EP3449034B1 - Produit de rinçage activateur et procédé de traitement d'un substrat - Google Patents

Produit de rinçage activateur et procédé de traitement d'un substrat Download PDF

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Publication number
EP3449034B1
EP3449034B1 EP17721028.3A EP17721028A EP3449034B1 EP 3449034 B1 EP3449034 B1 EP 3449034B1 EP 17721028 A EP17721028 A EP 17721028A EP 3449034 B1 EP3449034 B1 EP 3449034B1
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EP
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Prior art keywords
composition
ppm
activating rinse
substrate
metal
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EP17721028.3A
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German (de)
English (en)
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EP3449034A1 (fr
Inventor
Mark W. Mcmillen
Steven J. LEMON
Peter L. Votruba-Drzal
Matthew E. Wehrle
Nathan J. Silvernail
Richard F. Karabin
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PPG Industries Ohio Inc
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PPG Industries Ohio Inc
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Priority to EP22165169.8A priority Critical patent/EP4039850A1/fr
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Classifications

    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C22/00—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals
    • C23C22/05—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals using aqueous solutions
    • C23C22/06—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals using aqueous solutions using aqueous acidic solutions with pH less than 6
    • C23C22/07—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals using aqueous solutions using aqueous acidic solutions with pH less than 6 containing phosphates
    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C22/00—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals
    • C23C22/05—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals using aqueous solutions
    • C23C22/06—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals using aqueous solutions using aqueous acidic solutions with pH less than 6
    • C23C22/07—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals using aqueous solutions using aqueous acidic solutions with pH less than 6 containing phosphates
    • C23C22/08—Orthophosphates
    • C23C22/12—Orthophosphates containing zinc cations
    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C22/00—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals
    • C23C22/05—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals using aqueous solutions
    • C23C22/06—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals using aqueous solutions using aqueous acidic solutions with pH less than 6
    • C23C22/07—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals using aqueous solutions using aqueous acidic solutions with pH less than 6 containing phosphates
    • C23C22/08—Orthophosphates
    • C23C22/18—Orthophosphates containing manganese cations
    • C23C22/182—Orthophosphates containing manganese cations containing also zinc cations
    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C22/00—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals
    • C23C22/05—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals using aqueous solutions
    • C23C22/06—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals using aqueous solutions using aqueous acidic solutions with pH less than 6
    • C23C22/07—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals using aqueous solutions using aqueous acidic solutions with pH less than 6 containing phosphates
    • C23C22/08—Orthophosphates
    • C23C22/20—Orthophosphates containing aluminium cations
    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C22/00—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals
    • C23C22/05—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals using aqueous solutions
    • C23C22/06—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals using aqueous solutions using aqueous acidic solutions with pH less than 6
    • C23C22/07—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals using aqueous solutions using aqueous acidic solutions with pH less than 6 containing phosphates
    • C23C22/08—Orthophosphates
    • C23C22/22—Orthophosphates containing alkaline earth metal cations
    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C22/00—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals
    • C23C22/78—Pretreatment of the material to be coated

Definitions

  • An activating rinse for treating a metal substrate is disclosed.
  • Phosphate conversion coatings are well known for treating metal surfaces, particularly ferrous, zinc and aluminum metals and their alloys. When applied, these phosphate coatings form a phosphate layer, primarily of zinc and iron phosphate crystals, which provides corrosion resistance and/or enhances the adhesion of subsequently applied coatings.
  • the metal substrate Prior to application of the phosphate coating, the metal substrate is typically "conditioned” or “activated” by subjecting the surface of the metal substrate to a diluted aqueous dispersion, sometimes referred to as an activating rinse or activator, by introducing or immersing the metal substrate into a tank that contains the activating rinse.
  • activating rinse or activator a diluted aqueous dispersion
  • "Activation" of the surface of the metal substrate often is achieved due to the adsorption of colloidal titanium-phosphate particles, which are present in the activating rinse, to the metal's surface.
  • colloidal titanium-phosphate particles however, have a tendency to agglomerate in the activating rinse bath due to dissolved cations that are typically present in the activating rinse conditioner bath.
  • the phosphate conversion coating is typically applied to a substrate by immersing the substrate into a heated bath comprising metal phosphate particles.
  • US 2007/240604 A1 , EP 1 930 475 A1 and EP 1 930 474 A1 disclose each a surface conditioning treatment of a metal substrate prior to phosphating with a surface conditioning composition comprising a dispersion of solid metal phosphate particles of a divalent and/or trivalent metal wet pulverised in a dispersion medium and having a D 90 particle size of no more than 1 ⁇ m.
  • an activating rinse for treating a substrate is disclosed in claim 1.
  • the activating rinse comprises, or in some instances consists of, or in some instances consists essentially of: a dispersion of metal phosphate particles of divalent metals, trivalent metals or combinations thereof, the metal phosphate particles having a D 90 particle size that is not greater than 10 ⁇ m; a dispersant; and a metal sulfate salt.
  • activating rinse refers to a continuous aqueous medium having dispersed and/or suspended therein metal phosphate particles that is applied onto at least a portion of a substrate and/or into which at least a portion of a substrate is immersed to "activate” or “condition” the substrate in order to promote the formation of a metal phosphate coating on at least a portion of the substrate that was treated with the activating rinse.
  • to "activate” or “condition” the substrate surface means to create nucleation sites on the substrate surface. While not wishing to be bound by theory, it is believed that such nucleation sites promote the formation of metal phosphate crystals on the substrate surface when the substrate surface subsequently is treated with a metal phosphate pretreatment composition. For example, activation of the substrate surface is believed to create nucleation sites that promote the formation of zinc and zinc/iron phosphate crystals on the substrate surface when the substrate surface is pretreated with a zinc phosphate pretreatment composition.
  • the substrate that can be treated with the activating rinse includes a metal and/or a metal alloy substrate.
  • the metal and/or metal alloy can comprise or be aluminum, steel, or zinc.
  • a steel substrate could include cold rolled steel, electrogalvanized steel, and hot dipped galvanized steel.
  • the substrate may comprise a portion of a vehicle such as a vehicular body (e.g., without limitation, door, body panel, trunk deck lid, roof panel, hood, and/or roof) and/or a vehicular frame.
  • vehicle or variations thereof includes, but is not limited to, civilian, commercial, and military land vehicles such as cars and trucks.
  • the term "dispersion” refers to a two-phase transparent, translucent or opaque system in which metal phosphate particles are in the dispersed phase and an aqueous medium, which includes water, is in the continuous phase.
  • An "aqueous medium” is a liquid medium that is 50 weight percent or greater of water, with weight percent based on non-solid content of the activating rinse.
  • the aqueous medium may comprise 50 weight percent or less of other organic co-solvents, such as 10 weight percent or less. According to the present invention, the organic co-solvents are at least partially miscible with water.
  • water miscible organic solvents may be present, for example, alcohols with up to about 8 carbon atoms such as methanol, isopropanol, and the like, or glycol ethers such as the monoalkyl ethers of ethylene glycol, diethylene glycol, or propylene glycol, and the like.
  • the term “pulverized” refers to particles having variable aspect ratios, where the term “aspect ratio” refers to the ratio of the length to the width of a particle (i.e., the aspect ratio does not define a sphere).
  • the metal phosphate particles of the dispersion of metal phosphate particles of divalent or trivalent metals or combinations thereof may have a D 90 particle size that is not greater than 10 ⁇ m, such as not greater than 8 ⁇ m, such as not greater than 5 ⁇ m, such as not greater than 2 ⁇ m, such as not greater than 1 ⁇ m and in some cases may be at least 0.06 ⁇ m, such as at least 0.1 ⁇ m, such as at least 0.2 ⁇ m.
  • the metal phosphate particles of the dispersion of phosphate particles of divalent or trivalent metals or combinations thereof may have a D 90 particle size of 0.06 ⁇ m to 8 ⁇ m, such as 0.1 ⁇ m to 5 ⁇ m, such as 0.2 ⁇ m to 2 ⁇ m.
  • the term “D 90 " particle size refers to a volume-weighted particle distribution in which 90% of the particles in the particle distribution have a diameter smaller than the "D 90 " value.
  • the term “D 10 " particle size refers to a volume-weighted particle distribution in which 10% of the particles in the particle distribution have a diameter smaller than the “D 10 " value.
  • the term “D 50” particle size refers to a volume-weighted particle distribution in which 50% of the particles in the particle distribution have a diameter smaller than the "D 50 " value.
  • particle size may be measured using an instrument such as a Mastersizer 2000, available from Malvern Instruments, Ltd., of Malvern, Worcestershire, UK, or an equivalent instrument.
  • the Mastersizer 2000 directs a laser beam (0.633 mm diameter, 633 nm wavelength) through a dispersion of particles (in distilled, deionized or filtered water to 2-3% obscuration), and measures the light scattering of the dispersion (measurement parameters 25°C, 2200 RPM, 30 sec premeasurement delay, 10 sec background measurement, 10 sec sample measurement).
