KR102367049B1 - Pretreatment composition - Google Patents

Abstract

The present invention relates to a method of treating a substrate comprising contacting at least a portion of the surface of the substrate with a first composition comprising a source of lanthanide and an oxidizing agent. The invention also relates to a substrate obtainable by said process.

Description

Pretreatment composition {PRETREATMENT COMPOSITION}

CROSS-REFERENCE TO RELATED APPLICATIONS

This application relates to U.S. Provisional Application No. 62/374,188, filed on August 12, 2016 (titled "Sealing Composition") and U.S. Provisional Application No. 62/374,199, filed on August 12, 2016, entitled "Pretreatment" composition"), both of which are incorporated herein by reference in their entirety.

technical field

The present invention relates to a sealing composition and a method for treating a metal substrate. The present invention also relates to a coated metallic substrate.

It is common to use protective coatings on metal substrates for improved corrosion resistance and paint adhesion. Conventional techniques for coating the substrate include those involving pretreatment of the metal substrate with a chromium-containing composition. However, the use of such chromate-containing compositions poses environmental and health concerns.

Consequently, a chromate-free pretreatment composition was developed. The composition is generally based on a chemical mixture that reacts with and binds to the substrate surface to form a protective layer. For example, pretreatment compositions based on Group IIIB metals or Group IVB metals have become more common. Such compositions often contain free fluoride (i.e., fluoride available as an isolated ion in the pretreatment composition, as opposed to fluoride covalently or ionically bonded to another elemental cation (eg, a Group IIIB or IVB metal ion or hydrogen ion)). contains a source of Free fluoride may promote deposition of a Group IIIB or IVB metal coating by etching the surface of the metal substrate. Nevertheless, the corrosion resistance ability of these pretreatment compositions was generally significantly inferior to conventional chromium-containing pretreatments.

It would be desirable to provide metal substrate treatment compositions and methods that overcome at least some of the disadvantages of the prior art described above, including the environmental disadvantages associated with the use of chromates. It would also be desirable to provide metal substrate treatment compositions and methods that provide corrosion resistance properties equivalent to or even superior to those provided using phosphate- or chromium-containing conversion coatings. It would also be desirable to provide a related coated metallic substrate.

Disclosed herein is a system for treating a substrate comprising a first composition for contacting at least a portion of a substrate, the first composition comprising a lanthanide series elemental cation and an oxidizing agent.

Also disclosed herein is a method of treating a substrate comprising contacting at least a portion of the substrate with a first composition comprising a lanthanide series elemental cation and an oxidizing agent.

A substrate obtainable by the system and/or method is also disclosed.

1 shows a schematic diagram illustrating the thickness of a layer of a second composition on the surface of a substrate.
2 shows the XPS depth profile of a substrate treated with LiOH or Li ₂ CO ₃ . The two plots are averages across the surface with measurements taken at 50 nm. Data represent lithium present in the 0-45 nm depth range.

As described above, a system comprising, in some cases consisting essentially of, or in some cases consisting of a first composition comprising, in some cases consisting essentially of, in some cases consisting of a lanthanide series elemental cation and an oxidizing agent is provided herein. is disclosed in The system comprises a second composition comprising, in some cases consisting essentially of, or in some cases consisting of a Group IA metal cation, or a third composition comprising, in some cases consisting essentially of, or in some cases consisting of a Group IVB metal cation. may further comprise, in some cases consist essentially of, or in some cases consist. The first, second and third compositions may each be a sealing composition or a conversion composition as defined herein.

According to the method of the present invention, at least a portion of the substrate may be in contact with the first composition and optionally the second composition or the third composition. According to the present invention, the step of contacting with the first composition may precede or follow the step of contacting with the second and/or third composition. As described in more detail herein, in some cases there may be a cleaning step that occurs between the step of contacting the first composition and the second and/or third composition.

The present invention also relates to a substrate comprising a film formed from a pretreatment composition comprising a source of a lanthanide-based element and an oxidizing agent, wherein the level of the lanthanide-based element in the film is 100 counts higher than on the surface of the substrate without the film thereon. count) greater than [measured by X-ray fluorescence (60 sec timed assay, 15 Kv, 45 μA, filter 3, T(p) = 1.5 μs)].

The substrate may further comprise a film or layer formed from a Group IA metal cation or a Group IVB metal cation.

Suitable substrates that may be used in the present invention include metal substrates, metal alloy substrates, and/or metallized substrates such as nickel plated plastics. According to the invention, the metal or metal alloy may be or comprise steel, aluminum, zinc, nickel and/or magnesium. For example, the steel substrate may be cold rolled steel, hot rolled steel, electrogalvanized steel and/or hot-dip galvanized steel. In addition, 1XXX, 2XXX, 3XXX, 4XXX, 5XXX, 6XXX or 7XXX series of aluminum alloys and clad aluminum alloys can be used as the substrate. The aluminum alloy may comprise 0.01 wt % to 10 wt % copper. The aluminum alloy being treated can be such as 1XX.X, 2XX.X, 3XX.X, 4XX.X, 5XX.X, 6XX.X, 7XX.X, 8XX.X, or 9XX.X (eg, A356.0). Casting may also be included. Magnesium alloys of the AZ31B, AZ91C, AM60B or EV31A series can also be used as the substrate. Substrates used in the present invention may also include titanium and/or titanium alloys, zinc and/or zinc alloys, and/or nickel and/or nickel alloys. According to the present invention, the substrate may be a part of a vehicle, such as a vehicle body (eg, but not limited to, a door, a body panel, a trunk deck lid, a roof panel, a hood, a roof and/or a stringer; rivets, landing gear components and/or skins used on aircraft) and/or vehicle frames. As used herein, “vehicle” or variations thereof includes, but is not limited to, civil, commercial and military aircraft and/or land vehicles such as automobiles, motorcycles and/or trucks.

first composition

According to the present invention, the first composition may include a lanthanide series elemental cation. The first composition also comprises a Group IIA metal, a Group VB metal, a Group VIB metal, a Group VIIB metal and/or a Group XII metal (along with a lanthanide series cation, a Group IIIB metal cation and/or a Group IVB metal cation, collectively herein referred to as "the first composition metal cation").

According to the present invention, the lanthanide series metal cation may be present in the first composition in an amount (calculated as metal cation) of at least 5 ppm, such as at least 150 ppm, such as at least 300 ppm, based on the total weight of the first composition, and , may be present in the first composition in some cases in an amount (calculated as metal cations) of 25,000 ppm or less, such as 12,500 ppm or less, such as 10,000 ppm or less, based on the total weight of the first composition. According to the present invention, the lanthanide series metal cation is present in the first composition in an amount of 5 to 25,000 ppm, such as 150 to 12,500 ppm, such as 300 to 10,000 ppm, calculated as metal cations, based on the total weight of the first composition. can exist as

According to the present invention, the lanthanide series elemental cation may comprise, for example, cerium, praseodymium, terbium or a combination thereof; The Group IIA metal cation may include magnesium; Group IIIB metal cations may include yttrium, scandium, or combinations thereof; The Group IVB metal cation may include zirconium, titanium, hafnium, or combinations thereof; The Group VB metal cation may include vanadium; The Group VIB metal may include molybdenum; Group VIIB metal cations may include trivalent or hexavalent chromium or manganese; The Group XII metal cation may comprise zinc (collectively, “conversion composition metal cations”).

According to the present invention, the first composition comprises anions that may be suitable for forming salts with the metal cations of the first composition, such as halogens, nitrates, sulfates, phosphates, silicates (orthosilicates and metasilicates), carbonates, hydroxides. and the like may be further included. According to the present invention, the first composition metal salt may be present in the first composition in an amount of at least 50 ppm (calculated as metal salt), such as at least 1,000 ppm, based on the total weight of the first composition, in some cases, 30,000 ppm or less, such as 2,000 ppm or less. According to the present invention, the first composition metal salt may be present in an amount (calculated as metal salt) of 50 to 30,000 ppm, such as 1,000 to 2,000 ppm, based on the total weight of the first composition.

According to the present invention, halogen, if present, is present in the first composition in an amount of at least 5 ppm (calculated as anion), such as at least 50 ppm, such as at least 150 ppm, such as at least 500 ppm, based on the total weight of the first composition. and may be present in an amount of 25,000 ppm or less (calculated as anion), such as 18,500 ppm or less, such as 4,000 ppm or less, such as 2,000 ppm or less, based on the total weight of the first composition. According to the invention, halogen, if present, is present in the first composition from 5 to 25,000 ppm (calculated as anion), such as from 50 to 18,500 ppm, such as from 150 to 4,000 ppm, such as from 500 to 4,000 ppm, based on the total weight of the first composition. It may be present in an amount of 2,000 ppm.

According to the invention, the nitrate, if present, may be present in the first composition in an amount of at least 2 ppm (calculated as anion), such as at least 50 ppm, such as at least 250 ppm, based on the total weight of the first composition, It may be present in an amount of 10,000 ppm or less (calculated as anion), such as 5,000 ppm or less, such as 2,500 ppm or less, based on the total weight of the first composition. According to the present invention, the halogen, if present, is present in the first composition in an amount of 2 to 10,000 ppm (calculated as anion), such as 50 to 5,000 ppm, such as 250 to 2,500 ppm, based on the total weight of the first composition. can

According to the present invention, the first composition metal cation may be present in the first composition in an amount (calculated as metal cation) of at least 5 ppm, such as at least 150 ppm, such as at least 300 ppm, based on the total weight of the first composition, and , in some cases, may be present in the first composition in an amount (calculated as metal cations) of 25,000 ppm or less, such as 12,500 ppm or less, such as 10,000 ppm or less, based on the total weight of the first composition. According to the present invention, the first composition metal cation is present in the first composition in an amount of 5 to 25,000 ppm, such as 150 to 12,500 ppm, such as 300 to 10,000 ppm, calculated as metal cation, based on the total weight of the first composition. can exist as

According to the present invention, the first composition may comprise an oxidizing agent. Non-limiting examples of oxidizing agents include peroxide, persulfate, perchlorate, hypochlorite, nitric acid, sparged oxygen, bromate, peroxy-benzoate, ozone, or combinations thereof.

According to the present invention, the oxidizing agent may be present in an amount of 100 ppm or more, such as 500 ppm or more, based on the total weight of the first composition, and in some cases 13,000 ppm or less, such as 3,000 ppm or more, based on the total weight of the first composition. It may be present in the following amounts. In some cases, the oxidizing agent may be present in the first composition in an amount of 100 to 13,000 ppm, such as 500 to 3,000 ppm, based on the total weight of the first composition.

According to the invention, the first composition may exclude chromium or chromium-containing compounds. As used herein, the term “chromium-containing compound” means a material comprising hexavalent chromium. Non-limiting examples of such materials include chromic acid, chromium trioxide, chromic acid anhydride, dichromate salts such as ammonium dichromate, sodium dichromate, potassium dichromate, and calcium, barium, magnesium, zinc, cadmium and strontium dichromate. do. When the composition and/or each coating or layer formed therefrom is substantially free, essentially free, or completely free of chromium, it includes any form of chromium, such as the hexavalent chromium- It is not limited to the containing compound.

Thus, optionally, according to the present invention, the first composition and/or the coating or layer respectively deposited therefrom may be substantially free of and/or essentially free from one or more of any of the elements or compounds listed in the preceding paragraph. may not be included and/or may not be included completely. The first composition substantially free of chromium or a derivative thereof and/or a coating or layer respectively formed therefrom may be present in trace amounts, for example due to impurities or unavoidable contamination from the environment, although no chromium or derivative thereof is intentionally added. means there is In other words, the amount of the substance is small enough not to affect the properties of the conversion composition, and in the case of chromium, it is at a level at which said element or a compound thereof causes a burden on the environment, the first composition and/or the coating formed therefrom, respectively. Or it may further include those not present in the layer. The term "substantially free of" means that the composition and/or each coating or layer formed therefrom, if any, each, based on the total weight of the composition or layer, contains any or all of the elements listed in the preceding paragraph or is meant to contain less than 10 ppm of the compound. The term "essentially free" means that the conversion composition and/or the coating or layer respectively formed therefrom contains less than 1 ppm, if present, of any or all elements or compounds listed in the preceding paragraph. The term “completely free of” means that the composition and/or each coating or layer formed therefrom contains less than 1 ppb, if present, of any or all of the elements or compounds listed in the preceding paragraph.

According to the present invention, the first composition, in some cases, forms phosphate ions or phosphate-containing compounds and/or sludge formed when using treatment agents based on zinc phosphate, such as aluminum phosphate, iron phosphate, and/or or zinc phosphate. As used herein, “phosphate-containing compound” includes, but is not limited to, compounds containing elemental phosphorus, such as orthophosphates, pyrophosphates, metaphosphates, tripolyphosphates, organophosphonates, and the like, and includes, but is not limited to, monovalent, divalent or trivalent cations such as sodium, potassium, calcium, zinc, nickel, manganese, aluminum and/or iron. When a composition and/or a layer or coating comprising the same is substantially free, essentially free, or completely free of phosphate, it comprises a phosphate ion, or a compound containing phosphate in any form.

Accordingly, according to the present invention, the composition and/or the layer deposited therefrom may be substantially free, in some cases essentially free, or in some In some cases, it may not be completely included. Compositions substantially free of phosphate and/or layers deposited therefrom means that phosphate ions or phosphate-containing compounds are not intentionally added, but may be present in trace amounts, for example due to unavoidable contaminants or impurities from the environment. . That is, the amount of material is too small to affect the properties of the composition; This may further comprise that the phosphate is not present at a level that does not pose an environmental burden to the conversion composition and/or layers deposited therefrom. The term "substantially free of" means that the composition and/or layers deposited therefrom, if any, contain less than 5 ppm of any or all phosphate anions or compounds listed in the preceding paragraph, respectively, based on the total weight of the composition or layer. means to contain The term "essentially free" means that the conversion composition and/or the layer comprising it contains less than 1 ppm of any or all of the phosphate anions or compounds listed in the preceding paragraph. The term "completely free of" means that the composition and/or the layer comprising the same, if present, contains less than 1 ppb of any or all of the phosphate anions or compounds listed in the preceding paragraph.

Optionally, in accordance with the present invention, the first composition may contain one lanthanide series element and/or a single lanthanide series element source, and in some cases more than one lanthanide series element. and/or no more than one lanthanide series element and/or one or more lanthanide series elements, such that it may be substantially free, in some cases essentially free, or in some cases completely free of more than one source of lanthanide series elements. It may contain up to one source of lanthanide series elements.

In some cases, the first composition according to the present invention may be substantially free of, or in some cases completely free of, gelatin (eg, but not limited to bovine, porcine or fish).

In some cases, the first composition according to the present invention may be substantially free of, or in some cases completely free of, oxides. As used herein, the term "substantially free of," when used in reference to an oxide in a first composition, is not intentionally added to the first composition and, if present, contains no more than 5 ppm of the composition by total weight. It is meant to be present in the pretreatment composition in trace amounts. As used herein, the term “essentially free of,” when used in reference to an oxide in a first composition, is present in the first composition, even though the oxide is present in the pretreatment composition in an amount of no more than 1 ppm by total weight of the composition. means to exist in The term “completely free of,” as used herein, when used in reference to an oxide in the first composition, means that the oxide is present in the pretreatment composition in an amount of 1 ppb or less based on the total weight of the composition.

According to the present invention, the pH of the first composition may be 1.0 to 4.5, such as 3 to 4, and if necessary, it may be adjusted, for example, using any acid and/or base. According to the present invention, the pH of the first composition can be maintained by including an acidic substance, for example a water-soluble and/or water-dispersible acid, such as nitric acid, sulfuric acid, and/or phosphoric acid. According to the present invention, the pH of the composition is adjusted to a basic substance, for example a water-soluble and/or water-dispersible base such as sodium hydroxide, sodium carbonate, potassium hydroxide, ammonium hydroxide, ammonia, and/or amines such as triethylamine, methylethyl amine, or mixtures thereof.

