WO2008054353A2 - Compositions de revêtement pouvant être électrodéposées, et procédés apparentés - Google Patents

Compositions de revêtement pouvant être électrodéposées, et procédés apparentés Download PDF

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Publication number
WO2008054353A2
WO2008054353A2 PCT/US2006/031133 US2006031133W WO2008054353A2 WO 2008054353 A2 WO2008054353 A2 WO 2008054353A2 US 2006031133 W US2006031133 W US 2006031133W WO 2008054353 A2 WO2008054353 A2 WO 2008054353A2
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Prior art keywords
coating composition
catalyst nanoparticles
electrodepositable coating
composition according
resin
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PCT/US2006/031133
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English (en)
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WO2008054353A3 (fr
WO2008054353A9 (fr
Inventor
Cheng-Hung Hung
Alan J. Kaylo
Gregory J. Mccollum
Noel R. Vanier
Michael White
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Ppg Industries Ohio, Inc.
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Priority to EP06851821A priority Critical patent/EP1948743A2/fr
Publication of WO2008054353A2 publication Critical patent/WO2008054353A2/fr
Publication of WO2008054353A3 publication Critical patent/WO2008054353A3/fr
Publication of WO2008054353A9 publication Critical patent/WO2008054353A9/fr

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    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D5/00—Coating compositions, e.g. paints, varnishes or lacquers, characterised by their physical nature or the effects produced; Filling pastes
    • C09D5/44—Coating compositions, e.g. paints, varnishes or lacquers, characterised by their physical nature or the effects produced; Filling pastes for electrophoretic applications
    • C09D5/4488—Cathodic paints
    • C09D5/4496—Cathodic paints characterised by the nature of the curing agents

Definitions

  • the present invention relates to cationic electrodepositable coating compositions comprising a resinous phase and certain catalyst nanoparticles dispersed in an aqueous medium, wherein the catalyst nanoparticles have a specified B.E.T. specific surface area to methods of preparing such compositions; and to methods for applying such compositions.
  • Electrodeposition has gained prominence in the coating industry because, in comparison with non-electrophoretic coating methods, electrodeposition provides higher paint utilization, excellent corrosion resistance and low environmental contamination.
  • Electrodeposition processes used anionic electrodeposition where the workpiece to be coated serves as the anode.
  • cationic electrodeposition has become increasingly popular and today is the most prevalent method of electrodeposition.
  • cationic electrodeposition compositions in use today are based on active hydrogen-containing resins derived from a polyepoxide and a capped or blocked polyisocyanate curing agent. Typically, these cationic electrodeposition compositions also contain organotin catalysts to lower the temperature at which the blocking agent is released from blocked polyisocyanate and to activate cure of the electrodeposition composition.
  • organotin catalysts to lower the temperature at which the blocking agent is released from blocked polyisocyanate and to activate cure of the electrodeposition composition.
  • Most of the common dialkyltin oxide catalysts are high melting, amorphous solid materials which must be introduced into the composition in the form of a catalyst paste prepared by dispersing the solid catalyst into a pigment wetting resin under extremely high shear conditions. Preparation of stable catalyst pastes can be very costly and time intensive.
  • organotin catalysts can cause a multitude of surface defects in the cured electrodeposited coating composition.
  • dibutyltin oxide dispersions can flocculate in the electrodeposition bath, resulting in oversized dibutyltin oxide agglomerates or particles which can settle in areas of the electrodeposition tank where agitation is poor.
  • This flocculation phenomenon constitutes a loss of catalyst from the coating composition resulting in poor cure response.
  • the flocculate particles can settle in the uncured electrodeposited coating causing localized "hot spots" or pinholes in the surface of the cured coating.
  • electrodeposition bath stability can be adversely affected with the use of some organotin catalysts.
  • Triorganotin compounds are known for use as catalysts in electrodepositable coating compositions comprised of an active hydrogen- containing resin and a blocked polyisocyanate curing agent. Such triorganotin compounds, however, have been observed to have poor cure response when used in conjunction with resinous components having phenolic hydroxyl groups. Moreover, some trialkyltin compounds, for example, tributyltin compounds, are known to be volatile at typical curing temperatures. Also, some trialkyltin compounds can be toxic. Further, many triorganotin compounds typically have the disadvantage of high cost.
  • the present invention provides electrodepositable coating compositions comprising a resinous phase and catalyst nanoparticles dispersed in an aqueous medium, the resinous phase comprising: (a) a active hydrogen-containing, ionic salt group-containing resin; and (b) at least one curing agent; and catalyst nanoparticles for effecting cure between the resin (a) a curing agent (b), the catalyst nanoparticles being selected from the group consisting of bismuth oxide; bismuth silicate; bismuth titanate; molybdenum oxide; molybdenum silicate; molybdenum titanate; tungsten oxide; tungsten silicate; tungsten titanate; a combination of cerium - oxide, zinc oxide and silicon dioxide; a combination of cerium oxide and silicon dioxide; and combinations thereof, 1 wherein the catalyst nanoparticles have an average B. ET. specific surface area greater than 20 square meters per gram (m 2 /g).