  • the amount of light scattered by the dispersion is inversely proportional to the particle size.
  • a series of detectors measure the scattered light and the data are then analyzed by computer software (Malvern Mastersizer 2000 software, version 5.60) to generate a particle size distribution, from which particle size can be routinely determined.
  • the sample of dispersion of particles optionally may be sonicated prior to analysis for particle size.
  • the sonication process comprises: (1) mixing the dispersion of particles using a Vortex mixer (Fisher Scientific Vortex Genie 2, or equivalent); (2) adding 15 mL of distilled deionized, ultra-filtered water to a 20 mL screw-cap scintillation vial; (3) adding 4 drops of the dispersion to the vial; (4) mixing the contents of the vial using the Vortex mixer; (5) capping the vial and placing it into an ultrasonic water bath (Fisher Scientific Model FS30, or equivalent) for 5 minutes; (6) vortexing the vial again; and (7) adding the sample dropwise to the Mastersizer to reach an obscuration between 2-3 for particle size distribution analysis described above.
  • a Vortex mixer Fisher Scientific Vortex Genie 2, or equivalent
  • adding 15 mL of distilled deionized, ultra-filtered water to a 20 mL screw-cap scintillation vial
  • the metal phosphate particles may be substantially pulverized, such that more than 90% of the metal phosphate particles in the activating rinse composition are pulverized, such as more than 91%, such as more than 92%, such as more than 93%, such as more than 94%, such as more than 95%, such as more than 96%, such as more than 97%, such as more than 98%, such as more than 99%.
  • the metal phosphate particles may be completely pulverized, such that 100% of the particles are pulverized.
  • the metal phosphate (as total metal compound) may be present in the activating rinse in an amount of at least 50 ppm, based on total weight of the activating rinse, such as at least 150 ppm, and in some instances may be present in the activating rinse in an amount of no more than 5000 ppm, based on total weight of the activating rinse, such as no more than 1500 ppm.
  • the metal phosphate (as total metal compound) may be present in the activating rinse in an amount of 50 ppm to 5,000 ppm of total metal phosphate based on the total weight of the activating rinse, such as of 150 ppm to 1,500 ppm.
  • the divalent or trivalent metal of the metal phosphate may comprise zinc, iron, calcium, manganese, aluminum, nickel, or combinations thereof. If combinations of different metal phosphates are employed, they may comprise the same or different metals, and may be selected from the particular zinc, iron, calcium, manganese and aluminum phosphates mentioned in the following.
  • Suitable zinc phosphates useful in the activating rinse bath include, without limitation Zn 3 (PO 4 ) 2 , Zn 2 Fe(PO 4 ) 2 , Zn 2 Ca(PO 4 ) 2 , Zn 2 Mn(PO 4 ) 2 , or combinations thereof.
  • Suitable iron phosphates useful in the activating rinse bath include, without limitation FePO 4 , Fe 3 (PO 4 ) 2 , or combinations thereof.
  • Suitable calcium phosphates useful in the activating rinse bath include, without limitation CaHPO 4 , Ca 3 (PO 4 ) 2 , or combinations thereof.
  • Suitable manganese phosphates useful in the activating rinse bath include, without limitation Mn 3 (PO 4 ) 2 , MnPO 4 , or combinations thereof.
  • Suitable aluminum phosphates useful in the activating rinse bath include, without limitation AlPO 4 .
  • the activating rinse comprises a dispersant.
  • the dispersant is non-ionic.
  • the non-ionic dispersant used in the activating rinse includes a non-ionic polymer comprising residues of monomers including propylene oxide, ethylene oxide, styrene, a monoacid such as (meth)acrylic acid, a diacid such as maleic acid or itaconic acid, an acid anhydride such as acrylic anhydride or maleic anhydride, or combinations thereof.
  • suitable commercially available non-ionic dispersants include DISPERBYK ® -190 available from BYK-Chemie GmbH and ZetaSperse ® 3100 available from Air Products Chemicals Inc.
  • the activating rinse may be substantially free or completely free of ionic dispersants.
  • an activating rinse is substantially free of ionic dispersants if ionic dispersants are present in an amount less than 1% by weight, based on the total weight of the activating rinse.
  • an activating rinse is completely free of ionic dispersants if ionic dispersants are not present in the activating rinse, meaning 0% by weight based on the total weight of the activating rinse.
  • the activating rinse includes a metal sulfate salt, such as, for example, where the metal phosphate particles have a D 90 particle size of greater than 1 ⁇ m to 10 ⁇ m, or, for example, where the metal phosphate particles have a D 90 particle size of less than 1 ⁇ m.
  • the metal of the metal sulfate salt comprises nickel, copper, zinc, iron, cobalt, or combinations thereof.
  • the sulfate ion of the metal sulfate salt may be present in the activating rinse in an amount of at least 5 ppm based on the total weight of the activating rinse, such as at least 10 ppm, such as at least 20 ppm, such as at least 50 ppm, and in some cases, no more than the solubility limit of the metal sulfate salt in the activating rinse, such as no more than 5,000 ppm, such as no more than 1,000 ppm, such as no more than 500 ppm, such as no more than 250 ppm.
  • the sulfate ion of the metal sulfate salt may be present in an amount of 5 ppm to 5,000 ppm based on a total amount of sulfate in the metal sulfate salt, such as 10 ppm to 1,000 ppm, such as 20 ppm to 500 ppm, such as 50 ppm to 250 ppm.
  • the activating rinse may be in the form of a concentrate, wherein the concentrate has a viscosity sufficient to prevent the metal phosphate particles and metal sulfate salt (if present) from settling out.
  • the concentrated activating rinse may be diluted with water and/or an organic solvent.
  • the activating rinse may be a 1K ("One- Component", or “One Part") composition or a multi-component composition, such as, for example, 2K ("Two-Component", or 'Two Part") compositions.
  • a “1K” composition is a composition in which all of the ingredients may be premixed and stored.
  • a multi-component composition is one in which at least two of the ingredients are stored separately and are mixed together to form the treatment bath.
  • the activating rinse may be a 1K composition, wherein the 1K composition is formed from: a dispersion of metal phosphate particles of divalent metals, trivalent metals or combinations thereof, the metal phosphate particles having a D 90 particle size that is not greater than 10 ⁇ m; a dispersant; and a metal sulfate salt.
  • the 1K activating rinse may be a concentrate that is diluted to form the bath containing the activating rinse.
  • the activating rinse may be a 2K composition wherein a dispersion of metal phosphate particles of divalent metals, trivalent metals or combinations thereof, the metal phosphate particles having a D 90 particle size that is not greater than 10 ⁇ m, and a dispersant form a part of a first component.
  • a metal sulfate salt forms a part of a second component.
  • Additional components comprising any of the optional ingredients described below also may be added to the bath containing the activating rinse. Any of the components of the activating rinse may be a concentrate that is diluted to form the bath containing the activating rinse.
  • the activating rinse may include a wetting agent.
  • wetting agents may be present at amounts of up to 2 percent by weight, such as up to 0.5 percent by weight, based on the total weight of the activating rinse. In some instances, wetting agents may be present in amounts of 0.1 percent by weight to 2 percent by weight, based on total weight of the activating rinse, such as 0.3 percent by weight to 0.5 percent by weight.
  • a "wetting agent” reduces the surface tension at the interface between the surface of the particles of the dispersed phase and the aqueous medium to allow the aqueous medium to more evenly contact or "wet" the surface of the particles of the dispersed phase.
  • the activating rinse may have a pH of 6 to 12, such as 6.5 to 9, such as 7.5 to 8.5, such as 7 to 8.
  • An alkaline component may be present in the activating rinse in an amount sufficient to adjust the pH of the activating rinse.
  • Suitable alkaline components may include, for example, sodium hydroxide, sodium carbonate, sodium tripolyphosphate, potassium orthophosphate, or combinations thereof.
  • the activating rinse may also include a biocide.
  • Suitable biocides include, for example, methyl chloro isothiazolinone, methyl isothiazolinone, or combinations thereof.
  • the biocide may be present in an amount of at least 10 ppm based on active material in the activating rinse, such as at least 20 ppm, such as at least 80 ppm, such as at least 100 ppm, and in some instances, no more than 140 ppm, such as no more than 120 ppm, such as no more than 40 ppm, such as no more than 30 ppm.
  • the biocide may be present in an amount of 10 ppm to 140 ppm based on active material, such as 10 ppm to 40 ppm, such as 20 ppm to 30 ppm, such as 80 ppm to 140 ppm, such as 100 ppm to 120 ppm.
  • active material such as 10 ppm to 40 ppm, such as 20 ppm to 30 ppm, such as 80 ppm to 140 ppm, such as 100 ppm to 120 ppm.