The first composition may comprise an aqueous medium and may optionally contain other substances such as nonionic surfactants and excipients conventionally used in the art of conversion compositions. In the aqueous medium, there may be present a water-dispersible organic solvent, for example, an alcohol having up to about 8 carbon atoms, such as methanol, isopropanol, or the like, or a glycol such as ethylene glycol, diethylene glycol or propylene glycol. Ethers may be present. Water-dispersible organic solvents, when present, are typically used in amounts of up to about 10% by volume, based on the total volume of the aqueous medium.

Other optional materials include surfactants that function as defoamers or substrate wetting agents. Anionic, cationic, amphoteric, and/or nonionic surfactants may be used. The anti-foam surfactant may optionally be present at a level of 1 wt% or less, such as 0.1 wt% or less, and the wetting agent is typically at a level of 2 wt% or less, such as 0.5 wt% or less, based on the total weight of the first composition. exist.

The first composition may comprise a carrier, often an aqueous medium, such that the composition is in the form of a solution or dispersion of the lanthanide and/or group IIIB in the carrier. In this embodiment, the solution or dispersion may be contacted with the substrate by any of a variety of known techniques (eg, dipping, spraying, intermittent spraying, dipping and then spraying, spraying and then dipping, brushing or roll-coating). According to the invention, the solution or dispersion, when applied to a metallic substrate, is at a temperature of 40 to 160°F, such as 60 to 110°F, such as 70 to 90°F. For example, the conversion process can be carried out at room temperature or room temperature. The contact time is often from 1 second to 15 minutes, such as 4 minutes to 10 minutes, such as 5 seconds to 4 minutes.

According to the present invention, after contacting with the first composition, the substrate can optionally be dried in situ at room temperature (eg, air-dried), or by simply exposing the substrate to high temperatures, for example by using an air knife, by flashing water, such as by drying the substrate in an oven at 15° C. to 100° C., such as 20 to 90° C., or using, for example, infrared heat (eg, at 70° C. for 10 minutes), or The substrate can be dried by passing it between squeeze rolls. In accordance with the present invention, the substrate surface may be partially, or in some cases, completely dry, prior to any subsequent contact of the substrate surface with any water, solution, composition, etc. As used herein with reference to a substrate surface, “completely dry” or “completely dry” means that there is no moisture on the substrate surface visible to the human eye. In accordance with the present invention, following the step of contacting with the first composition, the substrate (wet or dry) may optionally be rinsed with tap water, deionized water, and/or an aqueous detergent solution to remove any residue, then optionally may be dried as described in the sentence above, for example air dried or dried with hot air. According to the present invention, this water rinse can be eliminated and the substrate (wet or dry) can be contacted with a subsequent treatment composition.

Optionally, the substrate (wet or dried as described above) treated with the first composition (and optionally the second or third composition or electrocoat, powder coat or liquid coating described herein) is subjected to an oven as described above. Alternatively, it may be heated in a heater at a temperature of 100 to 240 °C, such as 110 to 232 °C. Surprisingly, it was found that this substrate had a b ^* value of less than 3.09 (spectral component excluded, 25 mm aperture).

group IA a second composition comprising a metal cation

According to the present invention, the second composition may comprise a group IA metal cation, such as a lithium cation, which may be in the form of a salt. In addition, the second composition may further comprise one or more Group IA metal cations, Group VB metal cations and/or Group VIB metal cations in addition to lithium. The one or more Group IA metal cations, Group VB metal cations and/or Group VIB metal cations other than lithium may be in the form of a salt. Non-limiting examples of suitable anions for forming salts with lithium, Group IA cations other than lithium, Group VB cations and/or Group VIB cations include carbonates, hydroxides, nitrates, halogens, sulfates, phosphates and silicates (such as , orthosilicates and metasilicates); Molybdate and/or perchlorate may be included.

According to the present invention, the metal salts of the second composition (ie lithium, a group IA metal other than lithium, salts of groups VB and/or VIB) are each added to the second composition, 25 based on the total weight of the second composition. ppm or more, such as 150 ppm or more, such as 500 ppm or more (calculated as total compound), and in some cases, 30,000 ppm or less, such as 2,000 ppm or less, such as 1,500 ppm or less (total compound), based on the total weight of the second composition calculated as ). According to the present invention, the metal salts of the second composition (ie lithium, a group IA metal other than lithium, salts of groups VB and/or VIB) are each added to the second composition, 25 based on the total weight of the second composition. to 30,000 ppm, such as 150 to 2,000 ppm, such as 500 to 1,500 ppm (calculated as total compound).

According to the present invention, lithium cations, group IA metals other than lithium, group VB metal cations and group VIB metal cations are each added to the second composition by at least 5 ppm, such as at least 50 ppm, based on the total weight of the second composition, such as 150 ppm or greater, such as 250 ppm or greater, and in some cases 5,500 ppm or less, such as 1,200 ppm or less, such as 1,000 ppm or less, such as 500 ppm, based on the total weight of the second composition It may be present in the following amounts (calculated as cations). In some cases, in accordance with the present invention, lithium cations, Group IA metals other than lithium, Group VB metal cations and Group VIB metal cations are each contained in the second composition at 5 to 5,500 ppm, based on the total weight of the second composition, such as 50 to 1,000 ppm (calculated as cations), such as 150 to 500 ppm.

According to the present invention, the lithium salt of the present invention may comprise an inorganic lithium salt, an organic lithium salt or a combination thereof. According to the present invention, both the anion and the cation of the lithium salt can be dissolved in water. According to the present invention, for example, a lithium salt may have a solubility constant in water of at least 1x10 ^-11 at a temperature of 25°C (K; 25°C), for example at least 1x10 ^-4 and in some cases 5x10 ⁺² may be below. According to the invention, the lithium salt may have a solubility constant in water of 1x10 ^-11 to 5x10 ⁺² , such as 1x10 ^-4 to 5x10 ⁺² at a temperature of 25 °C (K; 25 °C). As used herein, "solubility constant" means the product of the equilibrium concentration of the ion in the saturated aqueous solution of each lithium salt. Each concentration increases with the power of each ion coefficient in the balanced equation. Solubility constants for various salts can be found in the Handbook of Chemistry and Physics .

According to the present invention, the second composition of the present invention may comprise an oxidizing agent such as hydrogen peroxide, persulfate, perchlorate, sparged oxygen, bromate, peroxy-benzoate, ozone, etc. or combinations thereof. For example, the second composition may comprise 0.1 to 15 weight percent, such as 2 to 10 weight percent, such as 6 to 8 weight percent, of an oxidizing agent based on the total weight of the second composition. Alternatively, in accordance with the present invention, the second composition may be substantially free, in some cases essentially free, or in some cases completely free of an oxidizing agent.

In accordance with the present invention, the second composition may exclude Group IIA metal cations or Group IIA metal-containing compounds, including but not limited to calcium. Non-limiting examples of such materials include Group IIA metal hydroxides, Group IIA metal nitrates, Group IIA metal halides, Group IIA metal sulfamates, Group IIA metal sulfates, Group IIA carbonates and/or Group IIA metal carboxylates. do. When the second composition and/or each coating or layer formed therefrom is substantially free, essentially free, or completely free of a Group IIA metal cation, it is free of any form of a Group IIA metal cation, such as a non It includes, but is not limited to, the Group IIA metal-containing compounds listed above.

According to the present invention, the second composition may exclude chromium or chromium-containing compounds. As used herein, the term “chromium-containing compound” refers to a material comprising hexavalent chromium. Non-limiting examples of such materials include chromic acid, chromium trioxide, chromic acid anhydride, dichromate salts such as ammonium dichromate, sodium dichromate, potassium dichromate, and calcium, barium, magnesium, zinc, cadmium, and strontium dichromate. include When the second composition and/or each coating or layer formed therefrom is each substantially free, essentially free, or completely free of chromium, it may be any form of chromium, such as, but not limited to, those listed above. hexavalent chromium-containing compounds.

Thus, optionally, according to the present invention, the second composition of the present invention and/or respectively a coating or layer deposited therefrom may be substantially free of any one or more of the elements or compounds listed in the paragraphs above and/or , may be essentially free of and/or completely free of. The second composition and/or coating or layer formed therefrom substantially free of chromium or derivatives thereof may be present in trace amounts, for example due to impurities or unavoidable contaminants from the environment, although chromium or derivatives thereof are not intentionally added. means there is That is, the amount of material is too small to affect the properties of the second composition; In the case of chromium, this may include that its element or compound is not present in the second composition and/or in a coating or layer formed therefrom, respectively, at a level that creates a burden on the environment. The term “substantially free of” means that the second composition and/or each coating or layer formed therefrom, if present, is less than 10 ppm each, based on the total weight of the composition or layer, of any or all of the preceding paragraphs. means containing an element or compound. The term "essentially free of" means that the second composition and/or each coating or layer formed therefrom, if present, contains less than 1 ppm of any or all of the elements or compounds listed in the preceding paragraph. The term “completely free of” means that the second composition and/or each coating or layer formed therefrom, if present, contains less than 1 ppb of any or all of the elements or compounds listed in the preceding paragraph.

According to the present invention, the second composition, in some cases, forms phosphate ions or phosphate-containing compounds and/or sludges formed when using treatment agents based on zinc phosphate, such as aluminum phosphate, iron phosphate, and/or or zinc phosphate. As used herein, “phosphate-containing compound” includes, but is not limited to, compounds containing elemental phosphorus, such as orthophosphates, pyrophosphates, metaphosphates, tripolyphosphates, organophosphonates, and the like, and includes, but is not limited to, monovalent, divalent or trivalent cations such as sodium, potassium, calcium, zinc, nickel, manganese, aluminum and/or iron. When a composition and/or a layer or coating comprising the same is substantially free, essentially free, or completely free of phosphate, it comprises a phosphate ion, or a compound containing phosphate in any form.

Thus, in accordance with the present invention, the second composition and/or the layer deposited therefrom may be substantially free, or in some cases essentially free, of any one or more of the ions or compounds listed in the paragraphs above or , which may not be fully included in some cases. A second composition substantially free of phosphate and/or a layer deposited therefrom has no intentional addition of phosphate ions or phosphate-containing compounds, but may be present in trace amounts, such as due to unavoidable contaminants or impurities from the environment. it means. That is, the amount of material is too small to affect the properties of the composition; This may further comprise that the phosphate is not present at a level that does not pose an environmental burden to the second composition and/or layers deposited therefrom. The term "substantially free of" means that the second composition and/or layer deposited therefrom, if any, contains less than 5 ppm of any or all phosphate anions listed in the preceding paragraph, respectively, based on the total weight of the composition or layer. or a compound. The term “essentially free of” means that the second composition and/or the layer comprising it contains less than 1 ppm of any or all phosphate anions or compounds listed in the preceding paragraph. The term “completely free of” means that the second composition and/or layer comprising it, if present, contains less than 1 ppb of any or all of the phosphate anions or compounds listed in the preceding paragraph.

According to the present invention, the second composition may, in some cases, exclude fluoride or fluoride source. As used herein, “fluoride source” includes monofluorides, bifluorides, fluoride complexes and mixtures thereof known to generate fluoride ions. When a composition and/or a layer or coating comprising the same is substantially free, essentially free, or completely free of fluoride, it includes any form of fluoride ion or source of fluoride, but for example Unintentional fluoride that may be present in the bath as a result of entry, for example, into a previous treatment bath in a process line, a tap water source (eg, fluoride added to the water supply to prevent tooth decay), fluoride from a pretreated substrate, etc. does not include That is, a bath that is substantially free, essentially free, or completely free of fluoride means that the composition used to make the bath prior to use on the process line is substantially free of, or essentially free of fluoride. It may have unintended fluorides, which may be derived from these external sources, even if not, or wholly not include.

For example, the second composition may be any fluoride-source, such as ammonium and alkali metal fluorides, acid fluorides, fluoroboric acid, fluorosilicic acid, fluorotitanic acid and fluorozirconic acid and their ammonium and alkali metals. salts, and other inorganic fluorides, including but not limited to zinc fluoride, zinc aluminum fluoride, titanium fluoride, zirconium fluoride, nickel fluoride, ammonium fluoride, sodium fluoride, potassium fluoride and hydrofluoric acid , and other similar materials known to those skilled in the art).

Fluoride present in the second composition that is not bound to a metal ion or hydrogen ion, such as a Group IVB metal ion, as defined herein as "free fluoride", is, for example, fluoride provided by Thermoscientific. Orion Dual Star Dual Channel Benchtop Meter with Ion Selective Electrode (“ISE”), symphony® Fluoride Selective Combination Electrode or similar supplied by VWR International. Star Dual Channel Benchtop Meter) can be used as an operating parameter in the second composition bath (see, e.g., Light and Cappuccino, Determination of fluoride in toothpaste using an ion-selective electrode , J. Chem. Educ., 52 :4, 247-250, April 1975]). Fluoride ISE can be normalized by immersing the electrode in a solution of known fluoride concentration, recording the reading in millivolts, and then plotting these millivolt readings on a logarithmic graph. The millivolt reading of the unknown sample can be compared to this calibration graph to determine the fluoride concentration. Alternatively, the fluoride ISE can be used with a meter that performs calibration calculations internally, so that the concentration of the unknown sample can be read directly after calibration.

Since fluoride ions are small anions with high charge density, they often form complexes with hydrogen ions or metal ions with high positive charge density such as Group IVB metal ions in aqueous solution. A fluoride anion in solution that is ionic or covalently bound to a metal cation or hydrogen ion is defined herein as "bound fluoride". As such, complexed fluoride ions cannot be measured with fluoride ISE unless the solution in which these ions are present is mixed with an ionic strength adjustment buffer (eg, citrate anion or EDTA) that releases fluoride ions from the complex. can't At that point, (all) fluoride ions can be measured with fluoride ISE, and that measurement is known as "total fluoride". Alternatively, the total fluoride may be calculated by comparing the weight of fluoride supplied to the sealant composition to the total weight of the composition.

In accordance with the present invention, the treatment composition may, in some cases, be substantially free of, in some cases essentially free, or in some cases completely free of cobalt ions or cobalt-containing compounds. As used herein, "cobalt-containing compound" includes compounds, complexes or salts containing the element cobalt, such as cobalt sulfate, cobalt nitrate, cobalt carbonate and cobalt acetate. When a composition and/or a layer or coating comprising the same is substantially free, essentially free, or completely free of cobalt, it includes any form of cobalt ions or cobalt containing compounds.

According to the present invention, the treatment composition may in some cases be substantially free of, in some cases essentially free of, or in some cases completely free of vanadium ions or vanadium-containing compounds. As used herein, "vanadium-containing compound" refers to compounds, complexes or salts containing elemental vanadium, such as vanadates and decabanadates comprising the counter ion of an alkali metal or ammonium cation (e.g., sodium ammonium decabanadate including). When a composition and/or a layer or coating comprising the same is substantially free, essentially free, or completely free of vanadium, it comprises any form of vanadium ions or vanadium containing compounds.

Optionally, the second composition of the present invention may further comprise a nitrogen-containing heterocyclic compound. Nitrogen-containing heterocyclic compounds include cyclic compounds having one nitrogen atom, such as pyrrole, and azole compounds having two or more nitrogen atoms, such as pyrazole, imidazole, triazole, tetrazole and pentaazole, one nitrogen azole compounds having an atom and one oxygen atom, such as oxazole and isoxazole, and azole compounds having one nitrogen atom and one sulfur atom, such as thiazole and isothiazole. Non-limiting examples of suitable azole compounds include 2,5-dimercapto-1,3,4-thiadiazole (CAS: 1072-71-5), 1H-benzotriazole (CAS: 95-14-7), 1H -1,2,3-triazole (CAS: 288-36-8), 2-amino-5-mercapto-1,3,4-thiadiazole (CAS: 2349-67-9) (also 5 -amino-1,3,4-thiadiazole-2-thiol), and 2-amino-1,3,4-thiadiazole (CAS: 4005-51-0). In some embodiments, for example, the azole compound comprises 2,5-dimercapto-1,3,4-thiadiazole. Also, according to the present invention, the nitrogen-containing heterocyclic compound may be in the form of a salt such as a sodium salt.