  • the present invention provides methods for electrocoating a conductive substrate serving as a cathode in an electrical circuit comprising the cathode and an anode, the cathode and anode being immersed in an aqueous electrocoating composition, the methods comprising passing electric current between the cathode and anode to cause deposition of the electrocoating composition onto the substrate as a substantially continuous film, the aqueous electrocoating composition comprising a resinous phase dispersed in an aqueous medium, the resinous phase comprising: (a) a active hydrogen group-containing, ionic group- containing electrodepositable resin; and (b) a curing agent, and catalyst nanoparticles for effecting cure between the resin (a) and the curing agent (b), the catalyst nanoparticles being selected from the group consisting of bismuth oxide; bismuth silicate; bismuth titanate; molybdenum oxide; molybdenum silicate; molybdenum titanate; tungsten
  • Fig. 1 is a flow diagram of certain embodiments of suitable methods for making catalyst nanoparticles in accordance with the present invention
  • FIG. 2 is a schematic diagram of an apparatus for producing catalyst nanoparticles in accordance with certain embodiments of the present invention
  • FIG. 3 is a perspective view of a plurality of quench gas injection ports in accordance with certain embodiments of the present invention.
  • Fig. 4 is a micrograph of a TEM image of a representative portion of the nanoparticles of Example 1 (10,000x magnification); and [0014] Fig. 5 is a micrograph of a TEM image of a representative portion of the nanoparticles of Example 2 (210,00Ox magnification).
  • any numerical range recited herein is intended to include all sub-ranges subsumed therein.
  • a range of "1 to 10" is intended to include all sub-ranges between and including the recited minimum value of 1 and the recited maximum value of 10, that is, having a minimum value equal to or greater than 1 and a maximum value of equal to or less than 10.
  • the present invention provides electrodepositable coating compositions comprising a resinous phase and catalyst nanoparticles dispersed in an aqueous medium, the resinous phase comprising: (a) at least one active hydrogen-containing, ionic salt group-containing resin; (b) at least one curing agent.
  • the catalyst nanoparticles effect or facilitate cure between the resin (a) and the curing agent (b), as described in detail below.
  • the catalyst nanoparticles are selected from the group consisting of bismuth oxide; bismuth silicate; bismuth titanate; molybdenum oxide; molybdenum silicate; molybdenum titanate; tungsten oxide; tungsten silicate; tungsten titanate; a combination of cerium oxide, zinc oxide and silicon dioxide; a combination of cerium oxide and silicon dioxide; and combinations thereof, such as composite particles of two or more of these compounds or combinations.
  • the catalyst nanoparticles comprise bismuth oxide. In other embodiments, the catalyst particles comprise bismuth oxide and silica. In other embodiments, the catalyst particles comprise bismuth oxide and bismuth silicate. In other embodiments, the catalyst particles comprise bismuth oxide, bismuth silicate and silica. [0021] In some embodiments, the catalyst nanoparticles may be a complex metal oxide comprising a homogeneous mixture, or solid state solution of two or more (up to x) metal oxides, labeled MO1, MO 2 , . . . . MO x , [0022] The catalyst nanoparticles have an average B. ET.
  • the BET specific surface area can be measured by any method well known to those skilled in the art, such as by nitrogen absorption according to ASTM D 3663-78 standard based upon the Brunauer, Emmett, and Teller method described in J. Am. Chem. Soc'y 60, 309 (1938).
  • the BET specific surface area can be measured using a Gemini Model 2360 surface area analyzer (available from Micromeritics Instrument Corp. of Norcross, Georgia).
  • the catalyst nanoparticles have a calculated equivalent spherical diameter of less than 500 nanometers, in other embodiments less than 100 nanometers and in still other embodiments less than 50 nanometers.
  • a calculated equivalent spherical diameter can be determined from the B. ET. specific surface area according to the following equation:
  • the catalyst nanoparticles can have an average primary particle size of less than 500 nanometers. In some embodiments, the catalyst nanoparticles can have an average primary particle size of less than 100 nanometers, and in other embodiments less than 50 nanometers. In some embodiments, the catalyst nanoparticles have an average primary particle size of less than 30 nanometers and in other embodiments less than 20 nanometers. The particles typically have an average primary particle size greater than 1 nm.
  • the average primary particle size can be determined by visually examining an electron micrograph of a transmission electron microscopy ("TEM") image, measuring the diameter of the particles in the image, and calculating the average particle size ("APS") based on the magnification of the TEM image.
  • TEM transmission electron microscopy
  • APS average particle size
  • the primary particle size of a particle refers to the smallest diameter sphere that will completely enclose the particle.
  • the phrase "primary particle size" refers to the size of an individual particle as opposed to an agglomeration of two or more individual particles.
  • compositions in accordance with the present invention can be incorporated into the compositions in accordance with the present invention to impart the desired properties and characteristics to the compositions.
  • particles of varying particle sizes can be used in the compositions according to the present invention.
  • the catalyst nanoparticles can be present in the coating composition in an amount sufficient to effect cure of the coating composition at or below a temperature of 360 0 F (182.2°C). In some embodiments, catalyst nanoparticles are present in the coating composition in an amount sufficient to effect cure of the coating composition at or below a temperature of 340°F (171.1 0 C). In other embodiments, catalyst nanoparticles are present in the coating composition in an amount sufficient to effect cure of the coating composition at or below a temperature of 320 0 F (160 0 C). In other embodiments, catalyst nanoparticles are present in the coating composition in an amount sufficient to effect cure of the coating composition at or below a temperature of 300 0 F (149°C).
