% by weight, such as at least 50% by weight, such as at least 60% by weight, and may be present in the in an amount of no more than 90% by weight, such as no more than 80% by weight, such as no more than 75% by weight, based on the total weight of the resin solids of the
  • the cationic salt group-containing film-forming polymer may be present in the cationic electrodepositable coating composition in an amount of 40% to 90% by weight, such as 50% to 80% by weight, such as 60% to 75% by weight, based on the total weight of the resin solids of the electrodepositable coating composition.
  • the“resin solids” include the ionic salt group-containing film-forming polymer, the curing agent (if present), and any additional water-dispersible non-pigmented component s) present in the electrodepositable coating composition.
  • the ionic salt group containing film forming polymer may comprise an anionic salt group containing film-forming polymer.
  • anionic salt group containing film-forming polymer refers to an anionic polymer comprising at least partially neutralized anionic functional groups, such as carboxylic acid and phosphoric acid groups that impart a negative charge.
  • the anionic salt group-containing film-forming polymer may comprise active hydrogen functional groups.
  • Anionic salt group-containing film-forming polymers that comprise active hydrogen functional groups may be referred to as active hydrogen-containing, anionic salt group- containing film-forming polymers.
  • the anionic salt group containing film-forming polymer may be used in an anionic electrodepositable coating composition.
  • the anionic salt group-containing film-forming polymer may comprise base- solubilized, carboxylic acid group-containing film-forming polymers such as the reaction product or adduct of a drying oil or semi -drying fatty acid ester with a dicarboxylic acid or anhydride; and the reaction product of a fatty acid ester, unsaturated acid or anhydride and any additional unsaturated modifying materials which are further reacted with polyol. Also suitable are the at least partially neutralized interpolymers of hydroxy-alkyl esters of unsaturated carboxylic acids, unsaturated carboxylic acid and at least one other ethylenically unsaturated monomer.
  • Still another suitable anionic electrodepositable resin comprises an alkyd-aminoplast vehicle, i.e., a vehicle containing an alkyd resin and an amine-aldehyde resin.
  • Another suitable anionic electrodepositable resin composition comprises mixed esters of a resinous polyol.
  • Other acid functional polymers may also be used such as phosphatized polyepoxide or phosphatized acrylic polymers. Exemplary phosphatized polyepoxides are disclosed in U.S. Patent Application Publication No. 2009-0045071 at [0004]-[00l 5] and U.S. Patent Application Serial No. 13/232,093 at [00l4]-[0040], the cited portions of which being incorporated herein by reference.
  • resins comprising one or more pendent carbamate functional groups, such as those described in U.S. Patent No. 6,165,338.
  • the anionic salt group-containing film forming polymer may be present in the anionic electrodepositable coating composition in an amount of at least 50% by weight, such as at least 55% by weight, such as at least 60% by weight, and may be present in an amount of no more than 90% by weight, such as no more than 80% by weight, such as no more than 75% by weight, based on the total weight of the resin solids of the electrodepositable coating composition.
  • the anionic salt group-containing film-forming polymer may be present in the anionic electrodepositable coating composition in an amount 50% to 90%, such as 55% to 80%, such as 60% to 75%, based on the total weight of the resin solids of the electrodepositable coating composition.
  • the electrodepositable coating composition of the present invention may further comprise a curing agent.
  • the curing agent may be reactive with the ionic salt group-containing film-forming polymer.
  • the curing agent comprises functional groups that react with the reactive functional groups, such as active hydrogen groups, of the ionic salt group-containing film-forming polymer to effectuate cure of the coating composition to form a coating.
  • the term“cure”,“cured” or similar terms, as used in connection with the electrodepositable coating compositions described herein means that at least a portion of the components that form the
  • electrodepositable coating composition are crosslinked to form a coating.
  • curing of the electrodepositable coating composition refers to subjecting said composition to curing conditions (e.g., elevated temperature) leading to the reaction of the reactive functional groups of the components of the electrodepositable coating composition, and resulting in the crosslinking of the components of the composition and formation of an at least partially cured coating.
  • suitable curing agents are at least partially blocked polyisocyanates, aminoplast resins and phenoplast resins, such as phenolformaldehyde condensates including allyl ether derivatives thereof.
  • Suitable at least partially blocked polyisocyanates include aliphatic polyisocyanates, aromatic polyisocyanates, and mixtures thereof.
  • the curing agent may comprise an at least partially blocked aliphatic polyisocyanate.
  • Suitable at least partially blocked aliphatic polyisocyanates include, for example, fully blocked aliphatic
  • polyisocyanates such as those described in U.S. Patent No. 3,984,299 at col. 1 line 57 to col. 3 line 15, this portion of which is incorporated herein by reference, or partially blocked aliphatic polyisocyanates that are reacted with the polymer backbone, such as is described in U.S. Patent No. 3,947,338 at col. 2 line 65 to col. 4 line 30, this portion of which is also incorporated herein by reference.
  • “blocked” is meant that the isocyanate groups have been reacted with a compound such that the resultant blocked isocyanate group is stable to active hydrogens at ambient temperature but reactive with active hydrogens in the film forming polymer at elevated temperatures, such as between 90°C and 200°C.
  • the polyisocyanate curing agent may be a fully blocked polyisocyanate with substantially no free isocyanate groups.
  • the polyisocyanate curing agent may comprise a diisocyanate, higher functional polyisocyanates or combinations thereof.
  • the polyisocyanate curing agent may comprise aliphatic and/or aromatic polyisocyanates.
  • Aliphatic polyisocyanates may include (i) alkylene isocyanates, such as trimethylene diisocyanate, tetram ethylene diisocyanate, pentamethylene diisocyanate, hexamethylene diisocyanate (“HDI”), 1,2- propylene diisocyanate, 1, 2-butylene diisocyanate, 2,3-butylene diisocyanate, 1, 3-butylene diisocyanate, ethylidene diisocyanate, and butylidene diisocyanate, and (ii) cycloalkylene isocyanates, such as 1, 3-cyclopentane diisocyanate, 1, 4-cyclohexane diisocyanate, 1,2- cyclohexane
  • Aromatic polyisocyanates may include (i) arylene isocyanates, such as m- phenylene diisocyanate, p-phenylene diisocyanate, 1,5 -naphthalene diisocyanate and 1,4- naphthalene diisocyanate, and (ii) alkarylene isocyanates, such as 4,4 '-diphenyl ene methane (“MDI”), 2,4-tolylene or 2,6-tolylene diisocyanate (“TDI”), or mixtures thereof, 4,4-toluidine diisocyanate and xylylene diisocyanate.