  • biocides may be included in the activating rinse in amounts based on manufacturer instructions.
  • the activating rinse may further comprise silica.
  • the silica may be a precipitated silica, such as a synthetic amorphous precipitated silica.
  • the silica may be friable under shear.
  • "friable under shear” means that particle size may be reduced with shear.
  • the silica may comprise, for example, Hi-Sil TM EZ 160G silica (commercially available from PPG Industries, Inc.).
  • the silica may be present in an amount of at least 50 ppm, based on total weight of the activating rinse, such as at least 100 ppm, such as at least 150 ppm, and in some instances, no more than 5000 ppm, based on total weight of the activating rinse, such as no more than 1000 ppm, such as no more than 500 ppm.
  • the silica may be present in the activating rinse in an amount of 50 ppm to 5,000 ppm based on the total weight of the activating rinse, such as 100 ppm to 1,000 ppm, such as from 150 ppm to 500 ppm.
  • the activating rinse may optionally further comprise components in addition to the dispersant (i.e., components different than the dispersant), such as nonionic surfactants and auxiliaries conventionally used in the art.
  • additional optional components include surfactants that function as defoamers.
  • Amphoteric and/or nonionic surfactants may be used.
  • Defoaming surfactants may be present, if at all, in amounts of at least at least 0.1 percent by weight, based on total weight of the activating rinse bath, such as at least 0.5 weight percent by weight, and in some instances, may be present in amounts of no more than 1 weight percent, such as no more than 0.7 percent by weight, based on the total weight of the activating rinse bath.
  • defoaming surfactants may be present, if at all, in amounts of 0.1 weight percent to 1 weight percent, such as 0.5 weight percent to 0.7 percent by weight, based on total weight of the activating rinse bath.
  • the activating rinse may further comprise a rheology modifier in addition to the dispersant (i.e., different than the dispersant).
  • the rheology modifier may comprise, for example, polyurethanes, acrylic polymers, lattices, styrene/butadiene, polyvinylalcohols, clays such as attapulgite, bentonite, and other montmorillonite, cellulose based materials such as carboxymethyl cellulose, methyl cellulose, (hydroxypropyl)methyl cellulose or gelatin, gums such as guar and xanthan, or combinations thereof.
  • the activating rinse may be substantially or, in some cases, completely, free of titanium-phosphate particles.
  • substantially free when used in reference to the absence of titanium-phosphate particles in the activating rinse, means that any titanium-phosphate particles present in the activating rinse are not purposefully added and are present in a trace amount of less than 5 ppm, based on the total weight of the activating rinse.
  • completely free when used in reference to the absence of titanium-phosphate particles, means that there are no titanium-phosphate particles at all.
  • the activating rinse of the present invention can be prepared fresh with the above-mentioned ingredients in the concentrations specified or can be prepared in the form of aqueous concentrates in which the concentration of the various ingredients is considerably higher such that the concentrates may be diluted with aqueous medium such as water or are diluted by feeding them into an activating bath containing an activating rinse that has been in use for some time.
  • the activating rinse bath may comprise a chelator.
  • the chelator may comprise, for example, carboxylates such as tartrates, citrates or gluconates, acetate based complexes such as ethylenediaminetetraacetate or nitrilotriacetate, phosphates such as pentasodium triphosphate or tetrapotassium pyrophosphate, phosphonates, polycarboxylates, the acids, esters, or salts of any of the aforementioned, or combinations thereof.
  • the present invention is also directed to a method for treating a metal substrate comprising contacting at least a portion of a surface of the substrate with the activating rinse that is disclosed herein.
  • the method may further include contacting at least a portion of the substrate surface that has been contacted with the activating rinse with a metal phosphate pretreatment composition.
  • the substrate surface to be treated in accordance with the methods of the present invention may be cleaned to remove grease, dirt, or other extraneous matter and/or rinsed prior to applying the activating rinse.
  • Cleaning the substrate surface is often done by employing mild or strong alkaline cleaners, such as are commercially available and conventionally used in metal pretreatment processes.
  • alkaline cleaners suitable for use in the present invention include Chemkleen TM 163, Chemkleen TM 177, Chemkleen TM 181ALP, Chemkleen TM 490MX, and Chemkleen TM 2010LP each of which is commercially available from PPG Industries, Inc.
  • 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.
  • the wet substrate surface optionally may be dried, such as air dried, for example, by using an air knife or warm air blower.
  • the activating rinse can be applied to the substrate surface by spray, roll-coating or immersion techniques.
  • the activating rinse may be applied onto the substrate at a temperature of, for example, 15°C to 50°C, such as 25°C to 35°C for any suitable period of time, such as at least 1 second, such as at least 10 seconds, such as at least 2 minutes, such as at least 5 minutes.
  • the method for treating a substrate may further include contacting at least a portion of the surface that has been contacted with the activating rinse with a metal phosphate pretreatment composition, such as a zinc phosphate pretreatment composition, to form a phosphate coating on the surface of the "activated" substrate.
  • a metal phosphate pretreatment composition such as a zinc phosphate pretreatment composition
  • pretreatment composition refers to a composition that, upon contact with a substrate, reacts with and chemically alters the substrate surface and binds to it to form a protective layer and which contains phosphates of zinc, iron and/or other divalent metals known in the art.
  • the pretreatment composition may comprise zinc ions and phosphate ions.
  • the zinc ion content of the pretreatment composition may be at least 500 ppm, based on total weight of the pretreatment composition, such as at least 800 ppm, and in some instances, may be no more than 1500 pp,, based on total weight of the pretreatment composition, such as no more than 1200 ppm.
  • the zinc ion content of the aqueous acidic compositions may be 500 ppm to 1500 ppm, based on total weight of the pretreatment composition, such as at least 800 ppm to 1200 ppm.
  • the source of the zinc ion may be conventional zinc ion sources, such as zinc nitrate, zinc oxide, zinc carbonate, zinc metal, and the like.
  • the phosphate content of the pretreatment composition may be at least 8000 ppm, based on total weight of the pretreatment composition, such as at least 12000 ppm, and in some cases may be no more than 20000 ppm, based on total weight of the pretreatment composition, such as no more than 14000 ppm.
  • the phosphate content of the pretreatment composition may be 8000 ppm to 20000 ppm, based on total weight of the pretreatment composition, such as 12000 ppm to 14000 ppm.
  • the source of phosphate ion may be phosphoric acid, monosodium phosphate, disodium phosphate, and the like.
  • the pretreatment composition of the present invention may have a pH of at least 2.5, such as at least 3.0, and in some cases, no more than 5.5, such as no more than 3.5.
  • the pretreatment composition may have a pH of 2.5 to 5.5, such as 3.0 to 3.5.
  • the pretreatment composition may also comprise an accelerator.
  • the accelerator may be present in an amount sufficient to accelerate the formation of the zinc phosphate coating and may be present in the pretreatment composition in an amount of at least 500 ppm, based on total weight of the pretreatment composition, such as at least 1000 ppm, such as at least 2500 ppm, and in some instances may be present in an amount of no more than 20000 ppm, based on total weight of the pretreatment composition, such as no more than 10000 ppm, such as no more than 5000 ppm
  • the accelerator may be present in the pretreatment composition in an amount of 500 ppm to 20000 ppm, based on total weight of the pretreatment composition, such as 1000 ppm to 10000 ppm, such as 2500 ppm to 5000 ppm.
  • Useful accelerators may include oximes such as acetaldehyde oxime and acetoxime, nitrites such as sodium nitrite and ammonium nitrite, peroxides such as hydrogen peroxide, or combinations thereof.
  • oximes such as acetaldehyde oxime and acetoxime
  • nitrites such as sodium nitrite and ammonium nitrite
  • peroxides such as hydrogen peroxide, or combinations thereof.
  • the pretreatment composition may also comprise fluoride ion, nitrate ion, and various metal ions, such as nickel ion, cobalt ion, calcium ion, magnesium ion, manganese ion, iron ion, copper ion, and the like.
  • Fluoride ion may be present in the pretreatment composition in an amount of at least 100 ppm, based on total weight of the pretreatment composition, such as at least 250 ppm, and in some instances may be present in an amount of no more than 2500 ppm, based on total weight of the pretreatment composition, such as no more than 1000 ppm, and in some cases may be present in an amount of 100 ppm to 2500 ppm, based on total weight of the pretreatment composition, such as 250 ppm to 1000 ppm.
  • nitrate ion may be present in the pretreatment composition in an amount of at least 1000 ppm, based on total weight of the pretreatment composition, such as at least 2000 ppm, and in some instances may be present in an amount of no more than 10000 ppm, based on total weight of the pretreatment composition, such as no more than 5000 ppm, and in some cases may be present in an amount of 1000 ppm to 10000 ppm, based on total weight of the pretreatment composition, such as 2000 ppm to 5000 ppm.