  • the cure temperature can vary based upon the amount and type of catalyst nanoparticles used.
  • the particles When the film-forming composition of the present invention is in a liquid medium, the particles have an affinity for the medium of the composition sufficient to keep the particles suspended therein.
  • the affinity of the particles for the medium is greater than the affinity of the particles for each other, thereby preventing agglomeration of the particles within the medium. This property is due to the nature of the particles themselves.
  • the particles are also substantially free of any surface treatment.
  • the particles used in the composition of the present invention may be added to the composition neat during the formulation thereof, and may be added at high loadings without appreciable viscosity increases, allowing for formulation of high solids coating compositions.
  • the shape (or morphology) of the particles can vary depending upon the specific embodiment of the present invention and its intended application. For example, generally spherical morphologies can be used, as well as particles that are cubic, platy, or acicular (elongated or fibrous). In general, the particles are substantially spherical in shape.
  • the catalyst nanoparticles may be prepared by various methods, including gas phase synthesis processes, such as, for example, flame pyrolysis, hot walled reactor, chemical vapor synthesis, among other methods. In certain embodiments, however, such particles are prepared by reacting together one or more organometallic and/or metal oxide precursors and any other ingredients in a fast quench plasma system.
  • the particles may be formed in such a system by: (a) introducing materials into a plasma chamber; (b) rapidly heating the materials by means of a plasma to a selection temperature sufficient to yield a gaseous product stream; (c) passing the gaseous product stream through a restrictive convergent-divergent nozzle to effect rapid cooling and/or utilizing an alternative cooling method, such as a cool surface or quenching stream, and (d) condensing the gaseous product stream to yield ultrafine solid particles.
  • an alternative cooling method such as a cool surface or quenching stream
  • Materials suitable for use in the quench streams include, but are not limited to, hydrogen gas, carbon dioxide, air, water vapor, ammonia, mono, di and polybasic alcohols, silicon-containing materials (such as hexamethyldisilazane), carboxylic acids and/or hydrocarbons.
  • the particular flow rates and injection angles of the various quench streams are not limited, so long as they impinge with each other within the gaseous product stream to result in the rapid cooling of the gaseous product stream to produce catalyst nanoparticles.
  • the quench streams primarily cool the gaseous product stream through dilution, rather than adiabatic expansion, thereby causing a rapid quenching of the gaseous product stream and the formation of ultrafine solid particles prior to passing the particles into and through a converging member, such as a converging-diverging nozzle, as described below.
  • a converging member such as a converging-diverging nozzle, as described below.
  • the particles are, at step 500, passed through a converging member, wherein the plasma system is designed to minimize the fouling thereof.
  • the converging member comprises a converging- diverging (De Laval) nozzle.
  • the gas may be inert, such as argon, helium, or neon, reductive, such as hydrogen, methane, ammonia, and carbon monoxide, or oxidative, such as oxygen, nitrogen, and carbon dioxide.
  • reductive such as hydrogen, methane, ammonia, and carbon monoxide
  • oxidative such as oxygen, nitrogen, and carbon dioxide.
  • Air, oxygen, and/or oxygen/argon gas mixtures are often used to produce ultrafine solid particles in accordance with the present invention.
  • the plasma gas feed inlet is depicted at 31.
  • Fig. 3 there is depicted a perspective view of a plurality of quench gas injection ports 40 in accordance with certain embodiments of the present invention.
  • six (6) quench gas injection ports are depicted, wherein each port disposed at an angle " ⁇ " apart from each other along the circumference of the reactor chamber 20.
  • " ⁇ " may have the same or a different value from port to port.
  • at least four (4) quench gas injection ports 40 are provided, in some cases at least six (6) quench gas injection ports are present.
  • each angle " ⁇ " has a value of no more than 90°.
  • the plasma chamber walls may be internally heated by a combination of radiation, convection and conduction.
  • cooling of the plasma chamber walls prevents unwanted melting and/or corrosion at their surfaces.
  • the system used to control such cooling should maintain the walls at as high a temperature as can be permitted by the selected wall material, which often is inert to the materials within the plasma chamber at the expected wall temperatures. This is true also with regard to the nozzle walls, which may be subjected to heat by convection and conduction.
  • the converging section of the nozzle has a high aspect ratio change in diameter that maintains smooth transitions to a first steep angle (such as > 45°) and then to lesser angles (such as ⁇ 45°degree.) leading into the nozzle throat.
  • the purpose of the nozzle throat is often to compress the gases and achieve sonic velocities in the flow.
  • the velocities achieved in the nozzle throat and in the downstream diverging section of the nozzle are controlled by the pressure differential between the plasma chamber and the section downstream of the diverging section of the nozzle. Negative pressure can be applied downstream or positive pressure applied upstream for this purpose.
  • a converging-diverging nozzle of the type suitable for use in the present invention is described in United States Patent No.
  • the catalyst is characterized in that the catalyst is substantially non-volatile at the curing temperature, that is, at temperatures at or below 360°F (182.2°C).
  • substantially non- volatile is meant that the catalyst does not volatilize from the film into the curing oven environment at these temperatures during the curing process.