  • MDI 4,4 '-diphenyl ene methane
  • TDI 2,4-tolylene or 2,6-tolylene diisocyanate
  • Triisocyanates such as triphenyl methane-4, 4', 4"- triisocyanate, l,3,5-triisocyanato benzene and 2,4,6-triisocyanato toluene
  • tetraisocyanates such as 4,4'-diphenyldimethyl methane-2, 2', 5, 5'-tetraisocyanate, and polymerized
  • polyisocyanates such as tolylene diisocyanate dimers and trimers and the like
  • the curing agent may comprise a blocked polyisocyanate selected from a polymeric polyisocyanate, such as polymeric HDI, polymeric MDI, polymeric isophorone diisocyanate, and the like.
  • the curing agent may also comprise a blocked trimer of hexamethylene diisocyanate available as Desmodur N3300® from Covestro AG. Mixtures of polyisocyanate curing agents may also be used.
  • the polyisocyanate curing agent may be at least partially blocked with at least one blocking agent selected from a 1, 2-alkane diol, for example 1, 2-propanediol; a 1, 3-alkane diol, for example l,3-butanediol; a benzylic alcohol, for example, benzyl alcohol; an allylic alcohol, for example, allyl alcohol; caprolactam; a dialkylamine, for example dibutylamine; and mixtures thereof.
  • the polyisocyanate curing agent may be at least partially blocked with at least one 1, 2-alkane diol having three or more carbon atoms, for example l,2-butanediol.
  • blocking agents include aliphatic, cycloaliphatic, or aromatic alkyl monoalcohols or phenolic compounds, including, for example, lower (e.g. Ci-C 6 ) aliphatic alcohols, such as methanol, ethanol, and n-butanol; cycloaliphatic alcohols, such as cyclohexanol; aromatic-alkyl alcohols, such as phenyl carbinol and methylphenyl carbinol; and phenolic compounds, such as phenol itself and substituted phenols wherein the substituents do not affect coating operations, such as cresol and nitrophenol. Glycol ethers and glycol amines may also be used as blocking agents.
  • lower (e.g. Ci-C 6 ) aliphatic alcohols such as methanol, ethanol, and n-butanol
  • cycloaliphatic alcohols such as cyclohexanol
  • aromatic-alkyl alcohols such as phenyl carbin
  • Suitable glycol ethers include ethylene glycol butyl ether, diethylene glycol butyl ether, ethylene glycol methyl ether and propylene glycol methyl ether.
  • Other suitable blocking agents include oximes, such as methyl ethyl ketoxime, acetone oxime and cyclohexanone oxime.
  • the curing agent may comprise an aminoplast resin.
  • Aminoplast resins are condensation products of an aldehyde with an amino- or amido-group carrying substance. Condensation products obtained from the reaction of alcohols and an aldehyde with melamine, urea or benzoguanamine may be used.
  • condensation products of other amines and amides may also be employed, for example, aldehyde condensates of triazines, diazines, triazoles, guanidines, guanamines and alkyl- and aryl -substituted derivatives of such compounds, including alkyl- and aryl -substituted ureas and alkyl- and aryl -substituted melamines.
  • Some examples of such compounds are N,N'-dimethyl urea, benzourea, dicyandi amide, formaguanamine, acetoguanamine, ammeline, 2-chloro-4,6-diamino-l,3,5- triazine, 6-methyl-2,4-diamino-l,3,5-triazine, 3,5-diaminotriazole, triaminopyrimidine, 2- mercapto-4,6-diaminopyrimidine, 3,4,6-tris(ethylamino)-l,3,5-triazine, and the like.
  • Suitable aldehydes include formaldehyde, acetaldehyde, crotonaldehyde, acrolein, benzaldehyde, furfural, glyoxal and the like.
  • the aminoplast resins may contain methylol or similar alkylol groups, and at least a portion of these alkylol groups may be etherified by a reaction with an alcohol to provide organic solvent-soluble resins.
  • Any monohydric alcohol may be employed for this purpose, including such alcohols as methanol, ethanol, propanol, butanol, pentanol, hexanol, heptanol and others, as well as benzyl alcohol and other aromatic alcohols, cyclic alcohol such as cyclohexanol, monoethers of glycols such as Cello-solves and Carbitols, and halogen- substituted or other substituted alcohols, such as 3-chloropropanol and butoxy ethanol.
  • Non-limiting examples of commercially available aminoplast resins are those available under the trademark CYMEL® from Allnex Belgium SA/NV, such as CYMEL 1130 and 1156, and RESIMENE® from INEOS Melamines, such as RESIMENE 750 and 753.
  • suitable aminoplast resins also include those described in ET.S. Patent No. 3,937,679 at col. 16, line 3 to col. 17, line 47, this portion of which being hereby incorporated by reference.
  • the aminoplast may be used in combination with the methylol phenol ethers.
  • Phenoplast resins are formed by the condensation of an aldehyde and a phenol.
  • Suitable aldehydes include formaldehyde and acetaldehyde.
  • Methylene-releasing and aldehyde-releasing agents such as paraformaldehyde and hexamethylene tetramine, may also be utilized as the aldehyde agent.
  • Various phenols may be used, such as phenol itself, a cresol, or a substituted phenol in which a hydrocarbon radical having either a straight chain, a branched chain or a cyclic structure is substituted for a hydrogen at the aromatic ring.
  • phenols may also be employed.
  • suitable phenols are p-phenylphenol, p-tert-butylphenol, p-tert-amylphenol, cyclopentylphenol and unsaturated hydrocarbon-substituted phenols, such as the monobutenyl phenols containing a butenyl group in ortho, meta or para position, and where the double bond occurs in various positions in the hydrocarbon chain.
  • the curing agent may be present in the cationic electrodepositable coating composition in an amount of at least 10% by weight, such as at least 20% by weight, such as at least 25% by weight, and may be present in an amount of no more than 60% by weight, such as no more than 50% by weight, such as no more than 40% by weight, based on the total weight of the resin solids of the electrodepositable coating composition.
  • the curing agent may be present in the cationic electrodepositable coating composition in an amount of 10% to 60% by weight, such as 20% to 50% by weight, such as 25% to 40% by weight, based on the total weight of the resin solids of the electrodepositable coating composition.
  • the curing agent may be present in the anionic electrodepositable coating composition in an amount of at least 10% by weight, such as at least 20% by weight, such as at least 25% by weight, and may be present in an amount of no more than 50% by weight, such as no more than 45% by weight, such as no more than 40% by weight, based on the total weight of the resin solids of the electrodepositable coating composition.
  • the curing agent may be present in the anionic electrodepositable coating composition in an amount of 10% to 50% by weight, such as 20% to 45% by weight, such as 25% to 40% by weight, based on the total weight of the resin solids of the electrodepositable coating composition.
  • the electrodepositable coating composition according to the present invention may optionally comprise one or more further components in addition to the film-forming binder described above.
  • the electrodepositable coating composition may optionally comprise a catalyst to catalyze the reaction between the curing agent and the polymers.
  • a catalyst to catalyze the reaction between the curing agent and the polymers.