  • nickel ion may be present in the pretreatment composition in an amount of at least 100 ppm, based on total weight of the pretreatment composition, such as at least 200 ppm, such as at least 300 ppm, and in some instances, may be present in the pretreatment composition in an amount of no more than 1800 ppm, such as no more than 1200 ppm, such as no more than 800 ppm, and in some instances, may be present in the pretreatment composition in an amount of 100 ppm to 1800 ppm, based on total weight of the pretreatment composition, such as 200 ppm to 1200 ppm, such as 300 ppm to 800 ppm.
  • calcium ion may be present in the pretreatment composition in an amount of at least 100 ppm, based on total weight of the pretreatment composition, such as at least 500 ppm, and in some cases, no more than 4000 ppm, based on total weight of the pretreatment composition, such as no more than 2500 ppm, and in some cases may be present in an amount of 100 ppm to 4000 ppm, based on total weight of the pretreatment composition, such as 500 ppm to 2500 ppm.
  • manganese ion may be present in the pretreatment composition in an amount of at least 100 ppm, based on total weight of the pretreatment composition, such as at least 200 ppm, such as at least 500 ppm, and in some cases no more than 1500 ppm, based on total weight of the pretreatment composition, such as no more than 1000 ppm, such as no more than 800 ppm, and in some cases, in an amount of 100 ppm to 1500 ppm, based on total weight of the pretreatment composition, such as from 200 ppm to 1000 ppm, such as 500 ppm to 800 ppm.
  • iron ion may be present in the pretreatment composition in an amount of at least 5 ppm, based on total weight of the pretreatment composition, such as at least 50 ppm, and in some cases, no more than 500 ppm, based on total weight of the pretreatment composition, such as no more than 300 ppm, and in some cases, may be present in the pretreatment composition in an amount of 5 ppm to 500 ppm, such as 50 ppm to 300 ppm.
  • copper ion may be present in the pretreatment composition in an amount of at least 1 ppm based on total weight of the pretreatment composition, such as at least 3 ppm, and in some cases, no more than 30 ppm, based on total weight of the pretreatment composition, such as no more than 15 ppm, and in some cases, may be present in the pretreatment composition in an amount of 1 ppm.
  • the pretreatment composition of the present invention can be prepared fresh with the above mentioned ingredients in the concentrations specified or can be prepared in the form of aqueous concentrates in which the concentration of the various ingredients is considerably higher such that the concentrates may be diluted with aqueous medium such as water or are diluted by feeding them into a zinc phosphating composition which has been in use for some time.
  • Typical concentrates may contain at least 10,000 ppm zinc ions, based on total weight of the pretreatment composition concentrate, such as at least 12,000 ppm zinc ions, such as at least 16,000 ppm zinc ions, and in some cases may contain no more than 100,000 ppm zinc ions, based on total weight of the pretreatment composition concentrate, such as no more than 30,000 ppm zinc ions, such as no more than 20,000 ppm zinc ions, and in some cases may contain 10,000 ppm to 100,000 ppm zinc ions, based on total weight of the pretreatment composition concentrate, such as 12,000 ppm to 30,000 ppm zinc ions, such as from 16,000 ppm to 20,000 ppm zinc ions.
  • the metal phosphate pretreatment composition may be applied to the activated substrate by spray application or immersion of the activated substrate in a phosphate bath comprising said composition at a temperature typically ranging from 20°C to 75°C typically for 1 to 3 minutes.
  • the bath typically may be an acidic phosphate bath and may comprise iron and/or other divalent metals known in the art in addition to zinc ions, as already discussed above.
  • the substrate may be optionally post-rinsed with a chromium or non-chromium containing solution, optionally rinsed with water and/or optionally dried. Paint may then be applied, if desired, such as, by electrodeposition or by conventional spray or roll coating techniques.
  • the present invention is also directed to a metal substrate treated with the pretreatment system that is disclosed herein.
  • the substrate may comprise nucleation sites formed from an activating rinse described above, and may further comprise a metal phosphate coating formed from a metal phosphate pretreatment composition described above applied over the nucleation sites formed on at least a portion of the substrate by the activating rinse.
  • the metal phosphate coating may comprise crystals having a crystal size of at least 0.4 ⁇ m, such as at least 0.5 ⁇ m, such as at least 0.6 ⁇ m, such as at least 0.9 ⁇ m, and in some cases no larger than 4 ⁇ m, such as no larger than 2.7 ⁇ m, such as no larger than 2.5 ⁇ m, such as no larger than 2 ⁇ m.
  • the metal phosphate coating may comprise crystals having a crystal size of 0.4 ⁇ m to 4 ⁇ m, such as 0.5 ⁇ m to 2.5 ⁇ m, such as 0.6 ⁇ m to 2 ⁇ m.
  • Crystal size of a phosphate coating may be determined by methods known to those skilled in the art. For example, a representative area of the panel (i.e., a coated area of approximately 1.27 cm by 1.27 cm with no obvious coating defects) may be selected and an image of the representative area may be acquired an image at either 5,000x or 10,000x magnification using a scanning electron microscope (SEM), such as, for example, a Tescan Vega 2 SEM. The magnification utilized will be dependent on the crystal size as high magnification (10,000x) will be required for crystal sizes that are not distinguishable at 5,000x magnification using an SEM.
  • SEM scanning electron microscope
  • each image may be measured using software known to those skilled in the art, such as, for example, ImageJ (version 1.46), and the representative crystal sizes may be averaged to determine crystal size.
  • ImageJ version 1.46
  • One skilled in the art will recognize that there can be variations in this procedure that retain the essential elements of microscopic imaging and averaging of representative crystal size.
  • the present invention is also directed to an activating stage such as those used in an automotive manufacturing facility.
  • the activating stage comprises immersion of the substrate in a bath which contains the activating rinse that is disclosed herein.
  • the activating rinse is contained within the immersion tank at a temperature of 15°C to 50°C.
  • At least a portion of a surface of the substrate is subjected to the activating rinse by immersing the substrate in the activating rinse for any suitable period of time, e.g. those already described above.
  • a portion of the activated substrate then may be subjected to a phosphatizing step by applying a metal phosphate pretreatment composition, e.g.
  • a zinc phosphate pretreatment composition to the activated substrate.
  • additional activating rinse can be sprayed onto a portion of the activated substrate via a spraying nozzle as the activated substrate is removed from the immersion tank.
  • the spraying nozzle could be a spray bank of nozzles which is positioned downstream from the immersion tank.
  • the activated substrate is phosphatized by applying a metal phosphate pretreatment composition to the activated substrate using techniques that are known in the art such as a spray and/or an immersion technique.
  • the activating stage may comprise a number of spraying nozzles that are used to apply the activating rinse bath onto a least a portion of a substrate.
  • a spray tank Disposed beneath the spraying nozzles is a spray tank which is adapted to collect the activating rinse that exits the spraying nozzles and/or any excess activating rinse that drips off the surface of the activated substrate.
  • the spray tank is connected to the spraying nozzles in a manner that allows the spraying nozzles to utilize the activating rinse that is collected in the spray tank thereby recycling the activating rinse bath.
  • the activated substrate is then phosphatized as described in the preceding paragraph.
  • a coating composition comprising a film-forming resin may be deposited onto at least a portion of the surface of the substrate that has been contacted with the pretreatment composition.
  • Any suitable technique may be used to deposit such a coating composition onto the substrate, including, for example, brushing, dipping, flow coating, spraying and the like.
  • depositing of a coating composition may comprise an electrocoating step wherein an electrodepositable composition is deposited onto a metal substrate by electrodeposition.
  • such depositing of a coating composition comprises a powder coating step.
  • the coating composition may be a liquid coating composition.
  • the coating composition may comprise a thermosetting film-forming resin or a thermoplastic film-forming resin.
  • film-forming resin refers to resins that can form a self-supporting continuous film on at least a horizontal surface of a substrate upon removal of any diluents or carriers present in the composition or upon curing at ambient or elevated temperature.
  • Conventional film-forming resins that may be used include, without limitation, those typically used in automotive OEM coating compositions, automotive refinish coating compositions, industrial coating compositions, architectural coating compositions, coil coating compositions, and aerospace coating compositions, among others.
  • thermosetting refers to resins that "set” irreversibly upon curing or crosslinking, wherein the polymer chains of the polymeric components are joined together by covalent bonds. This property is usually associated with a cross-linking reaction of the composition constituents often induced, for example, by heat or radiation. Curing or crosslinking reactions also may be carried out under ambient conditions. Once cured or crosslinked, a thermosetting resin will not melt upon the application of heat and is insoluble in solvents.
  • thermoplastic refers to resins that comprise polymeric components that are not joined by covalent bonds and thereby can undergo liquid flow upon heating and are soluble in solvents.