  • the electrodepositable coating composition of the present invention comprises (a) one or more active hydrogen-containing, ionic salt group-containing resins, and (b) one or more curing agents.
  • cyclic polyols can be used in preparing the polyglycidyl ethers of cyclic polyols.
  • examples of other cyclic polyols include alicyclic polyols, particularly cycloaliphatic polyols such as 1 ,2-cyclohexane diol and 1 ,2- bis(hydroxymethyl)cyclohexane.
  • the preferred polyepoxides have epoxide equivalent weights ranging from 180 to 2000, preferably from 186 to 1200.
  • Epoxy group-containing acrylic polymers can also be used. These polymers typically have an epoxy equivalent weight ranging from 750 to 2000.
  • the reaction product of the primary and/or secondary amine and the polyepoxide is 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; i.e., an acid of the formula:
  • the extent of neutralization of the cationic electrodepositable composition varies with the particular reaction product involved. However, sufficient acid should be used to disperse the electrodepositable composition in water. Typically, the amount of acid used provides at least 20 percent of all of the total neutralization. Excess acid may also be used beyond the amount required for 100 percent total neutralization.
  • the tertiary amine can be pre-reacted with the neutralizing acid to form the amine salt and then the amine salt reacted with the polyepoxide to form a quaternary salt group-containing resin. The reaction is conducted by mixing the amine salt with the polyepoxide in water. Typically, the water is present in an amount ranging from 1.75 to 20 percent by weight based on total reaction mixture solids.
  • the reaction temperature can be varied from the lowest temperature at which the reaction will proceed, generally room temperature or slightly thereabove, to a maximum temperature of 100 °C (at atmospheric pressure). At higher pressures, higher reaction temperatures may be used. Preferably, the reaction temperature is in the range of 60 to 100 0 C. Solvents such as a sterically hindered ester, ether, or sterically hindered ketone may be used, but their use is not necessary.
  • a portion of the amine that is reacted with the polyepoxide can be a ketimine of a polyamine, such as is described in U.S. Patent No. 4,104,147, column 6, line 23 to column 7, line 23.
  • the ketimine groups decompose upon dispersing the amine-epoxy resin reaction product in water.
  • Suitable active hydrogen-containing, cationic salt group- containing resins can include copolymers of one or more alkyl esters of acrylic acid or methacrylic acid optionally together with one or more other polymerizable ethylenically unsaturated monomers.
  • Suitable alkyl esters of acrylic acid or methacrylic acid include methyl methacrylate, ethyl methacrylate, butyl methacrylate, ethyl acrylate, butyl acrylate, and 2-ethyl hexyl acrylate.
  • Functional groups such as hydroxyl and amino groups can be incorporated into the acrylic polymer by using functional monomers such as hydroxyalkyl acrylates and methacrylates or aminoalkyi acrylates and methacrylates.
  • Epoxide functional groups (for conversion to cationic salt groups) may be incorporated into the acrylic polymer by using functional monomers such as glycidyl acrylate and methacrylate, 3,4- epoxycyclohexylmethyl(meth)acrylate, 2-(3,4- epoxycyclohexyl)ethyl(meth)acrylate, or allyl glycidyl ether.
  • epoxide functional groups may be incorporated into the acrylic polymer by reacting carboxyl groups on the acrylic polymer with an epihalohydrin or dihalohydrin such as epichlorohydrin or dichlorohydrin.
  • the acrylic polymer can be prepared by traditional free radical initiated polymerization techniques, such as solution or emulsion polymerization, as known in the art, using suitable catalysts which include organic peroxides and azo type compounds and optionally chain transfer agents such as alpha-methyl styrene dimer and tertiary dodecyl mercaptan.
  • Additional acrylic polymers which are suitable for forming the active hydrogen- containing, cationic resin (a) which can be used in the electrodepositable compositions of the present invention include those resins described in U.S. Patent Nos. 3,455,806 and 3,928,157.
  • Polyurethanes can also be used as the polymer from which the active hydrogen-containing, cationic resin can be derived.
  • the polyurethanes which can be used are polymeric polyols which are prepared by reacting polyester polyols or acrylic polyols such as those mentioned above with a polyisocyanate such that the OH/NCO equivalent ratio is greater than 1 :1 so that free hydroxyl groups are present in the product.
  • Smaller polyhydric alcohols such as those disclosed above for use in the preparation of the polyester may also be used in place of or in combination with the polymeric polyols.
  • polyurethane polymers suitable for forming the active hydrogen-containing, cationic resin (a) include the polyurethane, polyurea, and poly(urethane-urea) polymers prepared by reacting polyether polyols and/or polyether polyamines with polyisocyanates. Such polyurethane polymers are described in U.S. Patent No. 6,248,225.
  • Epoxide functional groups may be incorporated into the polyurethane by methods well known in the art. For example, epoxide groups can be incorporated by reacting glycidol with free isocyanate groups. Alternatively, hydroxyl groups on the polyurethane can be reacted with an epihalohydrin or dihalohydrin such as epichlorohydrin or dichlorohydrin in the presence of alkali.
  • Sulfonium group-containing polyurethanes can also be made by at least partial reaction of hydroxy-functional sulfide compounds, such as thiodiglycol and thiodipropanol, which results in incorporation of sulfur into the backbone of the polymer.