  • compositions include, without limitation, organotin compounds (e.g., dibutyltin oxide and dioctyltin oxide) and salts thereof (e.g., dibutyltin diacetate); other metal oxides (e.g., oxides of cerium, zirconium and bismuth) and salts thereof (e.g., bismuth sulfamate and bismuth lactate); or a cyclic guanidine as described in U.S. Patent No. 7,842,762 at col. 1, line 53 to col. 4, line 18 and col. 16, line 62 to col. 19, line 8, the cited portions of which being incorporated herein by reference.
  • organotin compounds e.g., dibutyltin oxide and dioctyltin oxide
  • salts thereof e.g., dibutyltin diacetate
  • other metal oxides e.g., oxides of cerium, zirconium and bismuth
  • salts thereof e
  • electrodepositable coating compositions include latent acid catalysts, specific examples of which are identified in WO 2007/118024 at [0031] and include, but are not limited to, ammonium hexafluoroantimonate, quaternary salts of SbF 6 (e.g., NACURE® XC-7231), t- amine salts of SbF 6 (e.g., NACURE® XC-9223), Zn salts of triflic acid (e.g., NACURE® A202 and A218), quaternary salts of triflic acid (e.g., NACURE® XC-A230), and
  • Latent acid catalysts may be formed by preparing a derivative of an acid catalyst such as para-toluenesulfonic acid (pTSA) or other sulfonic acids.
  • pTSA para-toluenesulfonic acid
  • a well-known group of blocked acid catalysts are amine salts of aromatic sulfonic acids, such as pyridinium para-toluenesulfonate. Such sulfonate salts are less active than the free acid in promoting crosslinking.
  • the catalysts may be activated by heating.
  • the electrodepositable coating composition may further comprise other optional ingredients, such as a pigment composition and/or various additives including fillers, plasticizers, anti-oxidants, biocides, UV light absorbers and stabilizers, hindered amine light stabilizers, defoamers, fungicides, dispersing aids, flow control agents, surfactants, wetting agents, pH adjusters, buffering agents, or combinations thereof.
  • the electrodepositable coating composition may be completely free of any of the optional ingredients, i.e., the optional ingredient is not present in the
  • the pigment composition may comprise, for example, iron oxides, lead oxides, strontium chromate, coal dust, titanium dioxide, talc, barium sulfate, as well as color pigments such as cadmium yellow, cadmium red, chromium yellow and the like.
  • the pigment content of the pigment composition which excludes the electrically conductive particles described above, may be expressed as the pigment-to-binder weight ratio, and may be within the range of 0.03 to 0.1, when pigment is used.
  • the other additives mentioned above may be present in the electrodepositable coating composition in amounts of 0.01% to 3% by weight, based on total weight of the resin solids of the electrodepositable coating composition.
  • the electrodepositable coating composition comprises an aqueous dispersion medium comprising water and/or one or more organic solvent(s).
  • Water can for example be present in amounts of 40% to 90% by weight, such as 50% to 80% by weight, such as 60 to 75% by weight, based on total weight of the
  • Suitable organic solvents include oxygenated organic solvents, such as monoalkyl ethers of ethylene glycol, diethylene glycol, propylene glycol, and dipropylene glycol which contain from 1 to 10 carbon atoms in the alkyl group, such as the monoethyl and monobutyl ethers of these glycols.
  • suitable organic solvents include oxygenated organic solvents, such as monoalkyl ethers of ethylene glycol, diethylene glycol, propylene glycol, and dipropylene glycol which contain from 1 to 10 carbon atoms in the alkyl group, such as the monoethyl and monobutyl ethers of these glycols.
  • suitable organic solvents include oxygenated organic solvents, such as monoalkyl ethers of ethylene glycol, diethylene glycol, propylene glycol, and dipropylene glycol which contain from 1 to 10 carbon atoms in the alkyl group, such as the monoethyl and monobutyl ethers of these glycols.
  • electrodepositable coating composition may be at least 1% by weight, such as at least 10% by weight, such as at least 20% by weight, and may be no more than 60% by weight, such as no more than 40% by weight, such as no more than 20% by weight, based on the total weight of the electrodepositable coating composition.
  • the total solids content of the electrodepositable coating composition may be from 1% to 60% by weight, such as 10% to 40% by weight, such as 20% to 30% by weight, based on the total weight of the electrodepositable coating composition.
  • the present invention is also directed to a method for coating a substrate comprising electrophoretically applying a coating deposited from an electrodepositable coating composition to at least a portion of the substrate using the electrocoating system 10 described above.
  • the electrodepositable coating composition of the present invention may be deposited upon an electrically conductive substrate by placing the electrodepositable coating composition in contact with an electrically conductive cathode and an electrically conductive anode, with the surface to be coated being either the anode or the cathode, depending upon the type of electrodepositable coating composition being applied. Following contact with the composition, an adherent film of the electrodepositable coating composition is deposited on the substrate when a sufficient voltage is impressed between the electrodes by a power source.
  • the applied voltage may be varied and can be, for example, as low as one volt to as high as several thousand volts, such as between 25 and 600 volts.
  • the current density may be between 0.5 ampere and 15 amperes per square foot.
  • the electrodepositable coating composition that may be used in the method of the present invention may comprise any of those known in the art, including those described above.
  • the electrodepositable coating composition may comprise a cationic film-forming resin comprising sulphonium groups and/or ammonium groups, or the electrodepositable coating composition may comprise an anionic electrodepositable coating composition comprising carboxylic acid and/or phosphoric acid groups.
  • the method may further comprise at least partially curing the electrophoretically applied coating deposited from the electrodepositable coating composition on the substrate.
  • at least partially curing the electrodepositable coating composition may comprise subjecting the substrate to elevated temperature.
  • the coated substrate may be heated to a temperature ranging from, for example, 250°F to 450°F
  • the coated substrate may be heated to a temperature ranging from, for example, 200°F to 450°F (93°C to 232.2°C), such as from 275°F to 400°F (l35°C to 204.4°C), such as from 300°F to 360°F (l49°C to l80°C).
  • a temperature ranging from, for example, 200°F to 450°F (93°C to 232.2°C), such as from 275°F to 400°F (l35°C to 204.4°C), such as from 300°F to 360°F (l49°C to l80°C).
  • the curing time may be dependent upon the curing temperature as well as other variables, for example, the film thickness of the electrodeposited coating, level and type of catalyst present in the composition, type of curing agent employed, and the like. For purposes of the present invention, all that is necessary is that the time be sufficient to effect cure of the coating on the substrate.
  • the curing time can range from 10 minutes to 60 minutes, such as 20 to 40 minutes.
  • the thickness of the resultant cured electrodeposited coating may range from 1 to 50 microns, such as 15 to 50 microns.
  • the method for coating a substrate may comprise (a) electrophoretically depositing onto at least a portion of the substrate a coating deposited from an electrodepositable coating composition using the electrocoating system 10 described above and (b) heating the coated substrate to a temperature and for a time sufficient to at least partially cure the electrodeposited coating on the substrate.