The nitrogen-containing heterocyclic compound may be present in the second composition at a concentration of at least 0.0005 g per liter of composition, such as at least 0.0008 g per liter of composition, such as at least 0.002 g per liter of composition, and in some cases , may be present in the second composition in an amount of 3 g or less per liter of composition, for example 0.2 g or less per liter of composition, such as 0.1 g or less per liter of composition. According to the present invention, the nitrogen-containing heterocyclic compound is present in an amount from 0.0005 g per liter of composition to 3 g per liter of composition, for example from 0.0008 g per liter of composition to 0.2 g per liter of composition, for example composition 1 L It may be present in the second composition (if present) at a concentration of 0.002 g of sugar to 0.1 g per liter of composition.

According to the present invention, the second composition may comprise an aqueous medium and, optionally, may contain other substances such as one or more organic solvents. Non-limiting examples of suitable such solvents include propylene glycol, ethylene glycol, glycerol, low molecular weight alcohols, and the like. When present, the organic solvent may be present in the second composition in an amount of at least 1 gram of solvent per liter of second composition, such as at least about 2 g of solvent per liter of second solution, and in some cases per liter of second composition. It may be present in an amount of up to 40 g of solvent, such as up to 20 g of solvent per liter of second solution. According to the present invention, the organic solvent, if present, can be from 1 g of solvent per liter of second composition to 40 g of solvent per liter of second composition, such as from 2 g of solvent per liter of second composition to per liter of second composition. The solvent may be present in the second composition in an amount of 20 g.

According to the present invention, the pH of the second composition may be 8 or more, such as 9 or more, such as 10 or more, such as 11 or more, and in some cases 13 or less, such as 12 or less, eg 11.5 or less. According to the present invention, the pH of the second composition may be between 8 and 13, for example between 10 and 12, for example between 11 and 11.5. The pH of the second composition may be adjusted as needed, for example using any acid and/or base. In accordance with the present invention, the pH of the second composition may be maintained through the inclusion of acidic substances including carbon dioxide, water-soluble and/or water-dispersible acids such as hydrochloric acid, nitric acid, sulfuric acid and/or phosphoric acid. According to the present invention, the pH of the second composition is selected from carbonates such as group I carbonates, group II carbonates, hydroxides such as lithium hydroxide, sodium hydroxide, potassium hydroxide or ammonium hydroxide, ammonia and and/or through the inclusion of a basic material comprising a water-soluble and/or water-dispersible base, including amines such as triethylamine, methylethylamine, or mixtures thereof.

As noted above, the second composition comprises a carrier, often an aqueous medium, so that the composition may be in the form of a solution or dispersion of lithium cations in a carrier. According to the present invention, the solution or dispersion may be contacted with the substrate by any of a variety of known techniques, such as dipping or impregnating, spraying, intermittent spraying, dipping followed by spraying, spraying followed by dipping, brushing or roll-coating. In accordance with the present invention, the solution or dispersion when applied to a metallic substrate may be at a temperature of from 40°F to about 160°F, such as from 60°F to 110°F. For example, the process of contacting the metal substrate with the second composition may be performed at room temperature or room temperature. The contact time is often from about 1 second to about 15 minutes, such as from about 5 seconds to about 2 minutes.

According to the invention, following contact with the second composition, the substrate may optionally be dried in situ, such as air dried at room temperature, or the substrate may be dried with hot air, eg with an air knife, at high temperature. flashing off the water by briefly exposing the substrate in an oven, such as at 15°C to 100°C, such as 20°C to 90°C, or in a heater assembly using, for example, infrared heat, for example 10 It can be dried at 70° C. for minutes, or by passing the substrate between squeegee rolls. According to the present invention, the substrate surface may be partially or in some cases completely dried before any subsequent contact of the substrate surface with any water, solution, composition, etc. As used herein in reference to a substrate surface, “completely dry” or “completely dry” means that there is no moisture on the substrate surface visible to the human eye. According to the present invention, following the step of contacting with the second composition, the substrate (wet or dry) may optionally be rinsed with tap water, deionized water, and/or an aqueous solution of a cleaning agent to remove any residue, then Optionally it may be dried as described in the sentence above, eg air dried or dried with hot air. According to the present invention, this water rinse can be removed and the substrate (wet or dry) can be contacted with the subsequent treatment composition.

Optionally, according to the present invention, after contacting with the second composition, the substrate, optionally before contacting at least a portion of the surface of the substrate with a subsequent treatment composition to form a film, layer and/or coating thereon, any Do not rinse with or come into contact with an aqueous solution (described below).

Optionally, according to the present invention, following the step of contacting with the second composition, the substrate may optionally be contacted with tap water, deionized water, RO water and/or any aqueous solution known to a person skilled in the art of substrate treatment, At this time, the water or aqueous solution may be at a temperature of room temperature (60°F) to 212°F. The substrate may then optionally be dried, for example air dried or dried with hot air as described in the preceding paragraph, such that the substrate surface is subjected to any subsequent contact with the substrate surface, such as any water, solution, or composition. may be partially or, in some cases, completely dried.

Figure 2 shows an XPS irradiation scan of a substrate surface treated with lithium hydroxide or lithium carbonate, confirming that no lithium is detected on the substrate surface. The substrate had about 2.2 μm thick oxidized aluminum on an aluminum-copper alloy (measured by TEM). According to the invention, the thickness of the layer formed by the treatment composition can be, for example, up to 550 nm, such as from 5 to 550 nm, such as from 10 to 400 nm, such as from 25 to 250 nm. The thickness of a layer formed from the treatment composition can be measured using a number of analytical techniques including, but not limited to, X-ray photoelectron spectroscopy (XPS) depth profiling or TEM (transmission electron microscopy). As used herein, “thickness” when used for a layer formed by a second composition of the present invention comprising a Group IA metal cation, as shown in FIG. 1 , is (a) formed over the original air/substrate interface. layer, (b) a modified layer formed below the pretreatment/substrate interface, or (c) a combination of (a) and (b). Although modified layer (b) is shown extending to the pretreatment/substrate interface in FIG. 1 , there may be an intervening layer between the modifying layer (b) and the pretreatment/substrate interface. Similarly, (c), a combination of (a) and (b), is not limited to continuous layers, but may include multiple layers with intervening layers between them, wherein the measurement of the thickness of layer (c) is Intervening layers can be excluded.

IVB A third composition comprising a metal cation

As noted above, the systems and methods of the present invention may include a third composition comprising a Group IVB metal cation. The third composition may also further comprise a Group IA metal cation and/or a Group VIB metal cation (along with the Group IVB metal cation, collectively referred to herein as a “third composition metal cation”).

According to the present invention, the Group IA metal cation may comprise lithium; The Group IVB metal cation may include zirconium, titanium, hafnium, or combinations thereof; The Group VIB metal may include molybdenum.

For example, the Group IVB metal cation used in the third composition may be a compound of zirconium, titanium, hafnium, or mixtures thereof. Suitable compounds of zirconium include, but are not limited to, hexafluorozirconic acid, alkali metals and ammonium salts thereof, ammonium zirconium carbonate, zirconyl nitrate, zirconyl sulfate, zirconium carboxylate and zirconium hydroxy carboxylates such as zirconium acetate; zirconium oxalate, ammonium zirconium glycolate, ammonium zirconium lactate, ammonium zirconium citrate, zirconium basic carbonate, and mixtures thereof. Suitable compounds of titanium include, but are not limited to, fluorotitanic acid and salts thereof. Suitable compounds of hafnium include, but are not limited to, hafnium nitrate.

According to the present invention, the Group IVB metal cation is present in the third composition at least 20 ppm metal (calculated as metal cation) based on the total weight of the third composition, such as at least 50 ppm metal, or, in some cases, 70 ppm It may be present in a total amount of more than one metal. According to the present invention, the Group IVB metal is present in the third composition up to 1,000 ppm metal (calculated as metal cations), such as 600 ppm metal or less, or, in some cases, 300 ppm, based on the total weight of the third composition. It may be present in a total amount of metal up to ppm. According to the present invention, group IVB metal cations are present in the third composition in an amount of from 20 to 1,000 ppm of metal (calculated as metal cations), such as from 50 to 600 ppm of metal, such as from 70 to 300, based on the total weight of the third composition. total amount of metal in ppm. As used herein, the term “total amount”, when used in reference to the amount of Group IVB metal cation, means the sum of all Group IV metals present in the third composition.

According to the present invention, the third composition may also comprise a Group IA metal cation, such as a lithium cation. According to the present invention, the source of the Group IA metal cation in the third composition may be in the form of a salt. Non-limiting examples of suitable lithium salts include lithium nitrate, lithium sulfate, lithium fluoride, lithium chloride, lithium hydroxide, lithium carbonate, lithium iodide, and combinations thereof.

According to the present invention, the Group I metal cation is present in the third composition in an amount of at least 2 ppm (as metal cation), such as at least 5 ppm, such as at least 25 ppm, such as at least 75 ppm, based on the total weight of the third composition. and in some cases 500 ppm or less (as metal cations), such as 250 ppm or less, such as 125 ppm or less, such as 100 ppm or less, based on the total weight of the third composition. According to the present invention, the Group IA metal cation is present in the third composition from 2 to 500 ppm (as metal cation), such as from 5 to 250 ppm, such as from 5 to 125 ppm, such as from 5 to 25, based on the total weight of the third composition. It may be present in an amount in ppm. The amount of the Group IA metal cation in the third composition may range between the recited values inclusive of the recited values.

According to the present invention, the third composition may also comprise a Group VIB metal cation. According to the present invention, the source of the Group VIB metal cation in the third composition may be in the form of a salt. Non-limiting examples of suitable molybdenum salts include sodium molybdate, lithium molybdate, calcium molybdate, potassium molybdate, ammonium molybdate, molybdenum chloride, molybdenum acetate, molybdenum sulfamate. , molybdenum formate, molybdenum lactate, and combinations thereof.

According to the present invention, the Group VIB metal cation may be present in the third composition in an amount of at least 5 ppm (as metal cation), such as at least 25 ppm, such as at least 100 ppm, based on the total weight of the third composition, and in some cases , in the third composition in an amount of 500 ppm or less (as metal cations), such as 250 ppm or less, such as 150 ppm or less, based on the total weight of the third composition. According to the present invention, the Group VIB metal cation may be present in the third composition in an amount of 5 to 500 ppm (as metal cation), such as 25 to 250 ppm, such as 40 to 120 ppm, based on the total weight of the third composition. there is. The amount of the Group VIB metal cation in the third composition may range between the recited values inclusive of the recited values.

According to the present invention, the third composition comprises anions that may be suitable for forming salts with the metal cations of the third composition, such as halogens, nitrates, sulfates, silicates (orthosilicates and metasilicates), carbonates, hydroxides, and the like. may additionally include.

According to the present invention, nitrate, if present, may be present in the third composition in an amount (calculated as nitrate anion) of at least 2 ppm, such as at least 50 ppm, such as at least 50 ppm, based on the total weight of the third composition. and may be present in an amount (calculated as nitrate anion) of 10,000 ppm or less, such as 5,000 ppm or less, such as 2,500 ppm or less, based on the total weight of the third composition. According to the invention, the halogen, if present, in the third composition is in an amount of from 2 to 10,000 ppm, such as from 25 to 5,000 ppm, such as from 50 to 2,500 ppm, calculated as nitrate anion, based on the total weight of the third composition. can exist as

According to the invention, the third composition may also comprise an electrolytic metal ion. As used herein, the term “positive metal ion” refers to a metal ion that will be reduced by the treated metal substrate when a third solution contacts the surface of the metallic substrate. As will be understood by one of ordinary skill in the art, the tendency of a species to reduce is referred to as the reduction potential, expressed in volts, and measured relative to a standard hydrogen electrode (which is arbitrarily designated as a reduction potential of zero). The reduction potentials for several elements are set forth in Table A below (according to CRC 82 ^nd Edition, 2001-2002). If one element or ion has a more positive voltage value (E ^* ) than the other element or ion compared in the table below, it is more easily reduced than the other element or ion being compared.

[Table A]

Thus, as will be apparent, the metallic substrate is of the materials listed above, such as cold rolled steel, hot rolled steel, zinc metal, steel coated with zinc compounds or zinc alloys, hot-dip galvanized steel, galvanized steel, zinc alloy coated steel , aluminum alloys, aluminum plated steels, aluminum alloy plated steels, magnesium and magnesium alloys, suitable electrolytic metals for deposition on top of the substrate include, for example, nickel, copper, silver, gold, and mixtures thereof.

According to the present invention, when the electrolytic metal ion comprises copper, both the soluble and insoluble compound can serve as a source of copper ions in the third composition. For example, the source of copper ions in the third composition may be a water-soluble copper compound. Specific examples of such compounds include, but are not limited to, copper sulfate, copper nitrate, copper thiocyanate, disodium copper ethylenediaminetetraacetate tetrahydrate, copper bromide, copper oxide, copper hydroxide, copper chloride, copper fluoride Ride, copper gluconate, copper citrate, copper roroyl sarcosinate, copper lactate, copper oxalate, copper tartrate, copper maleate, copper succinate, copper malonate, copper maleate, copper benzoate, copper salicylate, copper amino acid complex, copper fumarate, copper glycerophosphate, sodium copper chlorophylline, copper fluorosilicate, copper fluoroborate and copper iodate, and carboxylic acids (such as the homologous series of formic acid to decanoic acid) copper salts, and copper salts of polybasic acids of the oxalic acid to suberic acid series.

When copper ions supplied from the water-soluble copper compound are precipitated as impurities in the form of copper sulfate, copper oxide, etc., it is preferable to add a complexing agent that inhibits the precipitation of copper ions and stabilizes the ions as a copper complex in the composition. can

According to the present invention, the copper compound can be added as a copper complex salt, such as Cu-EDTA, which by itself can be stably present in the third composition, but by combining the complexing agent with a compound that is difficult to solubilize on its own. It is also possible to form copper complexes that can be stably present in the composition. Examples thereof include Cu-EDTA complexes formed by the combination of CuSO ₄ and EDTA·2Na.

According to the invention, the positive metal ion is present in the third composition at least 2 ppm (calculated as metal ion), such as at least 4 ppm, such as at least 6 ppm, such as at least 8 ppm, based on the total weight of the third composition; For example, it may be present in an amount of 10 ppm or more. According to the present invention, the positive metal ions are present in the third composition 100 ppm or less (calculated as metal ions), such as 80 ppm or less, such as 60 ppm or less, such as 40 ppm or less, based on the total weight of the third composition, For example, it may be present in an amount of up to 20 ppm. According to the invention, the positive metal ion is present in the third composition from 2 to 100 ppm (calculated as metal ion), such as 4 to 80 ppm, such as 6 to 60 ppm, such as 8, based on the total weight of the third composition. to 40 ppm. The amount of the electrolytic metal ion in the third composition may range between the recited values inclusive of the recited values.