  • the sulfur-containing polymer is then reacted with a monofunctional epoxy compound in the presence of acid to form the sulfonium group.
  • Appropriate monofunctional epoxy compounds include ethylene oxide, propylene oxide, glycidol, phenylglycidyl ether, and CARDURA® E, available from Resolution Performance Products.
  • the active hydrogen-containing, cationic salt group- containing polymer can be derived from a polyester.
  • polyesters can be prepared in a known manner by condensation of polyhydric alcohols and polycarboxylic acids.
  • Suitable polyhydric alcohols include, for example, ethylene glycol, propylene glycol, butylene glycol, 1 ,6-hexylene glycol, neopentyl glycol, diethylene glycol, glycerol, trimethylol propane, and pentaerythritol.
  • polyesters examples include succinic acid, adipic acid, azelaic acid, sebacic acid, maleic acid, fumaric acid, phthalic acid, tetrahydrophthalic acid, hexahydrophthalic acid, and trimellitic acid.
  • functional equivalents of the acids such as anhydrides where they exist or lower alkyl esters of the acids such as the methyl esters may be used.
  • the polyesters contain a portion of free hydroxyl groups
  • Sulfonium salt groups can be introduced by the reaction of an epoxy group-containing polymer of the types described above with a sulfide in the presence of an acid, as described in U.S. Patent Nos. 3,959,106 and 4,715,898. Sulfonium groups can be introduced onto the polyester backbones described using similar reaction conditions.
  • the active hydrogens associated with the cationic resin include any active hydrogens which are reactive with isocyanates at temperatures sufficient to cure the electrodepositable composition as previously discussed, i.e., at temperatures at or below 360°F (182.2°C).
  • the active hydrogens typically are derived from reactive hydroxyl groups, and primary and secondary amino, including mixed groups such as hydroxyl and primary amino.
  • the active hydrogens are derived from hydroxyl groups comprising phenolic hydroxyl groups.
  • the cationic resin can have an active hydrogen content of 1 to 4 milliequivalents, typically 2 to 3 milliequivalents of active hydrogen per gram of resin solids.
  • the extent of cationic salt group formation should be such that when the resin is mixed with an aqueous medium and other ingredients, a stable dispersion of the electrodepositable composition will form.
  • stable dispersion is meant one that does not settle or is easily redispersible if some settling occurs.
  • non- gelled is meant that the resin is substantially free from crosslinking, and prior to cationic salt group formation, the resin has a measurable intrinsic viscosity when dissolved in a suitable solvent.
  • a gelled resin having an essentially infinite molecular weight, would have an intrinsic viscosity too high to measure.
  • the active hydrogen-containing, cationic salt group- containing resin (a) can be present in the electrodepositable composition of the present invention in an amount ranging from 40 to 95 weight percent, typically from 50 to 75 weight percent based on weight of total resin solids present in the composition.
  • the electrodepositable composition of the present invention also comprises at least one curing agent, such as a polyisocyanate, polyester or carbonate.
  • the polyisocyanate curing agent may be a fully blocked polyisocyanate with substantially no free isocyanate groups, or it may be partially blocked and reacted with the resin backbone as described in U.S. Patent 3,984,299.
  • the polyisocyanate can be an aliphatic or an aromatic polyisocyanate or a mixture of the two. Diisocyanates are preferred, although higher polyisocyanates can be used in place of or in combination with diisocyanates.
  • Suitable aliphatic diisocyanates are straight chain aliphatic diisocyanates such as 1 ,4-tetramethylene diisocyanate, norbornane diisocyanate, and 1 ,6-hexamethylene diisocyanate.
  • cycloaliphatic diisocyanates can be employed. Examples include isophorone diisocyanate and 4,4'-methylene-bis-(cyclohexyl isocyanate).
  • suitable aromatic diisocyanates are p-phenylene diisocyanate, diphenylmethane-4,4'-diisocyanate and 2,4- or 2,6-toluene diisocyanate.
  • Isocyanate prepolymers for example, reaction products of polyisocyanates with polyols such as neopentyl glycol and trimethylol propane or with polymeric polyols such as polycaprolactone diols and triols (NCO/OH equivalent ratio greater than one) can also be used.
  • a mixture of diphenylmethane-4,4'-diisocyanate and polymethylene polyphenyl isocyanate can be used.
  • Any suitable alcohol or polyol can be used as a blocking agent for the polyisocyanate in the electrodepositable composition of the present invention provided that the agent will deblock at the curing temperature and provided a gelled product is not formed.
  • Any suitable aliphatic, cycloaliphatic, or aromatic alkyl alcohol may be used as a blocking agent for the polyisocyanate including, for example, lower aliphatic monoalcohols such as methanol, ethanol, and n-butanol; cycloaliphatic alcohols such as cyclohexanol; aromatic-alkyl alcohols such as phenyl carbinol and methylphenyl carbinol.
  • Glycol ethers may also be used as blocking agents. Suitable glycol ethers include ethylene glycol butyl ether, diethylene glycol butyl ether, ethylene glycol methyl ether and propylene glycol methyl ether.
  • Suitable blocking agents include oximes such as methyl ethyl ketoxime, acetone oxime and cyclohexanone oxime and lactams such as epsilon-caprolactam.