  • the method may optionally further comprise (c) applying directly to the at least partially cured electrodeposited coating one or more pigment-containing coating compositions and/or one or more pigment-free coating compositions to form an additional coating layer over at least a portion of the at least partially cured electrodeposited coating, and (d) curing the additional coating layer by allowing it to set at ambient temperature or by applying a sufficient energy from an external energy source to the coated substrate of step (c) to a condition and for a time sufficient to at least partially cure the additional coating layer.
  • external energy sources include thermal energy and radiation such as ultraviolet, infrared or microwave.
  • the optional additional coating layer may comprise one or more primer layer(s) and suitable topcoat layer(s) (e.g., base coat, clear coat layer, pigmented monocoat, and color-plus-clear composite compositions).
  • suitable additional coating layers include any of those known in the art, and each independently may be waterborne, solventborne, in solid particulate form (i.e., a powder coating composition), or in the form of a powder slurry.
  • the additional coating compositions may comprise a film forming polymer, crosslinking material and, if a colored base coat or monocoat, one or more pigments.
  • the primer layer(s) may optionally be disposed between the electrocoating layer and the topcoat layer(s).
  • the topcoat layer(s) may be omitted such that the composite comprises the electrocoating layer and one or more primer layer(s).
  • the topcoat layer(s) may be applied directly onto the electrodepositable coating layer.
  • the substrate may lack a primer layer such that the composite comprises the electrocoating layer and one or more topcoat layer(s).
  • a basecoat layer may be applied directly onto at least a portion of the
  • any of the topcoat layers may be applied onto an underlying layer despite the fact that the underlying layer has not been fully cured.
  • a clearcoat layer may be applied onto a basecoat layer even though the basecoat layer has not been subjected to a curing step (wet-on-wet). Both layers may then be cured during a subsequent curing step thereby eliminating the need to cure the basecoat layer and the clearcoat layer separately.
  • additional ingredients such as colorants and fillers may be present in the various coating compositions from which the top-coat layers result.
  • Any suitable colorants and fillers may be used.
  • the colorant may be added to the coating in any suitable form, such as discrete particles, dispersions, solutions and/or flakes.
  • a single colorant or a mixture of two or more colorants can be used in the coatings of the present invention.
  • the colorant can be present in a layer of the multi-layer composite in any amount sufficient to impart the desired property, visual and/or color effect.
  • Example colorants include pigments, dyes and tints, such as those used in the paint industry and/or listed in the Dry Color Manufacturers Association (DCMA), as well as special effect compositions.
  • a colorant may include, for example, a finely divided solid powder that is insoluble but wettable under the conditions of use.
  • a colorant may be organic or inorganic and may be agglomerated or non-agglomerated. Colorants may be incorporated into the coatings by grinding or simple mixing. Colorants may be incorporated by grinding into the coating by use of a grind vehicle, such as an acrylic grind vehicle, the use of which will be familiar to one skilled in the art.
  • Example pigments and/or pigment compositions include, but are not limited to, carbazole dioxazine crude pigment, azo, monoazo, disazo, naphthol AS, salt type (lakes), benzimidazolone, condensation, metal complex, isoindolinone, isoindoline and polycyclic phthalocyanine, quinacridone, perylene, perinone, diketopyrrolo pyrrole, thioindigo, anthraquinone, indanthrone, anthrapyrimidine, flavanthrone, pyranthrone, anthanthrone, dioxazine, triarylcarbonium, quinophthalone pigments, diketo pyrrolo pyrrole red (“DPP red BO”), titanium dioxide, carbon black, zinc oxide, antimony oxide, etc. and organic or inorganic UV opacifying pigments such as iron oxide, transparent red or yellow iron oxide, phthalocyanine blue and mixtures thereof.
  • DPP red BO
  • Example dyes include, but are not limited to, those that are solvent and/or aqueous based such as acid dyes, azoic dyes, basic dyes, direct dyes, disperse dyes, reactive dyes, solvent dyes, sulfur dyes, mordant dyes, for example, bismuth vanadate, anthraquinone, perylene, aluminum, quinacridone, thiazole, thiazine, azo, indigoid, nitro, nitroso, oxazine, phthalocyanine, quinoline, stilbene, and triphenyl methane.
  • solvent and/or aqueous based such as acid dyes, azoic dyes, basic dyes, direct dyes, disperse dyes, reactive dyes, solvent dyes, sulfur dyes, mordant dyes, for example, bismuth vanadate, anthraquinone, perylene, aluminum, quinacridone, thiazole, thiazine, azo, in
  • Example tints include, but are not limited to, pigments dispersed in water- based or water miscible carriers such as AQEiA-CHEM 896 commercially available from Degussa, Inc., CHARISMA COLORANTS and MAXITONER INDUSTRIAL
  • the colorant may be in the form of a dispersion including, but not limited to, a nanoparticle dispersion.
  • Nanoparticle dispersions can include one or more highly dispersed nanoparticle colorants and/or colorant particles that produce a desired visible color and/or opacity and/or visual effect.
  • Nanoparticle dispersions may include colorants such as pigments or dyes having a particle size of less than 150 nm, such as less than 70 nm, or less than 30 nm. Nanoparticles may be produced by milling stock organic or inorganic pigments with grinding media having a particle size of less than 0.5 mm. Example nanoparticle dispersions and methods for making them are identified in U.S. Patent No.
  • Nanoparticle dispersions may also be produced by crystallization, precipitation, gas phase condensation, and chemical attrition (i.e., partial dissolution).
  • a dispersion of resin-coated nanoparticles may be used.
  • a“dispersion of resin- coated nanoparticles” refers to a continuous phase in which is dispersed discreet“composite microparticles” that comprise a nanoparticle and a resin coating on the nanoparticle.
  • Example dispersions of resin-coated nanoparticles and methods for making them are identified in U.S. Patent Application Serial No. 10/876,031 filed June 24, 2004, which is incorporated herein by reference, and U.S. Provisional Patent Application Serial No.
  • compositions may provide other perceptible properties, such as reflectivity, opacity or texture.
  • special effect compositions may produce a color shift, such that the color of the coating changes when the coating is viewed at different angles.
  • Example color effect compositions are identified in U.S. Patent No. 6,894,086, incorporated herein by reference.
  • Additional color effect compositions may include transparent coated mica and/or synthetic mica, coated silica, coated alumina, a transparent liquid crystal pigment, a liquid crystal coating, and/or any composition wherein interference results from a refractive index differential within the material and not because of the refractive index differential between the surface of the material and the air.
  • a photosensitive composition and/or photochromic composition which reversibly alters its color when exposed to one or more light sources, can be used in a number of layers in the multi-layer composite.
  • Photochromic and/or photosensitive compositions can be activated by exposure to radiation of a specified wavelength. When the composition becomes excited, the molecular structure is changed, and the altered structure exhibits a new color that is different from the original color of the composition. When the exposure to radiation is removed, the photochromic and/or photosensitive composition can return to a state of rest, in which the original color of the composition returns.