According to the present invention, the source of fluoride may be present in the third composition. As used herein, the disclosed or reported amount of fluoride in the third composition is referred to as "free fluoride," measured in parts per million of fluoride. Free fluoride is defined as capable of being measured by fluoride-selective ISE. In addition to free fluoride, the third composition may also contain "bound fluoride" as described above. The sum of the concentrations of bound and free fluoride is equal to the total fluoride that can be measured as described herein. The total fluoride in the third composition may be supplied by hydrofluoric acid, and alkali metal and ammonium fluoride or hydrogen fluoride. Additionally, the total fluoride in the third composition may be derived from a Group IVB metal present in the third composition (eg, hexafluorozirconic acid or hexafluorotitanic acid). other complex fluorides such as H ₂ SiF ₆ or HBF ₄ A third composition may be added to provide total fluoride. Those skilled in the art will understand that the presence of free fluoride in the tertiary bath can affect the tertiary deposition and etching of the substrate, and therefore it is important to measure these bath parameters. The level of free fluoride will change with the pH, and addition of the chelator to the third bath, and is indicative of the degree of fluoride association with the metal ions/protons present in the third bath. For example, a third composition of the same total fluoride level may have a different free fluoride level that will be affected by the pH and chelator present in the third solution.

According to the present invention, the free fluoride of the third composition is at least 15 ppm, such as at least 50 ppm of free fluoride, such as at least 100 ppm of free fluoride, such as at least 200 ppm of free fluoride, based on the total weight of the third composition. may be present in quantity. According to the present invention, the free fluoride of the third composition is 2,500 ppm or less, such as 1,000 ppm or less free fluoride, such as 500 ppm or less free fluoride, such as 250 ppm or less free fluoride, based on the total weight of the third composition. It may be present in an amount of fluoride. According to the present invention, the free fluoride of the third composition is 15 to 2,500 ppm free fluoride, such as 50 to 1,000 ppm, such as 200 ppm or less free fluoride to 500 ppm free fluoride, based on the total weight of the third composition. fluoride, such as up to 100 ppm free fluoride to 250 ppm free fluoride.

The third composition may further comprise an amino compound. The amino compound may be a primary, secondary, tertiary or quaternary amine. Specific examples of the alpha amino compound may be sarcosine, glycine and oleyl imidazoline. According to the present invention, the alpha amino acid compound may be a substituted or unsubstituted glycine. The substituted glycine may be sarcosine, iminodiacetic acid, leucine or tyrosine. Illustrative, but non-limiting examples of beta amino acid compounds include taurine and N-methyl taurine. Illustrative, but non-limiting examples of gamma amino acid compounds include gamma aminobutyric acid. Illustrative, but non-limiting examples of cyclic amino compounds having an amine group and an acid group on the same ring include aminobenzoic acid and derivatives thereof. Illustrative, but non-limiting examples of beta amino alcohol compounds include imidazoline and its derivatives, choline, triethanolamine, diethanol glycine, and 2-amino-2-ethyl-1,3-propanediol. Illustrative, but non-limiting examples of gamma amino alcohol compounds include aminopropanol. Illustrative, non-limiting examples of cyclic amino compounds having an amine group and a hydroxyl group on the same ring include amino phenols and derivatives thereof.

The amino compound may be present in the third composition in an amount of 50 ppm or greater, such as 100 ppm or greater, based on the total weight of the third composition, and in some cases, 100,000 ppm or less, such as 10,000 ppm or less. According to the present invention, the amino compound may be present in the third composition in an amount of 50 to 100,000 ppm, such as 100 to 10,000 ppm, based on the total weight of the third composition.

According to the present invention, the third composition may, in some cases, comprise an oxidizing agent. Non-limiting examples of oxidizing agents include peroxide, persulfate, perchlorate, chlorate, hypochlorite, nitric acid, sparged oxygen, bromate, peroxy-benzoate, ozone, or combinations thereof. According to the present invention, the oxidizing agent, if present, may be present in an amount of at least 50 ppm, such as at least 500 ppm, based on the total weight of the third composition, and in some cases up to 13,000 ppm, based on the total weight of the third composition. , such as in an amount of 3,000 ppm or less. In some cases, the oxidizing agent, if present, may be present in the third composition in an amount of 100 to 13,000 ppm, such as 500 to 3,000 ppm, based on the total weight of the third composition. As used herein, the term “oxidizing agent,” when used in reference to a component of a third composition, comprises at least one of a metal present in a substrate contacted by the third composition, and/or a metal-complexing agent present in the third composition. Chemicals that can oxidize. The phrase “capable of oxidizing,” as used herein with reference to “oxidizing agent,” removes electrons from an atom or molecule present in a substrate or third composition, and, optionally, thereby reducing the number of electrons in such atom or molecule. means you can do it.

According to the invention, the third composition may exclude chromium or chromium-containing compounds. As used herein, the term “chromium-containing compound” refers to a material comprising trivalent and/or hexavalent chromium. Non-limiting examples of such materials include chromic acid, chromium trioxide, chromic acid anhydride, dichromate salts such as ammonium dichromate, sodium dichromate, potassium dichromate, and calcium, barium, magnesium, zinc, cadmium, strontium dichromate, chromium. (III) sulfate, chromium (III) chloride, and chromium (III) nitrate. When the third composition and/or each coating or layer formed therefrom is substantially free, essentially free, or completely free of chromium, it is chromium in any form, such as, but not limited to, those listed above. trivalent and hexavalent chromium-containing compounds.

Thus, optionally, according to the present invention, the third composition of the present invention and/or the coating or layer respectively deposited therefrom cannot comprise substantially any one or more of the elements or compounds listed in the paragraphs above and/or, essentially and/or completely inclusive. The third composition substantially free of chromium or derivatives thereof and/or coatings or layers respectively formed therefrom may be present in trace amounts, such as due to unavoidable contamination or impurities from the environment, although chromium or derivatives thereof are not intentionally added. there is. That is, the amount of material is too small to affect the properties of the third composition; In the case of chromium, this may further include that elements or compounds thereof are not present at levels that pose a burden on the environment to the third composition and/or respectively a coating or layer formed therefrom. The term “substantially free of” means that the third composition and/or each coating or layer formed therefrom, if present, is less than 10 ppm each, based on the total weight of the composition or layer, of any or all of the above listed paragraphs. means containing an element or compound. The term “essentially free” is meant to contain, if any, less than 1 ppm of any or all of the elements or compounds listed in the paragraphs above, a third composition and/or each coating or layer formed therefrom. The term "completely free of" means that the third composition and/or each coating or layer formed therefrom, if present, contains less than 1 ppb of any or all elements or compounds listed in the preceding paragraph.

According to the present invention, the third composition is, in some cases, formed when using treatment agents based on zinc phosphate or phosphate ions or phosphate-containing compounds and/or the formation of sludge, such as aluminum phosphate, iron phosphate, and/or or zinc phosphate. As used herein, “phosphate-containing compound” includes, but is not limited to, compounds containing elemental phosphorus, such as orthophosphates, pyrophosphates, metaphosphates, tripolyphosphates, organophosphonates, and the like, and includes, but is not limited to, monovalent, divalent or trivalent cations such as sodium, potassium, calcium, zinc, nickel, manganese, aluminum and/or iron. When a composition and/or a layer or coating comprising the same is substantially free, essentially free, or completely free of phosphate, it comprises a phosphate ion, or a compound containing phosphate in any form.

Thus, in accordance with the present invention, the third composition and/or the layer deposited therefrom may be substantially free, or in some cases essentially free, of any one or more of the ions or compounds listed in the paragraphs above or , which may not be fully included in some cases. The third composition and/or layer deposited therefrom, substantially free of phosphate, has no intentional addition of phosphate ions or phosphate-containing compounds, but may be present in trace amounts, such as due to unavoidable contaminants or impurities from the environment. it means. That is, the amount of material is too small to affect the properties of the composition; This may further comprise that the phosphate is not present at a level that does not pose an environmental burden to the third composition and/or layers deposited therefrom. The term "substantially free of" means that the third composition and/or layer deposited therefrom, if any, contains less than 5 ppm of any or all phosphate anions listed in the preceding paragraph, respectively, based on the total weight of the composition or layer. or a compound. The term "essentially free of" means that the third composition and/or the layer comprising it contains less than 1 ppm of any or all phosphate anions or compounds listed in the preceding paragraph. The term “completely free of” means that the third composition and/or layer comprising it, if any, contains less than 1 ppb of any or all of the phosphate anions or compounds listed in the preceding paragraph.

Optionally, according to the present invention, the third composition may further comprise a source of phosphate ions. For clarity, as used herein, “phosphate ion” refers to a phosphate ion derived from or derived from an inorganic phosphate compound. For example, in some cases, the phosphate ion may be present in an amount greater than 5 ppm, such as 10 ppm, such as 20 ppm, based on the total weight of the third composition. In some cases, the phosphate ion may be present in an amount of 60 ppm or less, such as 40 ppm or less, such as 30 ppm or less, based on the total weight of the third composition. In some cases, the phosphate ion may be present in an amount of 5 to 60 ppm, such as 10 to 40 ppm, such as 20 to 30 ppm, based on the total weight of the third composition.

According to the present invention, the pH of the third composition may be 6.5 or less, such as 5.5 or less, such as 4.5 or less, such as 3.5 or less. According to the present invention, the pH of the third composition may, in some cases, be between 2.0 and 6.5, such as between 3 and 4.5, and may be adjusted as needed, for example using any acid and/or base. According to the present invention, the pH of the third composition can be maintained through the inclusion of acidic substances, such as water-soluble and/or water-dispersible acids, such as nitric acid, sulfuric acid and/or phosphoric acid. According to the present invention, the pH of the composition is adjusted to a water-soluble and/or water-dispersible base such as sodium hydroxide, sodium carbonate, potassium hydroxide, ammonium hydroxide, ammonia, and/or amines such as triethylamine, methylethyl It can be maintained by including a basic material, including an amine, or mixtures thereof.

According to the present invention, the third composition may further comprise a resinous binder. Suitable resins include reaction products of at least one alkanolamine with an epoxy-functional material containing at least two epoxy groups, such as those disclosed in U.S. Patent No. 5,653,823. In some cases, the resin contains beta hydroxy ester, imide, or sulfide functionality incorporated using dimethylolpropionic acid, phthalimide, or mercaptoglycerin as an additional reactant in preparing the resin. Alternatively, the reaction mixture may be prepared by, for example, a diglycidyl ether of bisphenol A in a molar ratio of 0.6 to 5.0:0.05 to 5.5:1 (eg, EPON from Shell Chemical Company). 880), dimethylol propionic acid, and diethanolamine. Other suitable resinous binders include water-soluble and water-dispersible polyacrylic acids, such as those disclosed in US Pat. Nos. 3,912,548 and 5,328,525; phenol formaldehyde resins, such as those disclosed in US Pat. No. 5,662,746; water-soluble polyamides, such as those disclosed in WO 95/33869; copolymers of maleic or acrylic acid with allyl ether, such as those disclosed in Canadian Patent Application No. 2,087,352; and water-soluble and water-dispersible resins such as epoxy resins, aminoplasts, phenol-formaldehyde resins, tannins, and polyvinyl phenols such as those disclosed in U.S. Patent No. 5,449,415.

According to the present invention, the resin binder may often be present in the third composition in an amount of 0.005 to 30% by weight, such as 0.5 to 3% by weight, based on the total weight of the composition. Alternatively, in accordance with the present invention, the third composition may be substantially free of, or in some cases completely free of, any resin binder. The term “substantially free of,” as used herein, when used in conjunction with a reference to the absence of a resin binder in a third composition, if present, includes, if present, any resin binder in the third composition, based on the total weight of the composition. is meant to be present in a trace amount of less than 0.005% by weight. As used herein, the term “completely free” means that the third composition is completely free of resin binder.

The third composition may comprise an aqueous medium and may optionally contain other substances such as and nonionic surfactants and adjuvants conventionally used in the art of the third composition. In an aqueous medium, a water-dispersible organic solvent, for example, an alcohol having up to about 8 carbon atoms, such as methanol, isopropanol, and the like; or glycol ethers such as monoalkyl ethers such as ethylene glycol, diethylene glycol, or propylene glycol. When present, the water-dispersible organic solvent is typically used in an amount of up to about 10% by volume, based on the total volume of the aqueous medium.

Other optional materials include surfactants that act as defoamers or substrate wetting agents. Anionic, cationic, zwitterionic and/or nonionic surfactants may be used. The antifoam surfactant may optionally be present at a level of 1 wt% or less, such as 0.1 wt% or less, and the wetting agent is typically present at a level of 2 wt% or less, such as 0.5 wt% or less, based on the total weight of the third composition do.

Optionally, according to the present invention, the third composition and/or film deposited or formed therefrom contains at least 10 ppm, such as at least 20 ppm, based on the total weight of the third composition, such as silicon, such as silane, silica, silicate, etc. It may be further included in an amount of 50 ppm or more. According to the present invention, the third composition and/or a film deposited or formed therefrom may comprise silicon in an amount of less than 500 ppm, such as less than 250 ppm, such as less than 100 ppm, based on the total weight of the third composition. According to the present invention, the third composition and/or a film deposited or formed therefrom will contain silicon in an amount of from 10 to 500 ppm, such as from 20 to 250 ppm, such as from 50 to 100 ppm, based on the total weight of the third composition. can Alternatively, the third composition of the present invention and/or a film deposited or formed therefrom may be substantially free of, or in some cases completely free of, silicon.

The third composition may comprise a carrier, often an aqueous medium, such that the composition is in the form of a solution or dispersion of a Group IVB metal in the carrier. According to the present invention, the solution or dispersion may be brought into contact with the substrate by any of a variety of known techniques, such as dipping or impregnating, spraying, intermittent spraying, dipping and subsequent dipping, spraying and subsequent dipping, brushing, or roll-coating. can According to the invention, the solution or dispersion, when applied to a metallic substrate, is at a temperature of 40 to 185°F, such as 60 to 110°F, such as 70 to 90°F. For example, the third process may be performed at room temperature or room temperature. The contact time is often between 5 seconds and 15 minutes, such as between 10 seconds and 10 minutes, such as between 15 seconds and 3 minutes.

Following the step of contacting with the third composition, the substrate may be rinsed with tap water, deionized water, and/or an aqueous solution of a detergent to remove any residue. The substrate can optionally be air dried at room temperature, for example by using an air knife, by flashing off water by simple exposure of the substrate to high temperature, eg, 15 High temperature by drying in an oven at to 200° C., such as 20 to 90° C., or in a heater assembly using, for example, infrared heat, such as at 70° C. for 10 minutes, or by passing the substrate between squeegee rolls. Can be air dried. According to the present invention, following the step of contacting with the third composition, the substrate may optionally be rinsed with tap water, deionized water, and/or an aqueous detergent solution to remove any residue, then optionally, for example, in the paragraph above It can be air dried as described in or dried with hot air.

According to the invention, the film coverage of the residue of the pretreatment coating composition is generally from 1 to 1,000 mg/m ² , for example from 10 to 400 mg/m ² . The thickness of the pretreatment coating may be, for example, less than 1 μm, for example 1-500 nm, or 10-300 nm. The coating weight can be determined by removing the film from the substrate and determining the elemental composition using various analytical techniques (XRF, ICP, etc.). The pretreatment thickness can be determined using a few analytical techniques, such as, but not limited to, XPS depth profiling or TEM.

Additional Components of the Systems and Methods of the Invention

In accordance with the present invention, prior to contacting at least a portion of the surface of the substrate with one of the compositions, at least a portion of the surface of the substrate may be cleaned and/or deoxygenated to remove grease, dust and/or other foreign matter. At least a portion of the substrate surface may be cleaned by physical and/or chemical means, for example, mechanical polishing of the surface, and/or cleaning/degreasing of the surface with commercially available alkaline or acidic cleaning agents well known to those skilled in the art. . Examples of alkaline cleaners suitable for use in the present invention include Chemkleen™ 166HP, 166M/C, 177, 490MX, 2010LP and Surface Prep 1 (SP1), Ultrax 32, Ultra Lax 97, Ultrax 29 and Ultrax 92D (each of which is commercially available from PPG Industries, Inc., Cleveland, Ohio), and PRC-Desoto International ( DFM series, RECC 1001 and 88X1002 cleaners commercially available from PRC-Desoto International: Silmar, CA, and Turco 4215-NCLT and Ridolene (Henkel Technologies, Madison Heights, Michigan, USA). commercially available from Henkel Technologies). Such cleaning agents are often preceded or followed by a water rinse, such as tap water, distilled water, or a combination thereof.