  • the curing agent comprises one or more polyester curing agents.
  • Suitable polyester curing agents include materials having greater than one ester group per molecule.
  • the ester groups are present in an amount sufficient to effect cross-linking at acceptable cure temperatures and cure times, for example at temperatures up to 250 0 C, and curing times of up to 90 minutes. It should be understood that acceptable cure temperatures and cure times will be dependent upon the substrates to be coated and their end uses.
  • the polyester curing agent is substantially free of acid.
  • substantially free of acid is meant having less than 0.2 meq/g acid.
  • suitable polyester curing agents can include non-acidic polyesters prepared from a polycarboxylic acid anhydride, one or more glycols, alcohols, glycol mono-ethers, polyols, and/or monoepoxides.
  • Non-acidic polyesters can be prepared, for example, by reacting, in one or more steps, trimellitic anhydride (TMA) with glycidyl esters of branched monocarboxylic acids in a molar ratio of 1 :1.5 to 1 :3, if desired with the aid of an esterification catalyst such as stannous octoate or benzyl dimethyl amine, at temperatures of 50-150 0 C. Additionally, trimellitic anhydride can be reacted with 3 molar equivalents of a monoalcohol such as 2-ethylhexanol.
  • TMA trimellitic anhydride
  • glycidyl esters of branched monocarboxylic acids in a molar ratio of 1 :1.5 to 1 :3, if desired with the aid of an esterification catalyst such as stannous octoate or benzyl dimethyl amine, at temperatures of 50-150 0 C.
  • trimellitic anhydride can be reacted with
  • trimellitic anhydride (1 mol.) can be reacted first with a glycol or a glycol monoalkyl ether, such as ethylene glycol monobutyl ether in a molar ratio of 1 :0.5 to 1 :1 , after which the product is allowed to react with 2 moles of glycidyl esters of branched monocarboxylic acids.
  • a glycol or a glycol monoalkyl ether such as ethylene glycol monobutyl ether in a molar ratio of 1 :0.5 to 1 :1
  • polycarboxylic acid anhydride i.e., those containing two or three carboxyl functions per molecule
  • a mixture of polycarboxylic acid anhydrides can be reacted simultaneously with a glycol, such as 1 ,6- hexane diol and/or glycol mono-ether and monoepoxide, after which the product can be reacted with mono-epoxides, if desired.
  • these non-acid polyesters can also be modified with polyamines such as diethylene triamine to form amide polyesters.
  • polyamine-modified polyesters may be incorporated in the linear or branched amine adducts described above to form self-curing amine adduct esters.
  • the catalyst nanoparticles can be incorporated into the electrodepositable composition of the present invention by any method or means provided that the stability of the composition is not compromised.
  • the catalyst nanoparticles can be admixed with or dispersed in the reactants used to form the resin (a) during preparation of the resin (a).
  • the catalyst nanoparticles can be admixed with or dispersed in one or more of the reactants used to form the resin (a) prior to resin preparation.
  • the catalyst nanoparticles can be admixed with or dispersed in the resin (a) either prior to or subsequent to neutralization with an acid.
  • the catalyst nanoparticles also can be added neat to the electrodepositable composition subsequent to dispersion in the aqueous medium. Additionally, if desired, the catalyst nanoparticles can be added online to the electrodeposition bath in the form of an additive material. It should be understood that the catalyst can be incorporated into the electrodepositable composition by one or more of the above described methods.
  • the electrodepositable composition may optionally contain a coalescing solvent such as hydrocarbons, alcohols, esters, ethers and ketones.
  • the electrodepositable composition of the present invention may further contain pigments and various other optional additives such as plasticizers, surfactants, wetting agents, defoamers, and anti- cratering agents, as well as adjuvant resinous materials different from the resin (a) and the curing agent (b).
  • the present invention is directed to a method of coating a substrate further comprising a step of curing the composition after application to the substrate.
  • the components used to form the compositions in these embodiments can be selected from the components discussed above, and additional components also can be selected from those recited above.
  • [00128] Particles from solid precursors were prepared using a DC thermal plasma reactor system of the type described in United States Patent No. RE 37.853E.
  • the main reactor system included a DC plasma torch (Model SG-100 Plasma Spray Gun commercially available from Praxair Technology, Inc., Danbury, Connecticut) operated with 60 standard liters per minute of argon carrier gas and 28 kilowatts of power delivered to the torch.
  • Solid reactant feed compositions comprising the materials and amounts listed in Tables 1-5 were prepared and fed to the reactor at a rate of 2.5 grams per minute through a gas assistant powder feeder (Model 1264, commercially available from Praxair Technology, Inc., Danbury, Connecticut) located at the plasma torch outlet.
  • Coating compositions were prepared using the components and weights (in grams) shown in Table 10. Coatings were prepared by adding components 1 to 3 to a suitable vessel under agitation with a tong press for 3 minutes.

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Abstract

L'invention concerne une composition de revêtement pouvant être électrodéposée comprenant une phase résineuse et des nanoparticules de catalyseur dispersées dans un milieu aqueux, la phase résineuse comprenant (a) au moins une résine contenant un groupe de sel ionique contenant de l'hydrogène actif ; et (b) au moins un agent de durcissement ; et les nanoparticules de catalyseur pour effectuer un durcissement entre la résine (a) et l'agent de durcissement (b). Les nanoparticules de catalyseur ont une surface spécifique BET moyenne supérieure à 20 mètres carrés par gramme (m2/g). Des procédés pour préparer et utiliser la composition sont également proposés.