  • the photochromic and/or photosensitive composition may be colorless in a non-excited state and exhibit a color in an excited state. Full color-change may appear within milliseconds to several minutes, such as from 20 seconds to 60 seconds.
  • Example photochromic and/or photosensitive compositions include photochromic dyes.
  • the photosensitive composition and/or photochromic composition may be associated with and/or at least partially bound to, such as by covalent bonding, a polymer and/or polymeric materials of a polymerizable component.
  • the photosensitive composition and/or photochromic composition associated with and/or at least partially bound to a polymer and/or polymerizable component in accordance with the present invention have minimal migration out of the coating.
  • the additional coating layers may be applied by a topcoat system.
  • the topcoat system may comprise any equipment and/or method known in the art to apply a topcoat coating composition.
  • the topcoat system may comprise equipment to apply a powder coating composition or a liquid coating composition.
  • the topcoat system may comprise a spray gun, a brush, a roller, a tank for immersion coating, or combinations thereof.
  • the topcoat system may optionally further comprise a spraybooth, and the spraybooth may optionally comprise a ventilation system.
  • the coating composition may be a powder coating composition.
  • powder coating composition refers to a coating composition which is completely free of water and/or solvent. Accordingly, the powder coating composition disclosed herein is not synonymous to waterborne and/or solvent-borne coating compositions known in the art.
  • the powder coating composition comprises
  • powder coating compositions that may be used in the present invention include the polyester-based ENVIROCRON line of powder coating compositions (commercially available from PPG Industries, Inc.) or epoxy-polyester hybrid powder coating compositions.
  • Alternative examples of powder coating compositions that may be used in the present invention include low temperature cure thermosetting powder coating compositions comprising (a) at least one tertiary aminourea compound, at least one tertiary aminourethane compound, or mixtures thereof, and (b) at least one film-forming epoxy-containing resin and/or at least one siloxane-containing resin (such as those described in ET.S. Patent No.
  • curable powder coating compositions generally comprising (a) at least one tertiary aminourea compound, at least one tertiary aminourethane compound, or mixtures thereof, and
  • At least one film-forming epoxy-containing resin and/or at least one siloxane-containing resin such as those described in ET.S. Patent No. 7,432,333, assigned to PPG Industries, Inc. and incorporated herein by reference
  • those comprising a solid particulate mixture of a reactive group-containing polymer having a T g of at least 30°C such as those described in ET.S. Patent No. 6,797,387, assigned to PPG Industries, Inc. and incorporated herein by reference).
  • Suitable film forming polymers that may be used in the powder coating composition of the present invention comprise a (poly)ester (e.g., polyester triglycidyl isocyanurate), a (poly)urethane, an isocyanurate, a (poly)urea, a (poly)epoxy, an anhydride, an acrylic, a (poly)ether, a (poly)sulfide, a (poly)amine, a (poly)amide, (poly)vinyl chloride, (poly)olefm, (poly)vinylidene fluoride, or combinations thereof.
  • a (poly)ester e.g., polyester triglycidyl isocyanurate
  • a (poly)urethane e.g., an isocyanurate
  • a (poly)urea epoxy
  • an anhydride an acrylic, a (poly)ether, a (poly)s
  • the reactive functional group of the film forming polymer of the powder coating composition comprises hydroxyl, carboxyl, isocyanate (including blocked (poly)isocyanate), primary amine, secondary amine, amide, carbamate, urea, urethane, vinyl, unsaturated ester, maleimide, fumarate, anhydride, hydroxyl alkylamide, epoxy, or combinations thereof.
  • the coating is often heated to cure the deposited composition.
  • the heating or curing operation is often carried out at a temperature in the range of from l50°C to 200°C, such as from l70°C to l90°C, for a period of time ranging from 10 to 20 minutes.
  • the thickness of the resultant film is from 50 microns to 125 microns.
  • the coating composition may be a liquid coating composition.
  • liquid coating composition refers to a coating composition which contains a portion of water and/or solvent. Accordingly, the liquid coating
  • composition disclosed herein is synonymous to waterborne and/or solvent-borne coating compositions known in the art.
  • the liquid coating composition may comprise, for example, (a) a film forming polymer having a reactive functional group; and (b) a curing agent that is reactive with the functional group.
  • the liquid coating may contain a film forming polymer that may react with oxygen in the air or coalesce into a film with the evaporation of water and/or solvents. These film-forming mechanisms may require or be accelerated by the application of heat or some type of radiation such as
  • liquid coating compositions that may be used in the present invention include the SPECTRACRON® line of solvent-based coating compositions, the AQUACRON® line of water-based coating compositions, and the RAYCRON® line of UV cured coatings (all commercially available from PPG Industries, Inc.).
  • Suitable film forming polymers may comprise a (poly)ester, an alkyd, a (poly)urethane, an isocyanurate, a (poly)urea, a (poly)epoxy, an anhydride, an acrylic, a (poly)ether, a (poly)sulfide, a (poly)amine, a (poly)amide, (poly)vinyl chloride, (poly)olefm, (poly)vinylidene fluoride, (poly)siloxane, or combinations thereof.
  • the reactive functional group of the film forming polymer of the liquid coating composition may comprise hydroxyl, carboxyl, isocyanate (including blocked (poly)isocyanate), primary amine, secondary amine, amide, carbamate, urea, urethane, vinyl, unsaturated ester, maleimide, fumarate, anhydride, hydroxyl alkylamide, epoxy, or combinations thereof.
  • Suitable curing agents that may be used in the liquid coating composition of the present invention may comprise an aminoplast resin, a
  • polyisocyanate a blocked polyisocyanate, a polyepoxide, a polyacid, a polyol, or
  • a colorant and, if desired, various additives such as surfactants, wetting agents or catalyst can be included in the coating composition (electrodepositable, powder, or liquid).
  • the term“colorant” means any substance that imparts color and/or other opacity and/or other visual effect to the composition.
  • the colorant can be added to the composition in any suitable form, such as discrete particles, dispersions, solutions and/or flakes. A single colorant or a mixture of two or more colorants can be used.
  • Example colorants include pigments, dyes and tints, such as those used in the paint industry and/or listed in the Dry Color Manufacturers Association (DCMA), as well as special effect compositions.
  • a colorant may include, for example, a finely divided solid powder that is insoluble but wettable under the conditions of use.
  • a colorant can be organic or inorganic and can be agglomerated or non-agglomerated. Colorants can be incorporated by use of a grind vehicle, such as an acrylic grind vehicle, the use of which will be familiar to one skilled in the art.
  • Example pigments and/or pigment compositions include, but are not limited to, carbazole dioxazine crude pigment, azo, monoazo, disazo, naphthol AS, salt type (lakes), benzimidazolone, condensation, metal complex, isoindolinone, isoindoline and polycyclic phthalocyanine, quinacridone, perylene, perinone, diketopyrrolo pyrrole, thioindigo, anthraquinone, indanthrone, anthrapyrimidine, flavanthrone, pyranthrone, anthanthrone, dioxazine, triarylcarbonium, quinophthalone pigments, diketo pyrrolo pyrrole red (“DPPBO red”), titanium dioxide, carbon black and mixtures thereof.