As described above, in accordance with the present invention, at least a portion of the cleaned substrate surface may be mechanically and/or chemically deoxidized. As used herein, the term “deoxidation” refers to the removal of an oxide layer found on the surface of a substrate to promote uniform deposition of the conversion composition (described below) and to promote adhesion of the conversion composition coating to the substrate surface. do. Suitable deoxidizers will be familiar to those skilled in the art. A typical mechanical deoxidizer would be uniform roughening of the substrate surface, such as by scouring or using a cleaning pad. Typical chemical deoxidizers include, for example, acid-based deoxidizers such as phosphoric acid, nitric acid, fluoroboric acid, sulfuric acid, chromic acid, hydrofluoric acid and ammonium difluoride, or Amchem 7/17 deoxidizer (Madison, Michigan, USA). (available from Henkel Technologies, Heights), OAKITE deoxidizer LNC (commercially available from Chemetall), Turco deoxidizer 6 (commercially available from Henkel), or a combination thereof do. Often, the chemical deoxidizing agent comprises a carrier, often an aqueous medium, so that the deoxidizing agent can be in the form of a solution or dispersion in a carrier, in which case the solution or dispersion is immersed or impregnated, sprayed, intermittent sprayed, immersed followed by spraying, spraying It may be contacted with the substrate by any of a variety of known techniques, such as post dipping, brushing or roll-coating. According to the present invention, a person skilled in the art will know, based on the etch rate, for example, 50°F to 150°F (10°C to 66°C), such as 70°F to 130°F (21°C to 54°C), such as 80°F to 120°F. At temperatures of F (27° C. to 49° C.), the temperature range of the solution or dispersion, when applied to a metallic substrate, will be selected. The contact time may be from 30 seconds to 20 minutes, such as from 1 minute to 15 minutes, such as from 90 seconds to 12 minutes, such as from 3 minutes to 9 minutes.

After the cleaning and/or deoxidation step, the substrate may optionally be rinsed with tap water, deionized water and/or aqueous detergent solution to remove any residue. According to the invention, the wet substrate surface can be treated with a conversion composition (described below) and/or a sealing composition (described above), or the substrate can be treated with air prior to substrate surface treatment, for example using an air knife. Flashing off the water by drying, or lightly exposing the substrate to a high temperature, such as 15° C. to 100° C., such as 20° C. to 90° C., or 70° C. for 10 minutes, for example, in a heater assembly using infrared heat, for example. or by passing the substrate between squeegee rolls.

As noted above, at least a portion of the surface of the substrate may optionally be contacted with a second or third composition before or after contacting with the first composition of the present invention.

A color measurement may be determined for a substrate treated with the first composition (cerium) to characterize the degree of yellowing of the treated substrate. Color parameters were determined using an Xrite Ci7800 Benchtop Sphere Spectrometer (25 mm aperture commercially available from X-Rite, Incorporated, Granville, Michigan) or similar instrument. can be measured. The Xlite Ci7800 instrument measures according to the L ^* a ^* b ^* color space theory. The term b ^* indicates a more yellowish tint for positive values and a more blue tint for negative values. The term a ^* has a more greenish tint if negative and a more red tint if positive. The term L ^* denotes a black tint when L ^* =0 and a white tint when L ^* =100.

In accordance with the present invention, the substrates pretreated with the first composition typically had a b ^* value between 9 and 15. Application of the heating step may result in a b ^* value of the substrate in contact with the first composition, for example a b* of -20 to +8, such as -15 to +5, such as -10 to +4, such as -5 to +2.5. value was significantly reduced. Substrates treated according to the present invention may be, for example, ASTM E313-00 of +5 to +22 before heating, and +2 to +10, such as +3 to +9, such as +4 to +8, after heat treatment. YI-E313 (yellow index) measured by

The effect of heating the panel after contact with the cerium-containing composition has minimal effect on the values of a ^* and L ^* . The value for a ^* will be -15 to +15, such as -10 to +10, such as -5 to +5, irrespective of the heat treatment. The L ^* value, irrespective of heat treatment, will be between 50 and 90, such as between 60 and 80.

According to the present invention, a substrate comprising, in some cases consisting essentially of, or in some cases consisting of a film formed from a pretreatment composition comprising, in some cases consisting essentially of, or consisting of lanthanides and an oxidizing agent , where the level of lanthanide in the film is greater than 100 counts on the surface of the substrate without the film thereon [X-ray fluorescence (60 sec timed assay, 15 Kv, 45 μA, filter 3, T(p) ) = 1.5 μs)] are disclosed herein.

According to the present invention, the level of the lanthanide series element in the film formed on the surface of the substrate from the pretreatment composition is at least 100 counts greater than on the surface of the substrate without the film thereon [X-ray fluorescence (60 sec timed assay, 15 Kv, 45 μA, filter 3, T(p) = 1.5 μs)]. For example, greater than 340 counts, such as greater than 500 counts, such as greater than 1,000 counts, measured by X-ray fluorescence (60 second timed assay, 15 Kv, 45 μA, filter 3, T(p) = 1.5 μs); For example, the lanthanide series element may be present in a film formed on the substrate surface as indicated by counts greater than 1,200 counts. Surprisingly, it has been found herein that pretreatment of sanded substrates with the pretreatment compositions of the present invention surprisingly resulted in superior corrosion performance compared to unsanded substrates pretreated with conventional pretreatment compositions.

In accordance with the present invention, a substrate having a film formed from the pretreatment composition has a scribe creep on the surface of the substrate of at least 5% as compared to a substrate treated with a zirconium-containing pretreatment further comprising lithium and molybdenum. has a decrease (ASTM-B 368-09 Copper Acetate Salt Spray, 480 hours).

Surprisingly, it was found that the cured electrocoated panels treated with the zirconium-containing pretreatment composition were yellow as seen with the naked eye, whereas the cured electrocoated panels treated with the lanthanide-containing pretreatment composition, in contrast, were not the yellow color seen with the naked eye. became These results were not expected.

Moreover, it was also surprisingly found that heating the substrates pretreated with the conversion composition of the present invention at a temperature of 110 to 232° C. surprisingly reduced the yellowing seen on unheated panels pretreated with the conversion composition of the present invention. For example, surprisingly, the b ^* values and YI-E313 values of the panels (sanded and unsanded) treated with the conversion composition of the present invention were significantly reduced when these panels were pretreated with the conversion composition of the present invention , was found to decrease even further when these panels were heated to 110-232°C.

Surprisingly, electrocoated panels pretreated with a pretreatment composition comprising cerium exhibited scribe creep (ASTM-B 368- 09) was also found to cause a 27% reduction. These results were not expected.

Surprisingly, electrocoated panels pretreated with a pretreatment composition comprising cerium exhibited scribe creep (ASTM-B 368-09) after 480 h exposure to copper acetate spray, compared to electrocoated panels pretreated with zinc phosphate pretreatment. ) was also found to cause a 65% reduction in These results were not expected.

According to the present invention, the coating composition may comprise a thermosetting film-forming resin or a thermoplastic film-forming resin. As used herein, the term "film-forming resin" means a resin capable of forming a self-supporting continuous film on at least the horizontal surface of a substrate upon curing at room temperature or high temperature, or upon removal of any diluent or carrier present in the composition. means Conventional film forming resins that may be used include, but are not limited to, 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. include things that are As used herein, the term “thermoset” refers to a resin that irreversibly “curs” upon curing or crosslinking, wherein the polymer chains of the polymer components are bound together by covalent bonds. This property usually relates to the crosslinking reaction of the composition components, which is often induced, for example by heat or radiation. The curing or crosslinking reaction may also be carried out under ambient conditions. Once cured or crosslinked, thermosetting resins do not melt when heated and are insoluble in solvents. As used herein, the term “thermoplastic” refers to a resin comprising a polymeric component that is not bound by covalent bonds and is therefore capable of undergoing liquid flow upon heating and is soluble in solvents.

As described above, according to the present invention, the electrodepositable coating composition can be deposited on a substrate by an electrocoating step in which the electrodepositable coating composition is deposited on a metal substrate by electrodeposition. containing film-forming resin.

The ionic salt group-containing film-forming polymer may include cationic salt groups containing the film-forming polymer for use in cationic electrodepositable coating compositions. As used herein, the term “cationic salt group-containing film-forming polymer” means a polymer comprising at least partially neutralized cationic groups imparting a positive charge, such as sulfonium groups and ammonium groups. The cationic salt group-containing film-forming polymer may comprise active hydrogen functional groups, including, for example, hydroxyl groups, primary or secondary amine groups and thiol groups. Cationic salt group-containing film-forming polymers comprising active hydrogen functional groups may be referred to as active hydrogen-containing cationic salt group-containing film-forming polymers. Examples of polymers suitable for use as cationic salt group-containing film-forming polymers include, but are not limited to, alkyd polymers, acrylics, polyepoxides, polyamides, polyurethanes, polyureas, polyethers and polyesters, among others. not limited

The cationic salt group-containing film-forming polymer is present in an amount of 40 to 90% by weight, such as 50 to 80% by weight, such as 60 to 75% by weight, based on the total weight of resin solids of the electrodepositable coating composition. may be present in the electrodepositable coating composition. As used herein, “resin solids” includes the ionic salt group-containing film-forming polymer, the curing agent, and any additional water dispersible non-pigmenting components present in the electrodepositable coating composition.

Alternatively, the ionic salt group-containing film-forming polymer may include an anionic salt group-containing film-forming polymer for use in an anionic electrodepositable coating composition. As used herein, the term “anionic salt group-containing film-forming polymer” refers to an anionic polymer comprising at least partially neutralized anionic functional groups, such as carboxylic acid and phosphoric acid groups that impart a negative charge. The anionic salt group-containing film-forming polymer may comprise active hydrogen functional groups. An anionic salt group-containing film-forming polymer comprising active hydrogen functional groups may be referred to as an active hydrogen-containing anionic salt group-containing film-forming polymer.

Anionic salt group-containing film-forming polymers include base-dissolved carboxylic acid group-containing film-forming polymers, such as reaction products or adducts of dry oil or semi-dry fatty acid esters with dicarboxylic acids or anhydrides; and reaction products of a fatty acid ester, an unsaturated acid or anhydride, and any additional unsaturated modifying material further reacted with the polyol. Also suitable are hydroxy-alkyl esters of unsaturated carboxylic acids, at least partially neutralized interpolymers of unsaturated carboxylic acids and one or more other ethylenically unsaturated monomers. Still other suitable anionic electrodepositable resins include alkyd-aminoplast vehicles, i.e., vehicles containing alkyd resins and amine-aldehyde resins. Another suitable anionic electrodepositable resin composition comprises a mixed ester of a resinous polyol. Other acid functional polymers may also be used, such as phosphatized polyepoxides or phosphated acrylic polymers. Exemplary phosphated polyepoxides are disclosed in US Patent Publication No. 2009-0045071 ([0004]-[0015]) and US Patent Application Serial No. 13/232,093 ([0014]-[0040]) and , the cited portions of which are incorporated herein by reference.

The anionic salt group-containing film-forming polymer is anionic electrodepositable in an amount of 50 to 90%, such as 55 to 80%, such as 60 to 75%, based on the total weight of resin solids of the electrodepositable coating composition. may be present in the coating composition.

The electrodepositable coating composition may further comprise a curing agent. The curing agent can react with reactive groups, such as active hydrogen groups, of the ionic salt group-containing film-forming polymer to cure the coating composition to form a coating. Non-limiting examples of suitable curing agents are at least partially blocked polyisocyanates, aminoplast resins and phenolplast resins such as phenolformaldehyde condensates (including allyl ether derivatives thereof).

The curing agent may be present in the cationic electrodepositable coating composition in an amount of 10 to 60% by weight, such as 20 to 50% by weight, such as 25 to 40% by weight, based on the total weight of the resin solids of the electrodepositable coating composition. Alternatively, the curing agent is added to the anionic electrodepositable coating composition in an amount of 10 to 50% by weight, such as 20 to 45% by weight, such as 25 to 40% by weight, based on the total weight of the resin solids of the electrodepositable coating composition. may exist.

The electrodepositable coating composition comprises a pigment composition and, if necessary, various additives such as fillers, plasticizers, antioxidants, biocides, UV light absorbers and stabilizers, hindered amine light stabilizers, defoamers, fungicides, dispersing aids. , a flow control agent, a surfactant, a wetting agent, or a combination thereof.

The electrodepositable coating composition may include water and/or one or more organic solvents. Water may be present, for example, in an amount of 40 to 90% by weight, such as 50 to 75% by weight, based on the total weight of the electrodepositable coating composition. When used, the organic solvent may typically be present in an amount of less than 10% by weight, for example less than 5% by weight, based on the total weight of the electrodepositable coating composition. The electrodepositable coating composition may be provided in particular in the form of an aqueous dispersion. The total solids content of the electrodepositable coating composition may be 1% to 50% by weight, such as 5% to 40% by weight, such as 5% to 20% by weight, based on the total weight of the electrodepositable coating composition. As used herein, “total solids” refers to the non-volatile content of the electrodepositable coating composition, i.e., a material that does not volatilize when heated to 110° C. for 15 minutes.

The cationic electrodepositable coating composition can be deposited on an electrically conductive substrate by contacting the composition with an electrically conductive cathode and an electrically conductive anode, wherein the surface to be coated is the cathode. Alternatively, the anionic electrodepositable coating composition may be deposited on an electrically conductive substrate by contacting the composition with an electrically conductive cathode and an electrically conductive anode, wherein the surface to be coated is the anode. The adhesive film of the electrodepositable coating composition is deposited in a substantially continuous manner on the cathode or anode, respectively, when a sufficient voltage is applied between the electrodes. The applied voltage can vary and can be, for example, from a low of 1 volt to a high of several thousand volts, such as from 50 to 500 volts. The current density is generally 1.0 to 15 amps per square foot (10.8 to 161.5 amps per square meter) and tends to decrease rapidly during the electrodeposition process, indicating the formation of a continuous self-insulating film.

Once the cationic or anionic electrodepositable coating composition is electrodeposited onto at least a portion of the conductive substrate, the coated substrate is heated for a temperature and for a time sufficient to cure the electrodeposited coating on the substrate. For cationic electrodeposition, the coated substrate may be heated to a temperature of 110°C to 232°C, such as 275°F to 400°F (135°C to 204.4°C), such as 300°F to 360°F (149°C to 180°C). . For anionic electrodeposition, the coated substrate may be 200°F to 450°F (93°C to 232.2°C), such as 275°F to 400°F (135°C to 204.4°C), such as 300°F to 360°F (149°C to 180°C). , for example, to a temperature of 200°F to 210.2°F (93°C to 99°C). The curing time may depend on the curing temperature as well as other variables such as the film thickness of the electrodeposited coating, the level and type of catalyst present in the composition, and the like. For example, the curing time may be from 10 to 60 minutes, for example from 20 to 40 minutes. The thickness of the resulting cured electrodeposited coating may range from 2 to 50 μm.

Alternatively, as described above, according to the present invention, after the substrate is contacted with the sealing composition, the powder coating composition may be deposited on at least a portion of the surface of the substrate. As used herein, "powder coating composition" means a coating composition that is completely free of water and/or solvent. Accordingly, the powder coating compositions disclosed herein are not synonymous with water-based and/or solvent-based coating compositions known in the art.