PCT/US2006/031133 2005-08-26 2006-08-10 Compositions de revêtement pouvant être électrodéposées, et procédés apparentés WO2008054353A2 (fr)

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Families Citing this family (28)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US20070051634A1 (en) * 2005-08-26 2007-03-08 Ppg Industries Ohio, Inc. Electrodepositable coating compositions and related methods
US7803295B2 (en) * 2006-11-02 2010-09-28 Quantumsphere, Inc Method and apparatus for forming nano-particles
US20080210561A1 (en) * 2006-12-21 2008-09-04 Walter Mahler Stable aqueous dispersions of ethylene-aminoalkyl methacrylate copolymers
DE102008023444A1 (de) 2008-05-14 2009-11-19 Basf Coatings Ag Elektrotauchlackzusammensetzung
US8182668B1 (en) 2008-07-29 2012-05-22 Technion Research And Development Foundation Ltd. Method for producing a barium titanate layer by cathodic electrophoretic deposition from aqueous solution
US20100276827A1 (en) * 2009-04-29 2010-11-04 Kevin Smith Method for Producing Nanoparticles
DE102010005868A1 (de) * 2010-01-26 2011-07-28 KRONOS INTERNATIONAL, Inc., 51373 Bismut-haltiges katalytisches System zur Vernetzung von Polymeren
US20140150970A1 (en) 2010-11-19 2014-06-05 Ppg Industries Ohio, Inc. Structural adhesive compositions
US8796361B2 (en) 2010-11-19 2014-08-05 Ppg Industries Ohio, Inc. Adhesive compositions containing graphenic carbon particles
US10763490B2 (en) 2011-09-30 2020-09-01 Ppg Industries Ohio, Inc. Methods of coating an electrically conductive substrate and related electrodepositable compositions including graphenic carbon particles
US9832818B2 (en) 2011-09-30 2017-11-28 Ppg Industries Ohio, Inc. Resistive heating coatings containing graphenic carbon particles
US9761903B2 (en) 2011-09-30 2017-09-12 Ppg Industries Ohio, Inc. Lithium ion battery electrodes including graphenic carbon particles
US9475946B2 (en) 2011-09-30 2016-10-25 Ppg Industries Ohio, Inc. Graphenic carbon particle co-dispersions and methods of making same
US9988551B2 (en) 2011-09-30 2018-06-05 Ppg Industries Ohio, Inc. Black pigments comprising graphenic carbon particles
US10294375B2 (en) 2011-09-30 2019-05-21 Ppg Industries Ohio, Inc. Electrically conductive coatings containing graphenic carbon particles
US10240052B2 (en) 2011-09-30 2019-03-26 Ppg Industries Ohio, Inc. Supercapacitor electrodes including graphenic carbon particles
US8486363B2 (en) * 2011-09-30 2013-07-16 Ppg Industries Ohio, Inc. Production of graphenic carbon particles utilizing hydrocarbon precursor materials
US9938416B2 (en) 2011-09-30 2018-04-10 Ppg Industries Ohio, Inc. Absorptive pigments comprising graphenic carbon particles
US11430979B2 (en) 2013-03-15 2022-08-30 Ppg Industries Ohio, Inc. Lithium ion battery anodes including graphenic carbon particles
GB201410700D0 (en) * 2014-06-16 2014-07-30 Pq Silicas Uk Ltd Curable liquid compositions
US10377928B2 (en) 2015-12-10 2019-08-13 Ppg Industries Ohio, Inc. Structural adhesive compositions
US10351661B2 (en) 2015-12-10 2019-07-16 Ppg Industries Ohio, Inc. Method for producing an aminimide
CN106883760B (zh) * 2017-03-07 2019-06-18 瑞娃科技（重庆）有限公司 一种高光水洗净纳米树脂及其制备方法
US11225441B2 (en) * 2018-10-18 2022-01-18 Praxair S.T. Technology, Inc. Chromium-free silicate-based ceramic compositions with reduced curing temperature
US11123715B2 (en) * 2019-11-22 2021-09-21 King Fahd University Of Petroleum And Minerals Mesoporous composite catalysts containing bismuth silicate and transition metal oxide
CN114846044A (zh) * 2019-12-31 2022-08-02 Ppg工业俄亥俄公司 可电沉积的涂层组合物
CN115551954A (zh) * 2020-05-25 2022-12-30 巴斯夫涂料有限公司 具有改进催化活性的含铋电泳涂料
CA3199679A1 (fr) * 2020-11-09 2022-05-12 Huntsman Advanced Materials Americas Llc Sechage par pulverisation de resines epoxy ou phenoxy solides

Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2000034398A1 (fr) * 1998-12-04 2000-06-15 E.I. Du Pont De Nemours And Company Catalyseur a base d'oxyde de bismuth destine a des compositions pour revetement electrolytique cathodique
JP2000290542A (ja) * 1999-04-12 2000-10-17 Nof Corp カチオン電着塗料組成物および塗膜
GB2368302A (en) * 2000-09-20 2002-05-01 Kansai Paint Co Ltd Multi-layer coating film forming method
US6436201B1 (en) * 1998-01-29 2002-08-20 Kansai Paint Co., Ltd. Cationic electrodeposition paint composition

Family Cites Families (28)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4851262A (en) * 1987-05-27 1989-07-25 Carnegie-Mellon University Method of making carbide, nitride and boride powders