  • a coating composition comprising a film-forming resin may be deposited onto the substrate by an electrocoating step wherein an electrodepositable composition is deposited onto the metal substrate by electrodeposition.
  • an electrodepositable composition is deposited onto the metal substrate by electrodeposition.
  • the metal substrate being treated, serving as an electrode, and an electrically conductive counter electrode are placed in contact with an ionic, electrodepositable composition.
  • an adherent film of the electrodepositable composition will deposit in a substantially continuous manner on the metal substrate.
  • such electrodeposition may be carried out at a constant voltage in the range of from 1 volt to several thousand volts, typically between 50 and 500 volts.
  • Current density is usually between 1.0 ampere and 15 amperes per square foot (10.8 to 161.5 amperes per square meter) and tends to decrease quickly during the electrodeposition process, indicating formation of a continuous self-insulating film.
  • the electrodepositable coating composition may comprise a resinous phase dispersed in an aqueous medium wherein the resinous phase comprises: (a) an active hydrogen group-containing ionic electrodepositable resin, and (b) a curing agent having functional groups reactive with the active hydrogen groups of (a).
  • the electrodepositable compositions may contain for instance, as a main film-forming polymer, an active hydrogen-containing ionic, often cationic, electrodepositable resin.
  • an active hydrogen-containing ionic, often cationic, electrodepositable resin A wide variety of electrodepositable film-forming resins are known and can be used in the present invention so long as the polymers are "water dispersible,” i.e., adapted to be solubilized, dispersed or emulsified in water.
  • the water dispersible polymer is ionic in nature, that is, the polymer will contain anionic functional groups to impart a negative charge or may contain cationic functional groups to impart a positive charge.
  • film-forming resins suitable for use in anionic electrodepositable coating compositions are base-solubilized, carboxylic acid containing 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.
  • 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 are base-solubilized, carboxylic acid containing 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
  • Still another suitable electrodepositable film-forming resin comprises an alkyd-aminoplast vehicle, i.e., a vehicle containing an alkyd resin and an amine-aldehyde resin.
  • Yet another anionic electrodepositable resin composition comprises mixed esters of a resinous polyol, such as is described in United States Patent No. 3,749,657 at col. 9, lines 1 to 75 and col. 10, lines 1 to 13.
  • Other acid functional polymers can also be used, such as phosphatized polyepoxide or phosphatized acrylic polymers as are known to those skilled in the art.
  • the active hydrogen-containing ionic electrodepositable resin (a) is cationic and capable of deposition on a cathode.
  • cationic film-forming resins include amine salt group-containing resins, such as the acid-solubilized reaction products of polyepoxides and primary or secondary amines, such as those described in United States Patent Nos. 3,663,389 ; 3,984,299 ; 3,947,338 ; and 3,947,339 .
  • these amine salt group-containing resins are used in combination with a blocked isocyanate curing agent. The isocyanate can be fully blocked, as described in United States Patent No.
  • film-forming resins can also be selected from cationic acrylic resins, such as those described in United States Patent Nos. 3,455,806 and 3,928,157 .
  • quaternary ammonium salt group-containing resins can also be employed, such as those formed from reacting an organic polyepoxide with a tertiary amine salt as described in United States Patent Nos. 3,962,165 ; 3,975,346 ; and 4,001,101 .
  • examples of other cationic resins are ternary sulfonium salt group-containing resins and quaternary phosphonium salt-group containing resins, such as those described in United States Patent Nos. 3,793,278 and 3,984,922 , respectively.
  • film-forming resins which cure via transesterification such as described in European Patent No. EP0012463 can be used.
  • cationic compositions prepared from Mannich bases such as described in United States Patent No. 4,134,932 , can be used.
  • the resins present in the electrodepositable composition are positively charged resins which contain primary and/or secondary amine groups, such as described in United States Patent Nos. 3,663,389 ; 3,947,339 ; and 4,116,900 .
  • a polyketimine derivative of a polyamine such as diethylenetriamine or triethylenetetraamine, is reacted with a polyepoxide.
  • the reaction product is neutralized with acid and dispersed in water, free primary amine groups are generated.
  • equivalent products are formed when polyepoxide is reacted with excess polyamines, such as diethylenetriamine and triethylenetetraamine, and the excess polyamine vacuum stripped from the reaction mixture, as described in United States Patent Nos. 3,663,389 and 4,116,900 .
  • the active hydrogen-containing ionic electrodepositable resin may be present in the electrodepositable composition in an amount of 1 to 60 percent by weight, such as 5 to 25 percent by weight, based on total weight of the electrodeposition bath.
  • the resinous phase of the electrodepositable composition often further comprises a curing agent adapted to react with the active hydrogen groups of the ionic electrodepositable resin.
  • a curing agent adapted to react with the active hydrogen groups of the ionic electrodepositable resin.
  • both blocked organic polyisocyanate and aminoplast curing agents are suitable for use in the present invention.
  • Aminoplast resins may be used as the curing agent for anionic electrodeposition, are the condensation products of amines or amides with aldehydes.
  • suitable amines or amides are melamine, benzoguanamine, urea and similar compounds.
  • the aldehyde employed is formaldehyde, although products can be made from other aldehydes, such as acetaldehyde and furfural.
  • the condensation products contain methylol groups or similar alkylol groups depending on the particular aldehyde employed.
  • these methylol groups are etherified by reaction with an alcohol, such as a monohydric alcohol containing from 1 to 4 carbon atoms, such as methanol, ethanol, isopropanol, and n-butanol.
  • an alcohol such as a monohydric alcohol containing from 1 to 4 carbon atoms, such as methanol, ethanol, isopropanol, and n-butanol.
  • Aminoplast resins are commercially available from American Cyanamid Co. under the trademark CYMEL and from Monsanto Chemical Co. under the trademark RESIMENE.
  • the aminoplast curing agents are often utilized in conjunction with the active hydrogen containing anionic electrodepositable resin in amounts ranging from 5 percent to 60 percent by weight, such as from 20 percent to 40 percent by weight, the percentages based on the total weight of the resin solids in the electrodepositable composition.
  • blocked organic polyisocyanates are often used as the curing agent in cathodic electrodeposition compositions.
  • the polyisocyanates can be fully blocked as described in United States Patent No. 3,984,299 at col. 1, lines 1 to 68, col. 2, and col. 3, lines 1 to 15, or partially blocked and reacted with the polymer backbone as described in United States Patent No. 3,947,338 at col. 2, lines 65 to 68, col. 3, and col. 4 lines 1 to 30.
  • blocked is meant that the isocyanate groups have been reacted with a compound so 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 usually between 90°C and 200°C.
  • Suitable polyisocyanates include aromatic and aliphatic polyisocyanates, including cycloaliphatic polyisocyanates and representative examples include diphenylmethane-4,4'-diisocyanate (MDI), 2,4- or 2,6-toluene diisocyanate (TDI), including mixtures thereof, p-phenylene diisocyanate, tetramethylene and hexamethylene diisocyanates, dicyclohexylmethane-4,4'-diisocyanate, isophorone diisocyanate, mixtures of phenylmethane-4,4'-diisocyanate and polymethylene polyphenylisocyanate.
  • MDI diphenylmethane-4,4'-diisocyanate
  • TDI 2,4- or 2,6-toluene diisocyanate
  • p-phenylene diisocyanate tetramethylene and hexamethylene diisocyanates
  • Higher polyisocyanates such as triisocyanates can be used.
  • An example would include triphenylmethane-4,4',4"-triisocyanate.
  • Isocyanate prepolymers with polyols such as neopentyl glycol and trimethylolpropane and with polymeric polyols such as polycaprolactone diols and triols (NCO/OH equivalent ratio greater than 1) can also be used.
  • the polyisocyanate curing agents are typically utilized in conjunction with the active hydrogen containing cationic electrodepositable resin in amounts ranging from 5 percent to 60 percent by weight, such as from 20 percent to 50 percent by weight, the percentages based on the total weight of the resin solids of the electrodepositable composition.
  • the electrodepositable coating compositions described herein may in particular be in the form of an aqueous dispersion.
  • the average particle size of the resinous phase is generally less than 1.0 micrometer and usually less than 0.5 micrometers, often less than 0.15 micrometers.
  • the concentration of the resinous phase in the aqueous medium is often at least 1 percent by weight, such as from 2 to 60 percent by weight, based on total weight of the aqueous dispersion.
  • concentration of the resinous phase in the aqueous medium is often at least 1 percent by weight, such as from 2 to 60 percent by weight, based on total weight of the aqueous dispersion.
  • coating compositions are in the form of resin concentrates, they generally have a resin solids content of 20 to 60 percent by weight based on weight of the aqueous dispersion.