According to the present invention, a powder coating composition comprises (a) a film-forming polymer having reactive functional groups; and (b) a curing agent reactive with the functional group. Examples of the powder coating composition that can be used in the present invention include a polyester-based ENVIROCRON line of powder coating compositions (commercially available from PPG Industries, Inc.) or an epoxy-polyester hybrid powder coating composition. do. Alternative examples of powder coating compositions that can be used in the present invention include (a) one or more tertiary aminourea compounds, one or more tertiary aminourethane compounds, or mixtures thereof, and (b) one film-forming epoxy-containing low temperature curing thermosetting powder coating compositions comprising a resin and/or one or more siloxane-containing resins (such as those described in U.S. Patent Publication No. 7,470,752 assigned to PPG Industries, Inc. and incorporated herein by reference); 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 curable powder coating compositions (eg, those described in US Pat. No. 7,432,333 assigned to PPG Industries, Inc. and incorporated herein by reference); and those comprising solid particulate mixtures of reactive group-containing polymers having a T _g of at least 30° C. (eg, those described in U.S. Patent No. 6,797,387 assigned to PPG Industries, Inc. and incorporated herein by reference). ) is included.

After deposition of the powder coating composition, the coating is often heated to cure the deposited composition. The heating or curing operation is often carried out at a temperature of 150° C. to 200° C., such as 170° C. to 190° C. for a period of 10 to 20 minutes. According to the invention, the thickness of the resulting film is between 50 and 125 μm.

As mentioned above, according to the present invention, the coating composition may be a liquid coating composition. As used herein, “liquid coating composition” refers to a coating composition containing a portion of water and/or solvent. Accordingly, the liquid coating compositions disclosed herein are synonymous with water-based and/or solvent-based coating compositions known in the art.

According to the present invention, the liquid coating composition comprises, for example: (a) a film-forming polymer having reactive functional groups; and (b) a curing agent reactive with the functional group. In another example, the liquid coating may contain a film-forming polymer that can react with oxygen in the air or aggregate into a film with evaporation of water and/or solvent. This film-forming mechanism may be required or accelerated by the application of heat, or some type of radiation, such as ultraviolet or infrared. Examples of liquid coating compositions that can be used in the present invention include the SPECTRACRON® line of solvent-based coating compositions, the AQUACRON® line of water-based coating compositions and RAYCRON® of UV curable coatings. registered trademark) line (all commercially available from PPG Industries, Inc.).

Suitable film-forming polymers that may be used in the liquid coating compositions of the present invention are (poly)esters, alkyds, (poly)urethanes, isocyanurates, (poly)ureas, (poly)epoxy, anhydrides, acrylics, (poly) ether, (poly)sulfide, (poly)amine, (poly)amide, (poly)vinyl chloride, (poly)olefin, (poly)vinylidene fluoride, (poly)siloxane, or combinations thereof .

According to the present invention, the substrate contacted with the sealing composition may be contacted with the primer composition and/or the topcoat composition. The primer coat can be, for example, a chromate-based primer and a high-performance topcoat. In accordance with the present invention, the primer coat can be a conventional chromate-based primer coat, such as those available from PG Industries, Inc. (product code 44GN072), or a chrome-free primer, such as those available from PG (product code 44GN072). DESOPRIME CA7502, DESOPRIME CA7521, Def 02GN083, Def 02GN084). Alternatively, the primer coat may be a chromate-free primer coat, such as US Patent Application Serial Nos. 10/758,973 entitled "Carbon Containing Corrosion Resistant Coatings" and US Patent Application Serial Nos. 10/758,972 and 10/758,972 (both of which are entitled "Corrosion Resistant Coatings"), all of which are incorporated herein by reference), and other chrome-free primers known in the art, which may be MIL - It can pass the military requirements of -PRF-85582 class N or MIL-PRF-23377 class N and can also be used in the present invention.

As noted above, the substrates of the present invention may also include a topcoat. The term "topcoat," as used herein, is a blend of organic or inorganic polymers, typically one or more pigments, optionally containing one or more solvents or mixtures of solvents, and optionally containing one or more curing agents. It means a mixture of binders that can be A topcoat is typically a coating layer in a single or multi-layer coating system in which the outer surface is exposed to the atmosphere or environment and the inner surface is in contact with another coating layer or polymeric substrate. Examples of suitable topcoats include those conforming to MIL-PRF-85285D, such as those available from PPG (Def 03W127A and Def 03GY292). In accordance with the present invention, topcoats include high performance topcoats, such as those available from sebum (Defthane® ELT.TM. 99GY001 and 99W009). However, other topcoats and high performance topcoats may be used in the present invention, as will be understood by one of ordinary skill in the art with reference to this disclosure.

According to the present invention, the metallic substrate may also comprise a self-priming topcoat or an improved self-priming topcoat. The term "self-priming topcoat", also referred to as a "direct to substrate" or "direct to metal" coating, can be a blend of organic or inorganic polymers, typically one or more pigments. and may optionally contain one or more solvents or mixtures of solvents, and may optionally contain one or more curing agents. An "enhanced self-priming topcoat", also referred to as an "enhanced direct to substrate coating", is a mixture of fluorinated binders that are fully functionalized, such as fluoroethylene-alkyl vinyl ethers; or mixtures thereof with at least partially other binders, which may be blends of organic or inorganic polymers, typically one or more pigments, optionally containing one or more solvents or mixtures of solvents, optionally one It may contain more than a hardening|curing agent. An example of a self-priming topcoat is a topcoat conforming to TT-P-2756A. Examples of self-priming topcoats include those available from PG (03W169 and 03GY369) and examples of reinforced self-priming topcoats include Deftan® ELTTM/ESPT and products available from PG. It has code number 97GY121. However, other self-priming topcoats and improved self-priming topcoats may be used in coating systems according to the present invention, as will be appreciated by those skilled in the art with reference to this disclosure.

According to the present invention, a self-priming topcoat and a reinforced self-priming topcoat can be applied directly to the sealed substrate. The self-priming topcoat and the reinforced self-priming topcoat may optionally be applied to an organic or inorganic polymer coating such as a primer or paint film. Self-priming topcoat layers and reinforced self-priming topcoats are typically single or multiple layers in which the outer surface of the coating is exposed to the atmosphere or environment and the inner surface of the coating is typically in contact with the substrate or optional polymeric coating or primer. It is the coating layer of the coating system.

In accordance with the present invention, topcoats, self-priming topcoats and enhanced self-priming topcoats are subjected to wet or "not fully cured" conditions that dry or cure over time (solvent evaporates and/or chemical reaction is present). ) can be applied to the sealed substrate. The coating may be dried or cured, either naturally or by means of an accelerated means, such as an ultraviolet light curing system, to form a film or “cured” paint. Coatings can also be applied semi-cured or fully cured as an adhesive.

In addition, colorants and, if desired, various additives such as surfactants, wetting agents or catalysts may be included in the coating composition (electrolytic, powder or liquid). As used herein, the term “colorant” means any substance that imparts color and/or other opacity and/or other visual effect to a composition. Exemplary colorants include pigments, dyes and tints, such as special effect compositions, as well as those used in the paint industry and/or listed in the Dry Color Manufacturers Association (DCMA).

In general, the colorant may be present in the coating composition in any amount sufficient to impart the desired visual and/or color effect. The colorant may be included in an amount of 1 to 65% by weight, such as 3 to 40% by weight or 5 to 35% by weight, based on the total weight of the composition.

For the purposes of the following detailed description, it is to be understood that the present invention is capable of various alternative modifications and sequence of steps, except where expressly opposed. Also, except in any working examples or where otherwise indicated, all numbers, such as those representing values, amounts, %, ranges, subranges, and fractions, refer to the word "about" even if "about" is not explicitly stated. It can be read as starting with Accordingly, unless otherwise indicated, the numerical parameters set forth in the following specification and appended claims are approximations which may vary depending upon the desired properties obtained by the present invention. At the very least, and not as an attempt to limit the application of the doctrine of equivalents to the claims, each numerical parameter should at least be construed in light of the number of reported significant digits and by applying ordinary rounding techniques. When closed or open numerical ranges are described herein, all numbers, values, amounts, %, subranges and fractions that are within or subsumed within a numerical range include those numbers, values, amounts, %, subranges and fractions. Fractions are to be construed as being specifically incorporated into and belonging to the original disclosure herein as if expressly set forth in their entirety.

Notwithstanding that the numerical ranges and parameters setting forth the broad scope of the invention are approximations, the numerical values set forth in the specific embodiments are reported as precisely as possible. All figures, however, inherently contain certain errors necessarily resulting from the standard deviation found in their respective test measurements.

As used herein, unless otherwise indicated, plural terms may include their singular counterparts and vice versa. For example, although reference is made herein to "a first composition," "a second composition," and an "oxidizing agent," combinations (ie, multiples) of these components may be used. Also, herein, the use of "or" means "and/or" unless otherwise stated, although "and/or" may be used explicitly in certain instances.

As used herein, terms such as “including”, “comprising”, etc., in the context of this application, are to be understood as synonymous with “comprising” and are thus open-ended and include elements that are not further described and/or mentioned; The presence of materials, components and/or method steps is not excluded. As used herein, “consisting of” is understood to exclude the presence of any unspecified elements, components and/or method steps in the context of the present application. As used herein, "consisting essentially of" is understood in the context of the present application to include certain elements, materials, components and/or method steps, and "those which do not materially affect the basic and novel properties" of those described.

Unless otherwise disclosed herein, the term "substantially free of," when used in reference to the absence of a substance, includes a composition, a bath containing the composition, and/or a layer formed from and comprising the composition. If present, such material is present in any amount that may be derived or present as a result of decomposition of the substrate and/or equipment, as the case may be, the total weight of the composition and/or layer (drag-in). excluding substances), only in trace amounts of 5 ppm or less. Unless otherwise disclosed herein, the term "essentially free of," when used in reference to the absence of a substance, is within a composition, a bath containing the composition, and/or a layer formed from and comprising the composition. If present, it is meant that such substances are present in trace amounts of no more than 1 ppm, as the case may be, based on the total weight of the composition and/or layer. Unless otherwise disclosed herein, the term "completely free of," when used in reference to the absence of a substance, is present in a composition, a bath containing the composition, and/or a layer formed from and comprising the composition. if so, such material is absent from the composition, the bath containing the composition, and/or the layer formed from and comprising the composition (ie, the composition, the bath containing the composition, and/or formed from the composition). and the layer comprising it contains 0 ppm of the material).

As used herein, the terms “on”, “onto”, “applied on”, “applied onto”, “formed on”, “deposited on”, “deposited onto” on a surface formed, superimposed, deposited and/or provided, but not necessarily in contact therewith. For example, a coating layer “formed on” a substrate does not exclude the presence of one or more other intervening coating layers of the same or different composition positioned between the formed coating layer and the substrate.

As used herein, “salt” refers to an ionic compound consisting of a metal cation and a non-metal anion and having an overall electrical charge of zero. The salt may be hydrated or anhydrous.

As used herein, "aqueous composition" means a solution or dispersion in a medium comprising primarily water. For example, the aqueous medium may comprise water in an amount greater than 50 weight percent, or greater than 70 weight percent, or greater than 80 weight percent, or greater than 90 weight percent, or greater than 95 weight percent, based on the total weight of the medium. can The aqueous medium may, for example, consist essentially of water.

As used herein, “conversion composition” refers to a composition capable of reacting with or chemically modifying and bonding a substrate surface to form a film that provides corrosion protection.

As used herein, "conversion bath" refers to an aqueous bath that contains the conversion composition and may contain components that are by-products of the process of contacting a substrate with the conversion composition.

As used herein, the term “first composition metal cation” refers to a metal cation of a lanthanide series element, a Group IIA metal, a Group IIIB metal, a Group IVB metal, a Group VB metal, a Group VIB metal, a Group VIIB metal and/or a Group XII metal. refers to

As used herein, a “sealing composition” refers to, for example, a material deposited on a substrate surface or affecting a substrate surface in a manner that alters the physical and/or chemical properties of the substrate surface (eg, the composition provides corrosion protection). Giving refers to a composition, such as a solution or dispersion.

As used herein, the term "group IA metal" means an element belonging to group IA of the CAS version of the Periodic Table of the Elements, described, for example, in the Handbook of Chemistry and Physics, 63 ^rd edition (1983), which is actually IUPAC It corresponds to group 1 of numbering.

As used herein, the term “group IA metal compound” means a compound comprising one or more elements belonging to group IA of the CAS version of the Periodic Table of the Elements.

As used herein, the term "group IIIB metal" refers to, for example, yttrium and the CAS version of the Periodic Table of the Elements set forth in Handbook of Chemistry and Physics, 63 ^rd edition (1983), corresponding to group 3 in actual IUPAC numbering, and It refers to scandium. For the sake of clarity, "Group IIIB metal" explicitly excludes lanthanide series elements.

As used herein, the term “Group IIIB metal compound” refers to a compound comprising one or more elements belonging to Group IIIB of the CAS version of the Periodic Table of the Elements as defined above.

As used herein, the term "group IVB metal" means an element belonging to group IVB of the CAS version of the Periodic Table of the Elements, described, for example, in the Handbook of Chemistry and Physics, 63 ^rd edition (1983), which is actually IUPAC It corresponds to the 4th group of numbering.

As used herein, the term “group IVB metal compound” refers to a compound comprising one or more elements belonging to group IVB of the CAS version of the Periodic Table of the Elements.

As used herein, the term "group VB metal" refers to an element belonging to group VB of the CAS version of the Periodic Table of the Elements, described, for example, in the Handbook of Chemistry and Physics, 63 ^rd edition (1983), which is actually IUPAC It corresponds to group 5 of numbering.

As used herein, the term “group VB metal compound” refers to a compound comprising one or more elements belonging to group VB of the CAS version of the Periodic Table of the Elements.

As used herein, the term "group VIB metal" refers to, for example, group VIB of the CAS version of the Periodic Table of the Elements presented in the Handbook of Chemistry and Physics, 63 ^rd edition (1983), corresponding to group 6 in actual IUPAC numbering, for example. refers to elements belonging to

As used herein, the term “Group VIB metal compound” refers to a compound comprising one or more elements belonging to Group VIB of the CAS version of the Periodic Table of the Elements.

As used herein, the term “lanthanide series element” refers to elements 57 through 71 of the CAS version of the Periodic Table of the Elements, and includes elemental versions of the lanthanide series elements. In an aspect, the lanthanide series element may be an element having both the conventional states of +3 and +4, hereinafter referred to as +3/+4 oxidation states.

As used herein, the term “lanthanide compound” refers to a compound comprising one or more of elements 57 to 71 of the CAS version of the Periodic Table of the Elements.

The term “halogen,” as used herein, refers to any of the elements fluorine, chlorine, bromine, iodine and astatine in the CAS version of the Periodic Table of the Elements, which corresponds to Group VIIA of the Periodic Table.

As used herein, the term “halide” refers to a compound comprising one or more halogens.

As used herein, the term “aluminum,” when used in reference to a substrate, refers to a substrate made of or comprising aluminum and/or an aluminum alloy, and a clad aluminum substrate.

As used herein, the term "oxidizer," when used in reference to a component of a conversion composition, is a metal present in the substrate contacted by the conversion composition, a lanthanide series element present in the conversion composition, and/or a metal present in the conversion composition. -Refers to a chemical that can oxidize one or more of the complexing agents. The phrase "capable of oxidizing," as used herein with respect to "oxidizing agent," optionally removes electrons from atoms or molecules present in a substrate or conversion composition, thereby reducing the number of electrons in such atoms or molecules. means you can do it.

Unless otherwise indicated herein, the terms "total composition weight", "total weight of composition" or similar terms herein refer to the total weight of all components present in each composition, including optional carriers and solvents. do.