  • DPPBO red diketo pyrrolo pyrrole red
  • Example dyes include, but are not limited to, those that are solvent and/or aqueous based such as phthalo green or blue, iron oxide, bismuth vanadate, anthraquinone, perylene, aluminum and quinacridone.
  • Example tints include, but are not limited to, pigments dispersed in water- based or water miscible carriers such as AQUA-CHEM 896 commercially available from Degussa, Inc., CHARISMA COLORANTS and MAXITONER INDUSTRIAL
  • the colorant can be in the form of a dispersion including, but not limited to, a nanoparticle dispersion.
  • Nanoparticle dispersions can include one or more highly dispersed nanoparticle colorants and/or colorant particles that produce a desired visible color and/or opacity and/or visual effect.
  • Nanoparticle dispersions can include colorants such as pigments or dyes having a particle size of less than 150 nm, such as less than 70 nm, or less than 30 nm. Nanoparticles can be produced by milling stock organic or inorganic pigments with grinding media having a particle size of less than 0.5 mm. Example nanoparticle dispersions and methods for making them are identified in U.S. Patent No.
  • Nanoparticle dispersions can also be produced by crystallization, precipitation, gas phase condensation, and chemical attrition (i.e., partial dissolution).
  • a dispersion of resin-coated nanoparticles can be used.
  • a“dispersion of resin-coated nanoparticles” refers to a continuous phase in which is dispersed discreet “composite microparticles” that comprise a nanoparticle and a resin coating on the nanoparticle.
  • Example dispersions of resin-coated nanoparticles and methods for making them are identified in U.S. Patent Application Publication No. 2005-0287348 Al, filed June 24, 2004, U.S. Provisional Patent Application Serial No. 60/482,167 filed June 24,
  • Example special effect compositions that may be used include pigments and/or compositions that produce one or more appearance effects such as reflectance, pearlescence, metallic sheen, phosphorescence, fluorescence, photochromism, photosensitivity,
  • thermochromism goniochromism and/or color-change. Additional special effect
  • compositions can provide other perceptible properties, such as opacity or texture. According to the invention, special effect compositions can produce a color shift, such that the color of the coating changes when the coating is viewed at different angles.
  • Example color effect compositions are identified in U.S. Patent No. 6,894,086, incorporated herein by reference. Additional color effect compositions can include transparent coated mica and/or synthetic mica, coated silica, coated alumina, a transparent liquid crystal pigment, a liquid crystal coating, and/or any composition wherein interference results from a refractive index differential within the material and not because of the refractive index differential between the surface of the material and the air.
  • a photosensitive composition and/or photochromic composition which reversibly alters its color when exposed to one or more light sources.
  • Photochromic and/or photosensitive compositions can be activated by exposure to radiation of a specified wavelength. When the composition becomes excited, the molecular structure is changed, and the altered structure exhibits a new color that is different from the original color of the composition. When the exposure to radiation is removed, the photochromic and/or photosensitive composition can return to a state of rest, in which the original color of the composition returns.
  • the photochromic and/or photosensitive composition can be colorless in a non-excited state and exhibit a color in an excited state. Full color-change can appear within milliseconds to several minutes, such as from 20 seconds to 60 seconds.
  • Example photochromic and/or photosensitive composition can be colorless in a non-excited state and exhibit a color in an excited state. Full color-change can appear within milliseconds to several minutes, such as from 20 seconds to 60 seconds.
  • compositions include photochromic dyes.
  • the photosensitive composition and/or
  • photochromic composition can be associated with and/or at least partially bound to, such as by covalent bonding, a polymer and/or polymeric materials of a polymerizable component.
  • the photosensitive composition may migrate out of the coating and crystallize into the substrate, the photosensitive composition and/or
  • photochromic composition associated with and/or at least partially bound to a polymer and/or polymerizable component in according to the invention have minimal migration out of the coating.
  • Example photosensitive compositions and/or photochromic compositions and methods for making them are identified in ET.S. Patent Application Serial No. 10/892,919, filed July 16, 2004, incorporated herein by reference.
  • the colorant can be present in the coating composition in any amount sufficient to impart the desired visual and/or color effect.
  • the colorant may comprise from 1 to 65 weight percent, such as from 3 to 40 weight percent or 5 to 35 weight percent, with weight percent based on the total weight of the composition.
  • the method may optionally further comprise pretreating the substrate with a pretreatment composition prior to applying the electrodepositable coating composition using the electrocoating system.
  • a pretreatment composition refers to a composition that is capable of reacting with and chemically altering the substrate surface and binding to it to form a film that affords corrosion protection.
  • Non-limiting examples of a pretreatment composition include zinc phosphate pretreatment compositions such as, for example, those described in U.S. Patent Nos. 4,793,867 and 5,588,989, zirconium containing pretreatment compositions such as, for example, those described in U.S. Patent Nos. 7,749,368 and 8,673,091, and the like.
  • the pretreatment composition may be brought into contact with the substrate by any of a variety of known techniques, such as dipping or immersion, spraying, intermittent spraying, dipping followed by spraying, spraying followed by dipping, brushing, or roll-coating.
  • the pretreatment composition when applied to the substrate may be at a temperature ranging from, for example, 40°F to l60°F (4.4°C to 7l.l°C), such as 60°F to 1 lO°F (l5.6°C to 43.3°C), such as 70°F to 90°F (2l. l°C to 32.2°C).
  • the pretreatment process may be carried out at ambient or room temperature.
  • the contact time is often from 1 second to 15 minutes, such as 4 minutes to 10 minutes, such as 5 seconds to 4 minutes.
  • the substrate optionally may be dried in place, e.g., air dried at room temperature or be dried with hot air, for example, by using an air knife, by flashing off the water by brief exposure of the substrate to a high temperature, such as by drying the substrate in an oven at l5°C to l00°C, such as 20°C to 90°C, or in a heater assembly using, for example, infrared heat, such as for 10 minutes at 70°C, or by passing the substrate between squeegee rolls.
  • the substrate surface may be partially, or in some instances, completely dried prior to any subsequent contact of the substrate surface with any water, solutions, compositions, or the like.
  • the substrate optionally may be rinsed with tap water, deionized water, and/or an aqueous solution of rinsing agents in order to remove any residue and then optionally may be dried, for example air dried or dried with hot air as described in the preceding sentence.
  • such water rinses may be eliminated and the substrate (either wet or dried in place) may be contacted with subsequent treatment compositions.
  • the pretreatment composition may be applied to the substrate by a pretreatment system.
  • the pretreatment system may comprise tanks for immersion, brushes, rollers, spray guns, or combinations thereof to apply the pretreatment composition to the substrate.