JP2983370B2 (ja) * 1991-04-16 1999-11-29 関西ペイント株式会社 電着塗料組成物
US5749937A (en) * 1995-03-14 1998-05-12 Lockheed Idaho Technologies Company Fast quench reactor and method
US5788738A (en) * 1996-09-03 1998-08-04 Nanomaterials Research Corporation Method of producing nanoscale powders by quenching of vapors
US6344271B1 (en) * 1998-11-06 2002-02-05 Nanoenergy Corporation Materials and products using nanostructured non-stoichiometric substances
US5851507A (en) * 1996-09-03 1998-12-22 Nanomaterials Research Corporation Integrated thermal process for the continuous synthesis of nanoscale powders
US5905000A (en) * 1996-09-03 1999-05-18 Nanomaterials Research Corporation Nanostructured ion conducting solid electrolytes
US6569397B1 (en) * 2000-02-15 2003-05-27 Tapesh Yadav Very high purity fine powders and methods to produce such powders
US6652967B2 (en) * 2001-08-08 2003-11-25 Nanoproducts Corporation Nano-dispersed powders and methods for their manufacture
US5908912A (en) * 1996-09-06 1999-06-01 Ppg Industries Ohio, Inc. Electrodepositable coating composition containing bismuth and amino acid materials and electrodeposition method
US6669835B1 (en) * 1997-02-18 2003-12-30 Atofina Chemicals, Inc. Aqueous dispersions of polymerizable reactants and a water incompatible catalyst sorbed on an inorganic particulate carrier
US5984997A (en) * 1997-08-29 1999-11-16 Nanomaterials Research Corporation Combustion of emulsions: A method and process for producing fine powders
US6600127B1 (en) * 1999-09-15 2003-07-29 Nanotechnologies, Inc. Method and apparatus for direct electrothermal-physical conversion of ceramic into nanopowder
AU2002220566B8 (en) * 2000-09-25 2007-09-13 Chemetall Gmbh Method for pretreating and coating metal surfaces, prior to forming, with a paint-like coating and use of substrates so coated
US20020137872A1 (en) * 2000-12-08 2002-09-26 Schneider John R. Coating compositions providing improved mar and scratch resistance and methods of using the same
US6586483B2 (en) * 2001-01-08 2003-07-01 3M Innovative Properties Company Foam including surface-modified nanoparticles
WO2002100924A2 (fr) * 2001-02-12 2002-12-19 Nanoproducts Corporation Precurseurs de poudres travaillees
US7220793B2 (en) * 2002-02-20 2007-05-22 Ppg Industries Ohio, Inc. Curable film-forming composition exhibiting improved resistance to degradation by ultraviolet light
US20030166758A1 (en) * 2002-02-20 2003-09-04 Barkac Karen A. Curable powder film-forming composition exhibiting improved flow and leveling
US6916368B2 (en) * 2002-02-20 2005-07-12 Ppg Industries Ohio, Inc. Curable film-forming composition exhibiting improved scratch resistance
US6770705B2 (en) * 2002-02-20 2004-08-03 Ppg Industries Ohio, Inc. Curable film-forming composition exhibiting improved impact strength and chip resistance
US7141618B2 (en) * 2002-06-03 2006-11-28 Ppg Industries Ohio, Inc. Coating compositions with modified particles and methods of using the same
US6669823B1 (en) * 2002-06-17 2003-12-30 Nanophase Technologies Corporation Process for preparing nanostructured materials of controlled surface chemistry
US6727309B1 (en) * 2002-10-08 2004-04-27 3M Innovative Properties Company Floor finish composition
US20040156986A1 (en) * 2003-02-10 2004-08-12 Nanoproducts Corporation Color pigments nanotechnology
US6835458B2 (en) * 2003-04-16 2004-12-28 Ppg Industries Ohio, Inc. Coating composition having improved mar and scratch properties
US20050137291A1 (en) * 2003-12-17 2005-06-23 Schneider John R. Coating compositions with enhanced corrosion resistance and appearance
US20050137298A1 (en) * 2003-12-17 2005-06-23 Schneider John R. Imidazole-containing coating compositions with enhanced corrosion resistance

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US6436201B1 (en) * 1998-01-29 2002-08-20 Kansai Paint Co., Ltd. Cationic electrodeposition paint composition
WO2000034398A1 (fr) * 1998-12-04 2000-06-15 E.I. Du Pont De Nemours And Company Catalyseur a base d'oxyde de bismuth destine a des compositions pour revetement electrolytique cathodique
JP2000290542A (ja) * 1999-04-12 2000-10-17 Nof Corp カチオン電着塗料組成物および塗膜
GB2368302A (en) * 2000-09-20 2002-05-01 Kansai Paint Co Ltd Multi-layer coating film forming method

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WO2008054353A3 (fr) 2008-08-14
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WO2008054353A9 (fr) 2009-07-23

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