Accordingly, in view of the foregoing description, the present invention relates, inter alia, without limitation, to the following aspects 1-29:

Aspect

1. A system for treating a substrate comprising a first composition for contacting at least a portion of the substrate, the first composition comprising a lanthanide series elemental cation and an oxidizing agent.

2. The method according to the first aspect,

wherein the oxidizing agent is present in the first composition in an amount of 25 to 25,000 ppm based on the total weight of the first composition.

3. according to aspect 1 or 2,

wherein the lanthanide series element cation comprises cerium, praseodymium, or a combination thereof.

4. according to any one of aspects 1 to 3,

wherein the lanthanide series elemental cation is present in the first composition in an amount of from 50 to 200 ppm calculated as cations based on the total weight of the first conversion composition.

5. according to any one of aspects 1 to 4,

A second composition for treating at least a portion of the substrate, the system further comprising a second composition comprising a Group IA metal cation.

6. according to the fifth aspect,

wherein the Group IA metal cation comprises lithium, sodium, potassium, or a combination thereof.

7. according to aspect 5 or 6,

wherein the Group IA metal cation is present in the second composition in an amount of from 5 to 30,000 ppm as metal cations based on the total weight of the second composition.

8. according to any one of aspects 5 to 7,

wherein the second composition has a pH between 8 and 13.

9. according to any one of aspects 1 to 4,

A third composition for treating at least a portion of the substrate, the system further comprising a third composition comprising a Group IVB metal cation.

10. The ninth aspect,

wherein the Group IVB metal cation is zirconium, titanium, or a combination thereof.

11. according to aspect 9 or 10,

wherein the Group IVB metal cation is present in the third composition in an amount of 110 to 170 ppm as metal cations based on the total weight of the third composition.

12. The method according to any one of aspects 9 to 11,

wherein the third composition has a pH between 4 and 5.

13. The system of any one of aspects 9-12, wherein the third composition further comprises an amino compound.

14. according to any one of aspects 1 to 13,

A system substantially free of phosphate.

15. A substrate treated with the system according to any one of aspects 1 to 14.

16. The method of aspect 15,

The substrate treated with the system has at least a 5% reduction in scribe creep on the substrate surface as measured by the CASS test as compared to a substrate treated with a composition comprising zirconium.

17. according to aspect 15 or 16,

A substrate having at least a portion of the surface of the substrate sanded and treated with the system has a reduction of at least 55% in scribe creep on the surface of a sanded substrate as measured by a linear corrosion test as compared to a sanded substrate treated with a composition comprising zirconium having, the substrate.

18. according to any one of aspects 15-17,

At least a portion of the surface of the substrate was sanded and the substrate treated with the system had a 78% in scribe creep on the surface of the sanded substrate as measured by the ASTM G85 A2 corrosion test as compared to a sanded substrate treated with a composition comprising zirconium. A substrate having an or greater reduction.

19. A substrate treated with the system according to the fifth aspect.

20. Aspect 19, further comprising:

A substrate treated with the system has at least a 25% reduction in scribe creep on a substrate surface as measured by the ASTM G85 A2 test as compared to a substrate treated with a composition comprising zirconium.

21. A substrate treated with the system according to the ninth aspect.

22. Clause 21,

A substrate treated with the system had a 13% reduction in scribe creep on the substrate surface as measured by the CASS test, as compared to a substrate treated with a composition comprising one of a lanthanide series element cation and a Group IVB metal cation; a 47% reduction in scribe creep on the substrate surface as measured by SAE J2635 as compared to a substrate treated with a composition comprising one of a lanthanide series element cation and a Group IVB metal cation; and/or at least a 42% increase in crosshatch adhesion as compared to a substrate treated with a composition comprising one of a lanthanide series elemental cation and a Group IVB metal cation.

23. A method of treating a substrate comprising contacting at least a portion of the surface of the substrate with a first composition comprising a lanthanide series elemental cation and an oxidizing agent.

24. The method of aspect 23,

the substrate surface is contacted with the first composition, resulting in a level of lanthanide series element cations on the contacted substrate surface measured by X-ray fluorescence that is at least 100 counts greater than on the surface of the substrate not contacted with the first composition; , wherein the X-ray fluorescence is measured by an X-Met 7500 from Oxford Instruments (operating parameters 60 sec timed assay, 15 Kv, 45 μA, filter 3, T(p) = 1.5 μs). processing method.

25. Aspect 23 or 24,

and contacting at least a portion of the surface of the substrate with a second composition comprising a Group IA metal cation and/or a Group IVB metal cation.

26. according to any one of aspects 23 to 25,

wherein the step of contacting with the first composition is performed prior to the step of contacting with the second composition.

27. according to any one of aspects 23 to 25,

wherein the step of contacting with the second composition is performed prior to the step of contacting with the first composition.

28. The method according to any one of aspects 23 to 27,

wherein the step of contacting with the first composition is from 15 seconds to 4 minutes.

29. The method according to any one of aspects 23 to 28,

and heating the substrate at a temperature of 110 to 232° C. for 15 to 30 minutes.

30. A substrate treated by the treatment method according to aspect 29, wherein the substrate has a b ^* value of less than 3.09 measured with a 25 mm aperture, excluding spectral components.

While certain features of the invention have been described for purposes of illustration, it will be apparent to those skilled in the art that numerous modifications of the coating compositions, coatings and methods disclosed herein can be made without departing from the scope of the appended claims.

Although the present invention is illustrated in the following examples, it should not be construed that the invention is limited to the details of these examples. In the examples as well as throughout the specification, all parts and percentages are by weight, unless months are stated.

Example

Example One:

detergent bath

A detergent bath was prepared with ChemClean 2010LP (a phosphate-free alkaline cleaner commercially available from sebum) at a concentration of 1.25% v/v and ChemClean 181 ALP (a phosphate-free formulated surfactant additive commercially available from sebum) at 0.125% did For the spray wash, a 10 gallon bath was prepared. The bath consisted of deionized water. The bath temperature was 120° F. and was used for 2 minutes when the panel was run through the cleaner. The pressure of the spray wash was between 10 and 15 psi with the use of a series of “Vee Jet” spray nozzles.

zinc phosphate pretreatment bath 1 ( comparative example )

A 5 gallon vessel was filled approximately 3/4 full with deionized water. 700 mL of Chemfos 700A, 1.5 mL of Chemfos FE, 51 mL of Chemfos AFL, and 375 mL of Chemfos 700B (all commercially available from PPG) were added. 28.6 g of zinc nitrate hexahydrate and 2.5 g of sodium nitrite (both commercially available from Fischer Scientific) were added. The free acid of the bath was adjusted to 0.7 to 0.8 points of free acid, 15 to 19 points of total acid, and 2.2 to 2.7 gas points of nitrite. Free acid and total acid were determined as follows:

equipment:

Reeve Angel 802 filter paper or equipment

10 mL pipette

analysis funnel

25 to 50 mL burette

150 mL beaker

reagent:

0.1 N sodium hydroxide

Bromophenol blue indicator

phenolphthalein indicator

free acid Procedure for titration:

1. A sample of the phosphating bath was filtered.

2. Pipet 10 mL of the filtrate into a clear, dry 150 mL beaker.

3. Add 3-5 drops of bromophenol blue indicator to the beaker containing the filtrate.

4. The solution was titrated with 0.1 N sodium hydroxide solution from yellow-green to clear bright blue (green absent but prior to blue-violet) endpoint.

5. Record the number of mL of 0.1 N sodium hydroxide used as the free acid .

Procedure for total acid titration:

1. A sample of the phosphating bath was filtered.

2. Pipet 10 mL of the filtrate into a clear, dry 150 mL beaker.

3. Add 3-5 drops of phenolphthalein indicator to the beaker containing the filtrate.

4. The solution was titrated with 0.1 N sodium hydroxide solution until a permanent pink color appeared.

5. Record the number of mL of 0.1 N sodium hydroxide used as the total acid .

The amount of nitrite in solution was measured using a fermentation tube according to the protocol described in the Technical Data Sheet for Chemposs Liquid Additives (PPG Industries, Inc., Cleveland, Ohio). The fermentation tube was filled with the pretreatment bath of a 70 mL sample of the pretreatment bath just below the opening of the tube. About 2.0 g of sulfamic acid was added to the tube, and the tube was inverted to mix the sulfamic acid and pretreatment solution. Outgassing occurred, which displaced liquid at the top of the fermentation tube, and the level was read and recorded. The level corresponds to the gas point measured in solution in mL.

To adjust to obtain the correct amount of free and total acid, a CF700 B was used and adjusted according to the product data sheet. The bath temperature was 125° F., and when the panel was run through the bath, it was used for 2 minutes.

washing conditioner bath

1.1 g/L of Versabond RC (referred to as RC30, commercially available from PPG Industries, Inc.) was added to a 5 gallon (18.79 L) vessel filled with deionized water to obtain the zinc phosphate described above. It was used immediately before use of the bath. The bath had an oximeter of 80°F and was used for 1 minute as the panel ran through the bath.

Zirconium-containing pretreatment bath 2 ( comparative example )

Zircoband 1.5 (a zirconium-containing pretreatment composition available from PPG Industries, Inc.) was added to 5 gallons of deionized water according to the manufacturer's instructions to obtain a composition containing 175 ppm of zirconium.

The resulting solution was tested using a Thermo Scientific Orion Dual Star pH/ISE Bench Top Reader attached to a pH probe of 4.72 pH (Accumet catalog number 13-620-221). measured using). The temperature of the bath was 80° F., and when the panel was run through the bath, it was used for 2 minutes.

Zirconium-containing pretreatment bath 3 ( comparative example )

Zircoband 2.0 (a zirconium-containing pretreatment composition available from PPG Industries, Inc.) was added to 5 gallons of deionized water according to the manufacturer's instructions to add 175 ppm zirconium, 5 ppm lithium and 40 ppm Mo A composition containing

The resulting solution had a pH of 4.72. The temperature of the bath was 80° F., and when the panel was run through the bath, it was used for 2 minutes.

Cerium-containing pretreatment bath 4 ( Experimental example )

In a 2 L container of deionized water, 3 g of cerium(III) chloride heptahydrate (commercially available from Acros Organics) and 5 g of 29-32% hydrogen peroxide (available from Alfa Aesar) middle) was added. The temperature of the bath was room temperature and the bath was as it was when the panel was impregnated (ie, not stirred or agitated). When the panel was run through the bath, it was used for 2 minutes.

test panel manufacturing

Aluminum panel fabrication: X610 (ACT Test Panels LLC, Hillsdale, Michigan, USA) was cut in half to make a panel size of 4" x 6". The bottom 3 inches of each panel was sanded with P320 grit paper commercially available from 3M, which was then sanded with a 6" random orbital palm sander (Advanced) available from ATD. Tool design model (Advanced Tool Design Model)-ATD-2088).Sandpaper helped to measure any corrosion performance on sanded and unsanded parts of metal.Sandpaper was used for subsequent paint It is used in the art as a means of increasing the adhesion of a surface.

In each run, two half sanded X610 aluminum panels (cut to 4" x 6" from AC Test Panels LLC) were first washed as follows: All test panels were spray cleaned in a stainless steel spray cabinet using non-jet nozzles at 10-15 psi using at 2°C for 2 minutes, followed by an immersion rinse in deionized water for 15 seconds, followed by an immersion rinse in deionized water for 15 seconds. Spray cleaned.

The panel was then introduced into one of the pretreatment baths described above as follows:

Set 1 - Panels were immersed in cleaning conditioner bath 1 for 1 minute, followed immediately by pretreatment bath 1 for 2 minutes.

Set 2 - The panels were immersed in pretreatment bath 2 for 2 minutes.

Set 3 - The panels were immersed in pretreatment bath 3 for 2 minutes.

Set 4 - The panels were immersed in pretreatment bath 4 for 2 minutes.

After immersion in one of the pretreatment baths, all panels were then spray cleaned with deionized water for 20-30 seconds. A Hi-Velocity handheld blow-dryer (Model No. 078302-300-000) manufactured by Oster (R) was subjected to panel heating at a temperature of about 50 to 55°C. The panels were dried with warm air using high-setting until dry (about 1-5 minutes).

After drying, the panels were electrocoated with ED7000Z Electrocoat commercially available from PPG. Electrocoat was applied with a target of 0.60 mil thickness. The rectifier (Xantrex model XFR600-2) was set to a "Coulomb Controlled" setting. Conditions were set at a voltage setpoint of 23 coulomb zirconium for zinc phosphate and 24 coulomb, 0.5 amp limit for the experimental Ce chloride pretreatment, 220 V for zinc phosphate and 180 V for zirconium and experimental Ce chloride pretreatment, and a voltage of 30 seconds. It was set as the ramp time. The electrocoat was maintained at 90° F. using a stirring speed of 340 rpm. After applying the electrocoat, the panels were baked in an oven (Despatch Model LFD-1-42) at 177° C. for 25 minutes. The coating thickness was measured using a film thickness gauge (Fischer Technology Inc. model FMP40C).

The panels were evaluated for yellowing of the electrocoat layer by visual inspection by the naked eye. The scribe creep was measured by using ASTM-B 368-09 copper acetate salt spray to test the panels also for scribe creep blistering. Scribe creep was measured for each affected paint to the left and right of the scribe. The scribes were placed in the panel and then placed in the cabinet for a period of 20 days or 480 hours.

The scribes were measured according to the following protocol: The scribe length was 4 inches/10.16 cm. Readings for each affected paint were taken at each cm along the scribe yielding a total of 10 points of measurement. From this, the average of the two panels resulted in the average scribe creep reported in Table 1 below. Measurements were performed using a Fowler Sylvac digital caliper model S 235.

The table below provides scribe creep measurements from panels tested as described above.

[Table 1]

The data in Table 1 show that electrocoated panels pretreated with a pretreatment composition comprising cerium were exposed to 480 hours of exposure to copper acetate salt spray compared to electrocoated panels pretreated with a zirconium/molybdenum/lithium-containing pretreatment agent. Causes a 5% reduction in post-scribe creep (ASTM-B 368-09). In particular, the electrocoated panel treated with the zirconium-containing pretreatment composition is visually yellow to the naked eye, whereas the electrocoated panel treated with the lanthanide-containing pretreatment composition is not visually yellow to the naked eye.

The data in Table 1 also show that electrocoated panels pretreated with a pretreatment composition comprising cerium exhibited scribe creep (ASTM) after 480 h exposure to copper acetate spray, compared to electrocoated panels pretreated with a zirconium-containing pretreatment. -B 368-09) to cause a 27% reduction.

The data presented in Table 1 also show that electrocoated panels pretreated with a pretreatment composition comprising cerium, compared to electrocoated panels pretreated with a zinc phosphate pretreatment, scribe creep after 480 h exposure to a scribe creep copper acetate salt spray. (ASTM-B 368-09) results in a 65% reduction.

Example 2:

Example 2A

Aluminum 6111 panels (AC Test Panels LLC) were cut to 4" x 6" sample size. The bottom 3″ of the panel was sanded with P320 grit silicon carbide paper (commercially available from 3M) on a 6″ random orbital palm sander (Advanced Tool Design Model-ATD-2088). Half-sanding of the panel surface helped to measure any corrosion performance differences between the ground unsanded and sanded substrates. Surface sanding or sanding is performed in fields that facilitate adhesion of subsequent paint applications.

Each half-sanded 6111 aluminum panel was subjected to a standard ChemClean 2010LP/181ALP bath [1.25% by volume ChemClean in deionized water in a stainless steel spray tank using a non-jet nozzle at 10 to 15 psi at 120° F. for 2 minutes. 2010LP (a phosphate-free alkaline cleaner available from PPG Industries, Inc.) and 0.125% by volume of ChemClean 181 ALP (a phosphate-free formulated surfactant additive available from PPG Industries, Inc.) made by spray washing. Then, immersion cleaning in deionized water for 15 seconds and finally spray cleaning in deionized water for 15 seconds.