  • the pretreatment system may further comprise tanks, brushes, rollers, spray guns, or combinations thereof for applying rinse compositions, such as water, to the substrate.
  • the method may optionally further comprise priming the substrate with a priming composition prior to applying the
  • the priming composition may be used alone or in combination with the pretreatment composition or other treatments prior to applying the electrodepositable coating composition.
  • the priming composition may comprise a metal-rich coating composition.
  • metal-rich coating composition refers to film-forming compositions that include an organic or inorganic binder and at least 65% by weight metal particles, based on the total solids weight of the coating composition.
  • metal particles refers to elemental (i.e., zerovalent) metal and metal alloy particles.
  • the term “particles” refers to material in the form of particulates, such as powder or dust, as well as flakes, and may be in the form of any shape, such as, for example, spherical, ellipsoidal, cubical, rod-shaped, disk-shaped, prism-shaped, and the like.
  • the metal may comprise zinc, aluminum, or alloys thereof.
  • the priming composition may be brought into contact with the substrate by any of a variety of known techniques, such as dipping or immersion, spraying, electrostatic spraying, intermittent spraying, dipping followed by spraying, spraying followed by dipping, brushing, or roll-coating. It is appreciated that the metal-rich primer coatings can also be applied in dry forms such as powder or films.
  • the metal-rich primer coatings formed from the priming composition can be applied to a dry film thickness of, for example, 2.5 to 500 microns.
  • a film formed on the surface of the substrate may be dried by driving solvent out of the film by heating or by an air-drying period. Suitable drying conditions will depend on the particular priming composition and/or application, but an exemplary drying time of from about 1 to 5 minutes at a temperature of about 60 to 250°F (15.6 to l2l°C), such as 70 to 2l2°F (27 to l00°C) may be sufficient. More than one primer coating layer may be applied if desired. Between coats, the previously applied coat may be flashed; that is, exposed to ambient conditions for a desired amount of time.
  • the applied priming composition may be cured by any means known in the art.
  • the coating may be subjected to curing conditions sufficient to cure the priming composition.
  • the coating composition may be subjected to curing conditions such as ambient conditions, as discussed above, for a period of hours or days.
  • the substrate may be subjected to curing conditions such as radiation (e.g., UV radiation) or heated to a temperature and for a time sufficient to cure the priming coating.
  • the priming composition may be applied to the substrate by a priming system.
  • the priming system may comprise tanks for immersion, brushes, rollers, spray guns, or combinations thereof to apply the priming composition to the substrate.
  • the priming system may further comprise tanks, brushes, rollers, spray guns, or combinations thereof for applying rinse compositions, such as water, to the substrate.
  • the substrate may optionally be subjected to other treatments prior to electrocoating.
  • the substrate may be rinsed, cleaned, deoxidized, cleaned and deoxidized, anodized, acid pickled, plasma treated, laser treated, or ion vapor deposition (IVD) treated.
  • IVD ion vapor deposition
  • At least a portion of the surface of the substrate may be cleaned by physical and/or chemical means, such as mechanically abrading the surface and/or cleaning/degreasing the surface with commercially available alkaline or acidic cleaning agents that are well known to those skilled in the art.
  • These optional treatments may be used on their own or in combination with a pretreatment composition and/or a priming
  • the present invention is also directed towards a substrate coated using the electrocoating system described above.
  • the substrate may optionally be coated using the topcoat system.
  • the substrate comprises an electrocoating layer and an optional topcoat layer.
  • the present invention is also directed towards a substrate coated using the pretreatment system and electrocoating system, both as described above.
  • the substrate may optionally be coated using the topcoat system.
  • the substrate comprises a pretreatment layer, an electrocoating layer and an optional topcoat layer.
  • the present invention is also directed towards a substrate coated using the priming system and electrocoating system, both as described above.
  • the substrate may optionally be coated using the topcoat system.
  • the substrate comprises a priming layer, an electrocoating layer and an optional topcoat layer.
  • the present invention is also directed towards a substrate coated using the pretreatment system, priming system and electrocoating system, each as described above.
  • the substrate may optionally be coated using the topcoat system. Accordingly, the substrate comprises a pretreatment layer, a priming layer, an electrocoating layer and an optional topcoat layer.
  • the present invention is also directed towards a substrate coated according to the method of the present invention.
  • the present invention is also directed towards a system for coating a substrate comprising the electrocoating system as described above.
  • the system for coating a substrate may optionally further comprise the pretreatment system, the priming system, the topcoat system, or any combination thereof.
  • the system for coating a substrate may comprise the pretreatment system for pretreating the substrate; the priming system for priming the substrate; the electrocoating system for electrocoating the substrate; and the topcoat system for applying a topcoat coating to the substrate.
  • the system for coating a substrate may comprise any combination of the systems discussed above applied sequentially.
  • the system for coating a substrate may comprise the pretreatment system followed by the electrocoat system; the system for coating a substrate may comprise the pretreatment system followed by the electrocoat system followed by the topcoat system; the system for coating a substrate may comprise the priming system followed by the electrocoat system; the system for coating a substrate may comprise the priming system followed by the electrocoat system followed by the topcoat system; the system for coating a substrate may comprise the pretreatment system followed by the priming system followed by the electrocoat system; the system for coating a substrate may comprise the pretreatment system followed by the priming system followed by the electrocoat system followed by the topcoat system; or the system for coating a substrate may comprise the electrocoat system followed by the topcoat system.
  • the terms“on,”“onto,”“applied on,”“applied onto,”“formed on,”“deposited on,”“deposited onto,” mean formed, overlaid, deposited, or provided on but not necessarily in contact with the surface.
  • an electrodepositable coating composition“deposited onto” a substrate does not preclude the presence of one or more other intervening coating layers of the same or different composition located between the electrodepositable coating composition and the substrate.
  • the present invention thus relates inter alia, without being limited thereto, to the following aspects:
  • An electrocoating system for electrocoating a substrate comprising a tank configured to hold an electrodepositable coating composition; at least one pump in fluid communication with the tank, at least one return conduit connecting the tank with an inlet of the pump, at least one recirculating pipe comprising a first end in fluid communication with an outlet of the pump and a second end having at least one aperture, and the at least one recirculating pipe comprising at least one external electrode positioned at least partially outside of the tank, wherein:
  • the substrate has a first surface and a second surface
  • the pump is configured to receive the electrodepositable coating composition from the return conduit and deliver the electrodepositable coating composition into the tank through the recirculating pipe;
  • the external electrode is configured to provide an electric charge to the
  • the recirculating pipe is configured to extend into the interior of the tank and position the aperture of the second end to deliver at least a portion of the electrically charged electrodepositable coating composition to the first surface of the substrate.
  • the second end of the recirculating pipe comprises at least one nozzle comprising the aperture.
  • the second end of the recirculating pipe is branched and comprises at least two apertures configured to deliver at least a portion of the electrodepositable coating composition charged by the external electrode to different surface sections of the first surface of the substrate.