  • the electrodepositable coating compositions described herein are often supplied as two components: (1) a clear resin feed, which includes generally the active hydrogen-containing ionic electrodepositable resin, i.e., the main film-forming polymer, the curing agent, and any additional water-dispersible, non-pigmented components; and (2) a pigment paste, which generally includes one or more colorants (described below), a water-dispersible grind resin which can be the same or different from the main-film forming polymer, and, optionally, additives such as wetting or dispersing aids.
  • Electrodeposition bath components (1) and (2) are dispersed in an aqueous medium which comprises water and, usually, coalescing solvents.
  • the aqueous medium may contain a coalescing solvent.
  • Useful coalescing solvents are often hydrocarbons, alcohols, esters, ethers and ketones. Coalescing solvents that may be used may be alcohols, polyols and ketones. Specific coalescing solvents include isopropanol, butanol, 2-ethylhexanol, isophorone, 2-methoxypentanone, ethylene and propylene glycol and the monoethyl monobutyl and monohexyl ethers of ethylene glycol.
  • the amount of coalescing solvent is generally between 0.01 and 25 percent, such as from 0.05 to 5 percent by weight based on total weight of the aqueous medium.
  • 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 120 to 250°C, such as from 120 to 190°C, for a period of time ranging from 10 to 60 minutes.
  • the thickness of the resultant film is from 10 to 50 micrometers.
  • a powder coating composition may then be deposited onto at least a portion of the surface of the substrate that has been contacted with the pretreatment 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 (a) a film forming polymer having a reactive functional group; and (b) a curing agent that is reactive with the functional group.
  • 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.
  • curable powder coating compositions generally 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 US Patent No. 7,432,333 , assigned to PPG Industries, Inc.); and 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 US Patent No. 6,797,387 , assigned to PPG Industries, Inc.).
  • 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)olefin, (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 150°C to 200°C, such as from 170°C to 190°C, for a period of time ranging from 10 to 20 minutes.
  • the thickness of the resultant film is from 50 to 125 micrometers.
  • 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 solventborne coating compositions known in the art.
  • 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 solventborne 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 Ultraviolet or Infrared.
  • liquid coating compositions examples include the SPECTRACRON ® line of solventbased coating compositions, the AQUACRON ® line of waterbased coating compositions, and the RAYCRON ® line of UV cured coatings (all commercially available from PPG Industries, Inc.).
  • Suitable film forming polymers that may be used in the liquid coating composition of the present invention 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)olefin, (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 combinations thereof.
  • 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.
  • the terms "pigment” and "colored filler” can be used interchangeably.
  • 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.
  • 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 COLORANTS commercially available from Accurate Dispersions division of Eastman Chemical, Inc.
  • AQUA-CHEM 896 commercially available from Degussa, Inc.
  • CHARISMA COLORANTS and MAXITONER INDUSTRIAL COLORANTS commercially available from Accurate Dispersions division of Eastman Chemical, Inc.
  • 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. 6,875,800 B2 .
  • 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 United States Patent Application Publication 2005-0287348 A1, filed June 24, 2004 , U.S. Provisional Application No. 60/482,167 filed June 24, 2003 , and United States Patent Application Serial No. 11/337,062, filed January 20, 2006 .
  • 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 .
  • 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 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 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 U.S. Application Serial No. 10/892,919 filed July 16, 2004 .
  • 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 application of the activating rinse disclosed herein to a surface of the metal substrate prior to application of the metal phosphate pretreatment composition enables the bath containing the metal phosphate pretreatment composition to be maintained (and therefore the metal phosphate pretreatment composition to be applied) at a lower temperature than methods employing conventional activating rinses, such as Jernstedt type activators or other zinc phosphate activating rinses comprising metal phosphate particles having a D 90 particle size of greater than 10 ⁇ m.
  • conventional activating rinses such as Jernstedt type activators or other zinc phosphate activating rinses comprising metal phosphate particles having a D 90 particle size of greater than 10 ⁇ m.
  • the phosphate bath containing the metal phosphate pretreatment composition may be at a temperature of no greater than 60°C, such as no greater than 50°C, such as no greater than 40°C, such as no greater than 30°C, such as no greater than 25°C.
  • the temperature of the bath containing the metal phosphate pretreatment composition may range from 20°C to 60°C, such as from 25°C to 50°C, such as from 30°C to 40°C.
  • application of the activating rinse disclosed herein to a surface of the metal substrate prior to application of the metal phosphate pretreatment composition may enable the bath containing the metal phosphate pretreatment composition to be maintained at room temperature (20°C).
  • the term “substantially free” means that a particular material is not purposefully added to the activating rinse, and is only present as an impurity in a trace amount of less than 1% by weight based on a total weight of the activating rinse.
  • the term “completely free” means that an activating rinse does not comprise a particular material, i.e., the activating rinse comprises 0% by weight of such material.
  • Composition 2A 1.85 grams of the above dispersion of zinc phosphate was mixed per liter of deionized water, to give an activator bath with a zinc phosphate concentration of 0.5 grams per liter.
  • Composition 2B A micromedia milled (MMM) dispersion was prepared in the same manner as was Composition 2A. To make Composition 2B, 5.55 grams of the dispersion of zinc phosphate were mixed per liter of deionized water, to give an activator bath with a zinc phosphate concentration of 1.5 grams per liter.
  • MMM micromedia milled
  • Compositions 1A to ID, 2A and 2B are not according to the invention.
  • Activated panels then were immersed in a zinc phosphate pretreatment bath (made from Chemfos 700, commercially available from PPG Industries, Inc., prepared according to instructions provided by the supplier) at a bath temperature of either 22.8°C (73°F), 32.2°C (90°F), 37.8°C (100°F), or 51.7°C (125°F) (as indicated in Table 1) for 2 minutes. All panels then were spray rinsed with DI water for 20-30 seconds. Panels were warm air dried using a Hi-Velocity handheld blow-dryer made by Oster ® (model number 078302-300-000) on high-setting at a temperature of about 50-55°C until the panel was dry (about 1-5 minutes).
  • one of the panels was used to determine phosphate coating completeness.
  • the other panel was cut in half to yield two panels each 5.1 ⁇ 7.6 cm (2" ⁇ 3") and one of the half panels was used to determine coating weight and the other half panel was used to determine average crystal size.
  • Zinc phosphate coating weight was determined on one of the 5.1 ⁇ 7.6 cm (2" ⁇ 3") panels by the weigh-strip-weigh method. Treated panels were weighed on an analytical balance to the nearest 0.1 mg. Cold roll steel panels were immersed in a solution comprised of 100 g sodium hydroxide pellets and 25 milliliters 98% triethanolamine diluted to 1 liter total volume with deionized water for 1.5 minutes to dissolve all of the zinc phosphate coating off of the panels without dissolution of the substrate.
  • Hot dipped galvanized steel panels were immersed in a solution comprised of 16 g ammonium dichromate [(NH 4 ) 2 Cr 2 O 7 ] dissolved into 1 liter concentrated ammonium hydroxide for 2 minutes to dissolve all of the zinc phosphate coating off of the panels without dissolution of the substrate.
  • panels were rinsed thoroughly with deionized water, wiped gently with a tissue to remove any loosely-adherent phosphate coating, rinsed with deionized water again, and dried in warm air by using a Hi-Velocity handheld blow-dryer made by Oster ® (model number 078302-300-000) on high-setting at a temperature of about 50-55°C until the panel was dry, typically 1-5 minutes.
  • the dried panel was then weighed, and the weight loss was used to calculate the coating weight per unit area.
  • Zinc phosphate average crystal size was determined on 5.1 ⁇ 7.6 cm (2" ⁇ 3") panels by first selecting a representative area of the panel, i.e., a coated area of approximately 1.27 cm by 1.27 cm (0.5 inch by 0.5 inch) near the center of the 5.1 ⁇ 7.6 cm (2" ⁇ 3") panel with no obvious coating defects, then acquiring an image at either 5,000x or 10,000x magnification using a Tescan Vega 2 scanning electron microscope (SEM). The magnification was determined by the crystal size with the 10,000x magnification required for smaller crystal sizes.
  • SEM Tescan Vega 2 scanning electron microscope
  • Coating completeness (based on a qualitative scale estimating the % bare area), coating weight (mg/ft 2 ) and crystal size for the treated panels are reported in Table 1, below. In Tables 1 to 4 and 6, 1.0 mg/ft 2 is equal to 0.01 g/m 2 .
  • an activating rinse that includes either a metal sulfate salt or pulverized metal phosphate particles having a D 90 of less than 1 ⁇ m results in decreased coating weight and crystal size of a subsequently applied phosphate coating compared to the use of a conventional Jernstedt type activating rinse or an activating rinse that does not include a metal sulfate salt.
  • a metal sulfate salt or pulverized metal phosphate particles having a D 90 of less than 1 ⁇ m in the activating rinse allows for the subsequent application of a complete phosphate coating at low temperatures, such as 22.8°C (73°F), whereas activating rinses that do not include a metal sulfate salt or pulverized metal phosphate particles having a D 90 of less than 1 ⁇ m do not have complete phosphate coatings at such low temperatures.