  • the recirculating pipe comprises a plurality of apertures configured to deliver the electrodepositable coating composition charged by the external electrode to different sections of the first surface of the substrate.
  • electrocoating system according to any one of Aspects 1-5, wherein the electrocoating system comprises a plurality of recirculating pipes configured to deliver the electrodepositable coating composition charged by the external electrode to different sections of the first surface of the substrate.
  • aspects further comprising at least one power source to provide an electrical current to the electrocoating system.
  • tank, the return conduit, the pump and the recirculating pipe are directly coupled to form at least one continuous and uninterrupted loop configured for constrained flow of the electrodepositable coating composition through the return conduit, pump and recirculating pipe.
  • the tank comprises a base portion and at least one side wall extending up from the base portion.
  • the substrate comprises an open-polygon cross-sectional shape.
  • the substrate comprises a rectangular cross-sectional shape.
  • the substrate is a container.
  • the substrate has a cross-sectional area of at least 40 m 2 .
  • a method for coating a substrate comprising electrophoretically applying a coating deposited from an electrodepositable coating composition to at least a portion of the substrate using the electrocoating system according to any one of preceding Aspects 1 to 18.
  • the electrodepositable coating composition comprises a cationic film-forming resin comprising sulphonium groups.
  • a system for coating a substrate comprising the electrocoating system according to any one of Aspects 1 to 22, and further comprising at least one of:
  • a pretreatment system for pretreating the substrate prior to processing the substrate in the electrocoating system
  • a priming system for priming the substrate prior to processing the substrate in the electrocoating system
  • a topcoat system for applying a topcoat coating to the substrate after processing the substrate in the electrocoating system.
  • an intermodal shipping container is coated using the system and method of the present invention.
  • the intermodal shipping container has four enclosed sides (the top or roof of the container, two side walls, and an enclosed end), an opening at the opposing end which is covered by doors (which will be open during the electrodeposition process), and a floor which has rows of structural support members crossing over from the long sides of the container and is not enclosed.
  • the structural supports are the members which are utilized to attach and support the floor of the finished container (the floor is installed after painting).
  • the open-pocket shape of the container makes it difficult to fully coat the inside surfaces of the container during an electrodeposition process using standard technology, i.e., electrodes positioned along the inside walls of the tank. For the electrophoresis process to work effectively (coat the entire inside surface of the container), an electrical potential must be applied at a rate and voltage potential adequate to initiate and maintain the electrodeposition process.
  • the container To apply a coating deposited from the electrodepositable coating composition to all the surfaces of the container, the container must be fully immersed into an electrocoat bath large enough to fully immerse the container.
  • the electrocoat bath may exceed 80,000 gallons of electrodepositable coating composition.
  • the container may be lifted by the four exterior, top corners by a lifting device (e.g., a hoist or crane) and positioned above the electrocoat bath. Once in the proper horizontal position, it will be lowered into the electrocoat bath with care and manipulated in the tank during the immersion process to minimize the air bubbles that may form in the container. It is anticipated that the electrodepositable coating composition may be maintained at a temperature between 80°F and 95°F.
  • Cooling may be required as the electrodeposition process should generate heat.
  • anodes with membranes may be present in the bath to remove acid which is also released during the electrocoat deposition process. A proper ratio of bare anode surface area and membrane area will need to be maintained to provide proper pH control of the bath. The interior surface, and exposed external surface area of the external electrode (if the external electrode is an anode) will need to be included in this calculation.
  • the external electrode will be electrically charged in the same manner as a standard electrode in electrodeposition processes with the container electrically coupled to the other pole and serve as a counter-electrode.
  • the applied DC voltage may vary from 100V to 450V. Amperage will be dependent on coating application rate, immersion time, coulombic efficiency of the specified electrodepositable coating composition, application parameters, and applied thickness.
  • anodes of 316SS may have an effective electrical capacity of approximately 5 amps per ft 2 of exposed anode area.
  • use of the external anode may effectively double the effective surface area of each anode.
  • the fully charged electrodepositable coating composition that flows through the external anode and recirculating pipe may carry or drive the electrical energy to the cathode (i.e., the container) at greater distances than a static anode wherein the electrodepositable coating composition simply contacts the surface of the anode. This allows for the electrodepositable coating composition to coat the inside of the container where it is difficult to get adequate throwpower because of the limitations of standard electrocoat systems.

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  • Cooling, Air Intake And Gas Exhaust, And Fuel Tank Arrangements In Propulsion Units (AREA)

Abstract

La présente invention concerne un système d'électrodéposition pour revêtir par électrodéposition un substrat (500), le système comprenant un réservoir (100) configuré pour contenir une composition de revêtement apte à être déposée par électrodéposition ; au moins une pompe (200) en communication fluidique avec le réservoir, au moins un conduit de retour (210) raccordant le réservoir à une entrée de la pompe, au moins un tuyau de recirculation (300) comprenant une première extrémité en communication fluidique avec une sortie de la pompe et une seconde extrémité ayant au moins une ouverture, et le(s) tuyau(x) de recirculation comprenant au moins une électrode externe (400) positionnée au moins partiellement à l'extérieur du réservoir. L'invention concerne en outre des procédés de revêtement de substrats, des systèmes de revêtement d'un substrat, et des substrats revêtus.
PCT/US2019/056107 2018-10-15 2019-10-14 Système d'électrodéposition de substrats conducteurs WO2020081447A1 (fr)

Priority Applications (6)

Application Number Priority Date Filing Date Title
BR112021007150-4A BR112021007150A2 (pt) 2018-10-15 2019-10-14 sistema para eletrorevestir substratos condutivos
MX2021004316A MX2021004316A (es) 2018-10-15 2019-10-14 Sistema para electrorrecubrir sustratos conductores.
EP19797493.4A EP3867424A1 (fr) 2018-10-15 2019-10-14 Système d'électrodéposition de substrats conducteurs
US17/285,640 US20210388525A1 (en) 2018-10-15 2019-10-14 System for Electrocoating Conductive Substrates
KR1020217013624A KR20210072056A (ko) 2018-10-15 2019-10-14 전도성 기판 전기코팅 시스템
CN201980067955.XA CN113260741A (zh) 2018-10-15 2019-10-14 用于对导电基材进行电涂覆的系统

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US201862745494P 2018-10-15 2018-10-15
US62/745,494 2018-10-15

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EP (1) EP3867424A1 (fr)
KR (1) KR20210072056A (fr)
CN (1) CN113260741A (fr)
BR (1) BR112021007150A2 (fr)
MX (1) MX2021004316A (fr)
WO (1) WO2020081447A1 (fr)

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MX2021004316A (es) 2021-05-27
CN113260741A (zh) 2021-08-13
US20210388525A1 (en) 2021-12-16
EP3867424A1 (fr) 2021-08-25
BR112021007150A2 (pt) 2021-07-20

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