  • Panels were then immersed in a zinc phosphate pretreatment bath (made from Chemfos 700 LT, commercially available from PPG Industries, Inc., prepared according to instructions provided by the supplier) (bath temperature 30°C (86°F) for 30, 60, 90, or 120 seconds (as shown in Table 2). Panels then were spray rinsed with DI water for 20-30 seconds. Panels were warm air dried using a Hi-Velocity handheld blow-dryer made by Oster ® (model number 078302-300-000) on high-setting at a temperature of about 50-55°C until the panel was dry (about 1-5 minutes).
  • Zinc phosphate coating completeness of the treated panels was evaluated as described in Example 1.
  • Zinc phosphate coating weight on the treated panels was determined by the weigh-strip-weigh method described in Example 1.
  • Coating completeness and coating weight (mg/ft 2 ) of the treated panels are reported in Table 2, below.
  • Activator Phospate Coating Completeness Coating Weight (mg/ft 2 ) Zinc phosphate treatment time 30 seconds RC30, 1.1 g/L 25% 72 RC30, 3.3 g/L 50% 86 Composition 2A 90% 83 Com position 2B 95% 85 Zinc phosphate treatment time 60 seconds RC30, 1.1 g/L 60% 119 RC30, 3.3 g/L 90% 109 Composition 2A 100% 86 Composition 2B 100% 88 Zinc phosphate treatment time 90 seconds RC30, 1.1 g/L 100% 176 RC30, 3.3 g/L 100% 130 Composition 2A 100% 118 Composition 2B 100% 104 Zinc phosphate treatment time 120 seconds RC30, 1.1 g/L 100% 187 RC30, 3.3 g/L 100% 122 Composition 2A 100% 119 Composition 2B 100% 83
  • Panels were then immersed in a zinc phosphate pretreatment bath (made from Chemfos 700 AL, commercially available from PPG Industries, Inc., prepared according to instructions provided by the supplier) (bath temperature 30°C (86°F) and 51.7°C (125°F)) for 2 minutes (as shown in Table 2). Panels then were spray rinsed with DI water for 20-30 seconds. Panels were warm air dried using a Hi-Velocity handheld blow-dryer made by Oster ® (model number 078302-300-000) on high-setting at a temperature of about 50-55°C until the panel was dry (about 1-5 minutes).
  • a zinc phosphate pretreatment bath made from Chemfos 700 AL, commercially available from PPG Industries, Inc., prepared according to instructions provided by the supplier
  • Panels then were spray rinsed with DI water for 20-30 seconds.
  • Panels were warm air dried using a Hi-Velocity handheld blow-dryer made by Oster ® (model number 078302-300-000) on
  • one of the panels was used to determine phosphate coating completeness.
  • the other panel was cut in half to yield two panels each 5.1 ⁇ 7.6 cm (2" ⁇ 3") and one of the half panels was used to determine coating weight and the other half panel was used to determine average crystal size.
  • Zinc phosphate coating completeness and coating weight were determined by the weigh-strip-weigh method described in Example 1.
  • Zinc phosphate average crystal size was determined as described in Example 1.
  • an activating rinse that includes a metal sulfate salt results in decreased phosphate crystal size of a subsequently applied phosphate coating compared to the use of an activating rinse that does not include a metal sulfate salt. Additionally, the use of an activating rinse that includes a metal sulfate salt generally improved phosphate coating completeness of a subsequently applied phosphate coating at low-temperature compared to the use of an activating rinse that does not include a metal sulfate salt.
  • Panels were then immersed in a zinc phosphate pretreatment bath (made from Chemfos 700 AL, commercially available from PPG Industries, Inc., prepared according to instructions provided by the supplier) (bath temperature 30°C (86°F) or 51.7°C (125°F), as shown in Table 2) for 2 minutes. Panels then were spray rinsed with DI water for 20-30 seconds. Panels were warm air dried using a Hi-Velocity handheld blow-dryer made by Oster ® (model number 078302-300-000) on high-setting at a temperature of about 50-55°C until the panel was dry (about 1-5 minutes).
  • ED7000 electrocoat made from materials provided by PPG Industries, Inc. and applied according to the manufacturer's instructions. Two panels were subsequently coated with a typical automotive decorative layering system topcoat. The panels that were not topcoated were subjected to GMW 14872 cyclic corrosion testing for 48 days. The topcoated panels were exposed to Volvo Florida Exposure corrosion testing for six months.
  • Comparative Example I was made according to Example 2 of US Publication 2012/0160129A1 to Inbe. RC and Composition 2A were made as described above.
  • Comparative I The dispersion of Comparative I was characterized as follows and was compared to the activation properties of Composition 2A.
  • Particle size (D 10 , D 50 , and D 90 ) were measured using a Mastersizer 2000 (available from Malvern Instruments, Ltd., of Malvern, Worcestershire, UK). A laser beam (0.633 mm diameter, 633 nm wavelength) was directed through a dispersion of particles (in deionized water to 2-3% obscuration). The light scattering of the dispersion was measured (measurement parameters 25°C, 2200 RPM, 30 sec premeasurement delay, 10 sec background measurement, 10 sec sample measurement) and the data were analyzed by computer software (Malvern Mastersizer 2000 software, version 5.60) to generate a particle size distribution, from which particle sizes (mean, D 10 , D 50 , and D 90 ) were determined and are reported in Table 5. TABLE 5.
  • Activated panels (Comparative Example I or Composition 2A) then were immersed in a zinc phosphate pretreatment bath (made from Chemfos 700AL, commercially available from PPG Industries, Inc., prepared according to instructions provided by the supplier) at a bath temperature of 25.5°C (78°F) for 2 minutes. All panels then were spray rinsed with DI water for 20-30 seconds. Panels were warm air dried using a Hi-Velocity handheld blow-dryer made by Oster ® (model number 078302-300-000) on high-setting at a temperature of about 50-55°C until the panel was dry (about 1-5 minutes).
  • a zinc phosphate pretreatment bath made from Chemfos 700AL, commercially available from PPG Industries, Inc., prepared according to instructions provided by the supplier
  • All panels then were spray rinsed with DI water for 20-30 seconds. Panels were warm air dried using a Hi-Velocity handheld blow-dryer made by Oster ® (model number 078302-300-000) on high-setting
  • one of the panels was used to determine phosphate coating completeness.
  • the other panel was cut in half to yield two panels each 5.1 ⁇ 7.6 cm (2" ⁇ 3") and one of the half panels was used to determine coating weight and the other half panel was used to determine average crystal size.
  • Zinc phosphate coating completeness and coating weight were determined as described in Example 1.
  • Zinc phosphate average crystal size was determined as described in Example 1. Data are reported in Table 6, below. TABLE 6.
  • Cold rolled steel Composition 2A 100% 1.20 94
  • Composition 2A gave 100% coating completeness on CRS and 95% coating completeness on aluminum alloy 6022 panels.
  • Comparative I gave only 60% coating completeness on CRS and 40% coating completeness on aluminum alloy 6022 panels.
  • Both Composition 2A and Comparative I gave 100% coating completeness on EG steel panels, but the skilled artisan understands that EG panels are typically 100% coated.
  • crystal size was smaller and coating weight was lower on panels treated with Composition 2A than those treated with Comparative I, regardless of substrate.

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Claims (12)

  1. Liquide de rinçage activateur pour traitement d'un substrat métallique, comprenant :
    - une dispersion de particules de phosphate de métal, présentant une taille de particules D90 d'au plus 10 µm, lequel phosphate de métal comprend des métaux divalents ou trivalents ou des combinaisons de tels métaux,
    - un agent dispersant comprenant un dispersant non-ionique, lequel dispersant non-ionique comprend un polymère non-ionique comportant des résidus de monomères, y compris d'oxyde de propylène, d'oxyde d'éthylène, de styrène, d'un monoacide tel que l'acide acrylique ou l'acide méthacrylique, d'un diacide tel que l'acide maléique ou l'acide itaconique, d'un anhydride d'acide tel que l'anhydride acrylique ou l'anhydride maléique, ou de combinaisons de tels monomères,
    - et un sel de type sulfate de métal,
    étant entendu que le métal du sulfate de métal comprend du nickel, du cobalt, du zinc, du fer, du cuivre, ou des combinaisons de ceux-ci, et étant entendu que la taille de particules D90, déterminée selon le procédé indiqué dans la description, se rapporte à une distribution en volume des particules dans laquelle 90 % des particules ont un diamètre de valeur inférieure à D90.
  2. Liquide de rinçage activateur conforme à la revendication 1, dans lequel des dispersants ioniques se trouvent présents en une proportion inférieure à 1 %, en poids rapporté au poids total du liquide de rinçage activateur.
  3. Liquide de rinçage activateur conforme à l'une des revendications précédentes, dans lequel l'ion sulfate du sel de type sulfate de métal se trouve présent en une proportion de 5 à 5000 ppm par rapport au poids total du liquide de rinçage activateur.
  4. Liquide de rinçage activateur conforme à l'une des revendications précédentes, dans lequel les particules de phosphate de métal présentent une taille de particules D90 d'au plus 1 µm.
  5. Liquide de rinçage activateur conforme à l'une des revendications précédentes, dans lequel plus de 90 % des particules de phosphate de métal présentes dans la composition du liquide de rinçage activateur sont pulvérisées, étant entendu que des particules « pulvérisées » désignent des particules présentant un rapport variable de leur longueur à leur largeur.
  6. Liquide de rinçage activateur conforme à l'une des revendications précédentes, lequel liquide de rinçage activateur comprend un système multi-composant, dans lequel la dispersion de particules de phosphate de métal et l'agent dispersant forment une partie d'un premier composant et le sel de type sulfate de métal forme une partie d'un deuxième composant.
  7. Liquide de rinçage activateur conforme à l'une des revendications précédentes, pour lequel la taille de particules D90 est mesurée à partir d'un échantillon du liquide de rinçage activateur qui a subi une sonication.
  8. Procédé de traitement d'un substrat métallique, comportant le fait de mettre au moins une partie d'une surface du substrat en contact avec un liquide de rinçage activateur conforme à l'une des revendications précédentes.
  9. Procédé conforme à la revendication 9, comportant en outre le fait de mettre au moins une partie de la surface du substrat, qui a été mise en contact avec le liquide de rinçage activateur, en contact avec une composition de prétraitement par phosphate de métal, dans lequel la mise en contact de la surface du substrat avec la composition de prétraitement par phosphate de métal comporte de préférence le fait de plonger le substrat dans un bain qui comprend la composition de prétraitement par phosphate de métal et dont la température vaut de 20 à 60 °C et de préférence de 20 à 25 °C.
  10. Substrat métallique traité avec un liquide de rinçage activateur conforme à l'une des revendications 1 à 8.
  11. Substrat conforme à la revendication 10, comprenant en outre un revêtement au phosphate lequel revêtement au phosphate comprend de préférence des cristaux de phosphate présentant une taille de cristal de 0,4 à 4 µm, et de préférence de 0,9 à 2,7 µm.
  12. Substrat conforme à l'une des revendications 10 et 11, lequel substrat est de l'acier galvanisé par immersion à chaud.
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Families Citing this family (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
KR20190039998A (ko) * 2016-08-12 2019-04-16 피피지 인더스트리즈 오하이오 인코포레이티드 전처리 조성물
CA3090532A1 (fr) * 2018-02-09 2019-08-15 Ppg Industries Ohio, Inc. Systeme pour traiter un substrat metallique
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Family Cites Families (35)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3984922A (en) 1944-10-10 1976-10-12 Leo Rosen Rotors
DE1546840C3 (de) 1965-02-27 1975-05-22 Basf Ag, 6700 Ludwigshafen Verfahren zum Herstellen von Überzügen
US3975346A (en) 1968-10-31 1976-08-17 Ppg Industries, Inc. Boron-containing, quaternary ammonium salt-containing resin compositions
US4001101A (en) 1969-07-10 1977-01-04 Ppg Industries, Inc. Electrodeposition of epoxy compositions
US3663389A (en) 1970-04-17 1972-05-16 American Cyanamid Co Method of electrodepositing novel coating
US3984299A (en) 1970-06-19 1976-10-05 Ppg Industries, Inc. Process for electrodepositing cationic compositions
US3962165A (en) 1971-06-29 1976-06-08 Ppg Industries, Inc. Quaternary ammonium salt-containing resin compositions
US3947338A (en) 1971-10-28 1976-03-30 Ppg Industries, Inc. Method of electrodepositing self-crosslinking cationic compositions
US3947339A (en) 1971-12-01 1976-03-30 Ppg Industries, Inc. Method of electrodepositing primary amine group-containing cationic resins
US3749657A (en) 1972-01-04 1973-07-31 Ppg Industries Inc Treatment of electrodeposition rinse water
US3793278A (en) 1972-03-10 1974-02-19 Ppg Industries Inc Method of preparing sulfonium group containing compositions
US3928157A (en) 1972-05-15 1975-12-23 Shinto Paint Co Ltd Cathodic treatment of chromium-plated surfaces
DE2707405C3 (de) 1976-07-19 1987-12-03 Vianova Kunstharz Ag, Werndorf Verfahren zur Herstellung von Bindemitteln für die Elektrotauchlackierung
BE857754A (fr) 1976-08-18 1978-02-13 Celanese Polymer Special Co Composition de resine pour revetements, notamment par electrodeposition cathodique
DE2711425A1 (de) 1977-03-16 1978-09-21 Basf Ag Lackbindemittel fuer die kathodische elektrotauchlackierung
US4134866A (en) 1977-06-03 1979-01-16 Kansai Paint Company, Limited Aqueous cationic coating from amine-epoxy adduct, polyamide, and semi-blocked polyisocyanate, acid salt
ZA796485B (en) 1978-12-11 1980-11-26 Shell Res Ltd Thermosetting resinous binder compositions,their preparation,and use as coating materials
JP3451334B2 (ja) * 1997-03-07 2003-09-29 日本パーカライジング株式会社 金属のりん酸塩皮膜化成処理前の表面調整用前処理液及び表面調整方法
JP3451337B2 (ja) * 1998-07-21 2003-09-29 日本パーカライジング株式会社 金属のりん酸塩被膜化成処理前の表面調整用処理液及び表面調整方法
MY129412A (en) * 1998-07-21 2007-03-30 Nihon Parkerizing Conditioning liquid and conditioning process used in pretreatment for formation of phosphate layer on the metallic surface
US6723178B1 (en) * 1999-08-16 2004-04-20 Henkel Corporation Process for forming a phosphate conversion coating on metal
US6797387B2 (en) 2000-09-21 2004-09-28 Ppg Industries Ohio Inc. Modified aminoplast crosslinkers and powder coating compositions containing such crosslinkers
US6875800B2 (en) 2001-06-18 2005-04-05 Ppg Industries Ohio, Inc. Use of nanoparticulate organic pigments in paints and coatings
US6894086B2 (en) 2001-12-27 2005-05-17 Ppg Industries Ohio, Inc. Color effect compositions
US7091286B2 (en) 2002-05-31 2006-08-15 Ppg Industries Ohio, Inc. Low-cure powder coatings and methods for using the same
ES2561465T3 (es) * 2004-02-20 2016-02-26 Chemetall Gmbh Disolución concentrada para preparar un acondicionador de superficies
US7438972B2 (en) 2004-06-24 2008-10-21 Ppg Industries Ohio, Inc. Nanoparticle coatings for flexible and/or drawable substrates
EP1930474B1 (fr) * 2005-08-19 2015-09-16 Chemetall GmbH Composition de conditionnement de surface, procédé de fabrication idoine, et procédé de conditionnement de surface
JP2007077500A (ja) * 2005-08-19 2007-03-29 Nippon Paint Co Ltd 表面調整用組成物及び表面調整方法
EP1930473B1 (fr) * 2005-08-19 2016-04-06 Nippon Paint Co., Ltd. Composition de conditionnement de surface et son procédé de production, et procédé de conditionnement de surface
JP2007204835A (ja) * 2006-02-03 2007-08-16 Nippon Paint Co Ltd 表面調整用組成物及び表面調整方法
US20100031851A1 (en) 2006-04-07 2010-02-11 Toshio Inbe Surface conditioning composition, method for producing the same, and surface conditioning method
JP5462467B2 (ja) * 2008-10-31 2014-04-02 日本パーカライジング株式会社 金属材料用化成処理液および処理方法
US9255332B2 (en) * 2013-09-05 2016-02-09 Ppg Industries Ohio, Inc. Activating rinse and method for treating a substrate
TWI722689B (zh) 2019-11-29 2021-03-21 財團法人工業技術研究院 適用於偏移正交振幅調變濾波器組多載波空間多工系統之偵測器及干擾消除方法

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RU2713522C1 (ru) 2020-02-05
BR112018071755A2 (pt) 2019-02-19
AU2017257618A1 (en) 2018-11-15
US20170306498A1 (en) 2017-10-26
MX2023007056A (es) 2023-06-23
SG11201808795UA (en) 2018-11-29
EP3449034A1 (fr) 2019-03-06
CN109072442A (zh) 2018-12-21
WO2017189519A1 (fr) 2017-11-02
KR20210030508A (ko) 2021-03-17
ES2927223T3 (es) 2022-11-03
EP4039850A1 (fr) 2022-08-10
KR20190002545A (ko) 2019-01-08
MX2018012690A (es) 2019-07-01

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