Immediately after spray cleaning, the cleaned panels were introduced into the pretreatment bath.

A first set of panels was pretreated with Zircoband 1.5 (a zirconium-containing pretreatment composition available from PPG Industries, Inc.). A 5-gallon bath was prepared according to the manufacturer's instructions to give a pH of 4.72, a zirconium concentration of 200 ppm, and a free fluoride concentration of 101 ppm. The panels were pretreated by immersion into a pretreatment bath at 80° F. with slow shaking for 2 minutes.

A second set of panels was pretreated with a cerium chloride pretreatment composition. The cerium chloride pretreatment bath consisted of a 29-32% solution of 0.15 wt% cerium(III) chloride heptahydrate (commercially available from Across Organics) and 0.25 wt% hydrogen peroxide (commercially available from Alpha Assar) in deionized water. lost. The panels were pretreated by immersion in a 3 gallon pretreatment bath at room temperature without any agitation for 2 minutes.

Upon removal from the pretreatment bath, the pretreated panels were spray rinsed with deionized water for 20-30 seconds. High-Velocity Handheld Hair Dryer (Model No. 078302-300-000) manufactured by Auster® at a temperature of about 50-55° C. until completely dry (about 3-5 minutes) high-setting The panel was air-dried.

The pretreated panels were electrocoated with cationic ED6280Z paint (commercially available from PPG) using a DC rectifier (Xantrex model XFR600-2). A coating dry film thickness of 0.8 mil was achieved by passing a 24.5 or 20.0 C charge for zirconium and cerium pretreatment, respectively, at a current limit of 0.5 A and an applied potential of 220 V after a 30 second ramp time. The ED6280Z paint bath was maintained at 90° F. at a stirring rate of 340 rpm. The electrocoated panels were spray cleaned with deionized water. The panels were baked in an electric oven (Despatch model LFD-1-42) at 177° C. for 25 minutes. Coating thicknesses were measured using a Permascope (Fischer Technology, Inc. model FMP40C).

Two corrosion test methods were used to evaluate the corrosion performance of the panels: the ASTM G85 A2 annular acidified salt mist test for 3 weeks, and linear corrosion for 6 weeks. For the linear corrosion test, the panel was placed horizontally in a desiccator containing a thin layer of 12 N hydrochloric acid (HCl) at room temperature for 1 hour so that only the HCl vapor was in contact with the sample, and within 5 minutes, the panel was placed at 40 °C. and in a wet cabinet maintained at 80% relative humidity for 6 weeks in a vertical orientation. Duplicate panels were included in each trial. Prior to corrosion testing, the panels were scribed in an X-array. The scribe was positioned with a top leg on the ground surface and a bottom leg on the sanded surface. Each leg is 40 mm long.

Corrosion damage is measured as the perpendicular distance from the scribe to the tip of the filament or blister. Each panel provided two sets of five measurements: one from the top leg for the ground surface, and another set from the bottom leg for the sanded surface. Measurements were taken from the 5 longest corrosion sites. Average corrosion damage was calculated based on a total of 10 measurements from duplex panels. All readings were taken using a Polar Sealback digital caliper model S 235.

Average corrosion damage is reported in Table 1.1 below. Based on the control zirconium pretreatment, the cerium chloride pretreated panels showed better corrosion performance on the sanded 6111 aluminum alloy and the unsanded 6111 aluminum alloy.

[Table 1.1]

Example 2B

Aluminum 6111 panels (AC Test Panels LLC) were cut to 4" x 6" sample size. The bottom 3″ of the panel was sanded with P320 grit silicon carbide paper (commercially available from 3M) on a 6″ random orbital palm sander (Advanced Tool Design Model-ATD-2088). Half-sanding of the panel surface helped to measure any corrosion performance differences between the ground unsanded and sanded substrates. Surface sanding or polishing is performed in fields that facilitate adhesion of subsequent paint applications.

Each half-sanded 6111 aluminum panel was heated in a standard ChemClean 2010LP/181ALP bath [1.25 vol % Chem Clean 2010LP (a phosphate-free alkaline cleaner available from PPG Industries, Inc.) and ChemClean 181 ALP at 0.125% by volume (a phosphate-free formulated surfactant additive available from PPG Industries, Inc.) composed of] was spray washed. Then, immersion cleaning in deionized water for 15 seconds and finally spray cleaning in deionized water for 15 seconds.

Immediately after spray cleaning, the cleaned panels were introduced into the pretreatment bath.

A first set of panels was pretreated with Zircoband 1.5 (a zirconium-containing pretreatment composition available from PPG Industries, Inc.). A 5-gallon bath was prepared according to the manufacturer's instructions to give a pH of 4.72, a zirconium concentration of 200 ppm, and a free fluoride concentration of 101 ppm. The panels were pretreated by immersion in a pretreatment bath at 80° F. for 2 minutes with slow shaking. The panel was spray cleaned with deionized water for 20 to 30 seconds, and a high-velocity handheld hair dryer manufactured by Oster (Model No. 078302-300-000) was thoroughly rinsed at a temperature of about 50 to 55°C. Air dried using high-setting until dry (about 3-5 minutes).

The second through fifth sets of panels were pretreated in a two-step pretreatment process in which the panels were pretreated with two separate pretreatment compositions prepared as 3-gallon baths having the compositions described above.

The cerium chloride pretreatment bath consisted of 0.15 wt% cerium(III) chloride heptahydrate (commercially available from Across Organics) and 0.25 wt% hydrogen peroxide, 29-32% solution (commercially available from Alpha Assar) in deionized water. was composed

The lithium hydroxide pretreatment bath consisted of 0.17 wt % lithium hydroxide monohydrate (commercially available from Across Organics) in deionized water.

The lithium carbonate pretreatment bath consisted of 0.15 wt % lithium carbonate (commercially available from Across Organics) in deionized water.

A second set of panels was subjected to a cerium chloride/lithium hydroxide two-step pretreatment process. The panels were first pretreated by immersing in the cerium chloride pretreatment composition at room temperature for 2 minutes without shaking. The panels were spray cleaned with deionized water, followed by a full immersion pretreatment in a lithium hydroxide pretreatment composition at room temperature for 1 minute. High-Velocity Handheld Hair Dryer (Model No. 078302-300-000) manufactured by Auster® at a temperature of about 50-55° C. until completely dry (about 3-5 minutes) high-setting was used to air-dry the panel.

A third set of panels was subjected to a cerium chloride/lithium carbonate two-step pretreatment process. The panels were pretreated by impregnating the cerium chloride pretreatment composition at room temperature for 2 minutes without shaking. The panels were spray cleaned with deionized water, followed by a full immersion pretreatment in the lithium carbonate pretreatment composition for 1 minute at room temperature. High-Velocity Handheld Hair Dryer (Model No. 078302-300-000) manufactured by Auster® at a temperature of about 50-55° C. until completely dry (about 3-5 minutes) high-setting was used to air-dry the panel.

A fourth set of panels was pretreated with a lithium hydroxide/cerium chloride two-step pretreatment process. The panels were first pretreated by impregnating the lithium hydroxide pretreatment composition at room temperature for 1 minute, followed by immersion in the cerium chloride pretreatment composition for 2 minutes. The panel was spray cleaned with deionized water for 20 to 30 seconds, and a high-velocity handheld hair dryer manufactured by Oster (Model No. 078302-300-000) was thoroughly rinsed at a temperature of about 50 to 55°C. Air dried using until dryness (about 3 to 5 minutes).

A fifth set of panels was pretreated with a lithium carbonate/cerium chloride two-step pretreatment process. The panels were first pretreated by immersion in the lithium carbonate pretreatment composition at room temperature for 1 minute, followed by immersion in the cerium chloride pretreatment composition for 2 minutes. The panel was spray cleaned with deionized water for 20 to 30 seconds, and a high-velocity handheld hair dryer manufactured by Oster (Model No. 078302-300-000) was thoroughly rinsed at a temperature of about 50 to 55°C. Air dried using high-setting until dry (about 3-5 minutes).

[Table 2.1]

The pretreated panels were electrocoated with cationic ED6280Z paint (commercially available from PG) using a DC rectifier (Xantrex model XFR600-2). A coating dry film thickness of 0.8 mil was achieved with the coat out parameters listed in Table 2.2. The ED6280Z paint bath was maintained at 90°F with a stirring speed of 340 rpm. The electrocoated panels were spray cleaned with deionized water. The panels were baked in an electric oven at 177° C. (Despatch model LFD-1-42) for 25 minutes. Coating thickness was measured using a permasscope (Fischer Technology, Inc. model FMP40C).

[Table 2.2]

Two corrosion test methods were used to evaluate the corrosion performance of the panels: the ASTM G85 A2 annular acidified salt mist test for 3 weeks, and linear corrosion for 6 weeks. For the linear corrosion test, the panel was placed horizontally in a desiccator containing a thin layer of 12 N hydrochloric acid (HCl) at room temperature for 1 hour so that only the HCl vapor was in contact with the sample, and within 5 minutes, the panel was placed at 40 °C. and in a wet cabinet maintained at 80% relative humidity for 6 weeks in a vertical orientation. Prior to corrosion testing, the panels were scribed in an X-array. The scribe was positioned with a top leg on the ground surface and a bottom leg on the sanded surface. Each leg is 40 mm long.

Corrosion damage is measured as the perpendicular distance from the scribe to the tip of the filament or blister. Each panel provided two sets of five measurements: one from the top leg for the ground surface, and another set from the bottom leg for the sanded surface. Measurements were taken from the 5 longest corrosion sites. Average corrosion damage was calculated based on a total of 10 measurements from duplex panels. All readings were taken using a Polar Sealback digital caliper model S 235.

Average corrosion damage is given in Table 2.3. Compared to the control zirconium pretreatment, all experimental two-step pretreatments showed good corrosion performance for the sanded 6111 aluminum alloy.

[Table 2.3]

Example 3:

bath manufacturing

Standard ChemClean 2010LP / 181ALP Cleaner : Wash the detergent bath with ChemClean 2010LP at a concentration of 1.25% v/v in deionized water (a phosphate-free alkaline cleaner commercially available from sebum) and ChemClean 181 ALP at 0.125% (a phosphate-free commercially available phosphate-free cleaner from sebum) in deionized water. formulated surfactant additives). For spray washing, a 10-gallon bath was prepared. The temperature of the bath was 120° F., and when the panel was run through the cleaner, it was used for 2 minutes. The pressure of the spray wash was between 10 and 15 psi.

Control Zircoband 1.5 ( ZB - 1.5, commercially available zirconium pretreatment composition) : 16.73 g of 45% hexafluorozirconic acid (commercially available from Honeywell International Inc.) in 5 gallons of deionized water. ), 30.02 g of a 2 wt % copper solution (prepared by dissolving copper nitrate hemipentahydrate commercially available from Fisher Scientific in deionized water), 15.4 g of Kempos AFL (commercially available from PPG), and 29.8 g Chemfil buffer (commercially available from sebum) was added. The resulting solution had a pH of 4.68 and free fluoride of 103 ppm.

Cerium Chloride Pretreatment Composition : 3 g of cerium(III) chloride heptahydrate (commercially available from Across Organics) and 5 g of 29-32% hydrogen peroxide (commercially available from Alpha Assar) in a 2 L container of deionized water added.

test panel manufacturing

Set A panels were Zinc Hot Dipped Galvanized Unexposed, pretreated with Chempos® 700 Zinc Phosphate Pretreatment purchased from AC Test Panels (Zinc Hot Dipped Galvanized Unexposed). 70G70UHDG) (Item No. 40085).

Zinc Hot Dipped Galvanized Exposed (HD60G60E) item number 53170 from AC Test Panels was cut in half to make a panel size of 4" x 6".

For each run, two Zinc Hot Dipped Galvanized Exposed (cut from AC Test Panels LLC to 4" x 6") were first washed as follows: a bath temperature of 49° C. and 10 The panels were spray cleaned in a stainless-steel spray cabinet using the standard ChemClean 2010LP/181ALP bath described above for 2 minutes at 15 to 15 psi spray pressure (using a series of “non-jet” spray nozzles), followed by 15 in deionized water. Immersion rinse for seconds and spray rinse with deionized water for 15 seconds.

The washed panels were then impregnated with one of the two pretreatment compositions described above:

Set B: The panels were immersed in a Zircoband 1.5 (ZB-1.5) pretreatment bath for 2 minutes at a bath temperature of 80° F.

Set C: The panels were immersed in a cerium chloride pretreatment bath for 1 minute at room temperature.

All panels from sets B and C were then spray cleaned with deionized water for 20-30 seconds. A high-velocity handheld hair dryer (model number 078302-300-000) manufactured by Auster® was heated at a temperature of about 50 to 55° C. until the panels were dried (about 1 to 5 minutes). In the setting, the panels were warm air dried.

All panels from sets A, B and C were electrocoated with ED7000Z Electrocoat commercially available from PPG. Electrocoat was applied with a target of 0.60 mil thickness. The rectifier (Zantrex model XFR600-2) was set to the "Coulomb controlled" setting. Conditions are 23 coulomb for set A (zinc phosphate pretreatment), and 24 coulomb for set B (zirconium pretreatment) and set C (cerium chloride pretreatment), 0.5 amp limit, 220 V for set A and set B and set C was set to a voltage setpoint of 180 V, and a ramp time of 30 seconds. The electrocoat was maintained at 90° F. with a stirring speed of 340 rpm. After applying the electrocoat, the panels were baked in an oven at 177° C. (Despatch model LFD-1-42) for 25 minutes. The coating thickness was measured using a film thickness gauge (Fischer Technology, Inc. model FMP40C).

The coated panels were tested for scribe creep blistering using the GMW 14872 Annular Damage Test Method. Scribe creep was measured for each affected paint to the left and right of the scribe. The scribes were placed on the panel and then placed in the cabinet for a length of 40 cycles.

Two test panels were evaluated to obtain average scribe creep. The length of the scribe was 4 inches (10.16 cm). Readings for each affected paint were taken every 1 cm along the scribe, resulting in a total of 10 points of measurement for each panel. Measurements were obtained using a Polar Sealback digital caliper model S 235. The average scribe creep for each panel was the average scribe creep for 10 measurements. From this, the average of the average scribe creep of each of the two panels resulted in the average scribe creep for each set shown in Table 3.1 below.

[Table 3.1]

The data in Table 3.1 show a reduction of at least 21% in average scribe creep on panels treated with the system of the present invention (i.e., cerium pretreatment composition) compared to panels treated with either the zinc phosphate pretreatment composition or the zirconium pretreatment composition (GMW 14872 Cyclic) as measured by the damage test).

Example 4:

bath composition

Standard Ultrax 14 AWS Cleaner : The bath was prepared in 1.25% v/v concentration in deionized water ( mild alkaline cleaner combined with a surfactant commercially available from PPG).

AMC66AW Deoxidizer : The bath was prepared with AMC66 (acid deoxidizer without nitric acid commercially available from sebum) at a concentration of 2% v/v. The panels were run through the bath at 120° F. for 1 minute.

Control X-Bond (commercially available zirconium pretreatment composition) : 24.13 g of 45% hexafluorozirconic acid (commercially available from Honeywell International, Inc.), 16 g of Kempos AFL in 5 gallons of deionized water (commercially available from sebum), and 33 g of chemfil buffer (commercially available from sebum) were added. The resulting solution had a pH of 4.63 and free fluoride of 91.2 ppm.

In a standard Chemseal 59 : 1 gallon sleeve , 1% v/v Chemseal 59 ( an acidic sealant commercially available from PPG) was prepared at pH = 4.2.

Cerium Chloride (Experimental Pretreatment Composition) : 3 g of cerium(III) chloride heptahydrate (commercially available from Across Organics) and 6 g of 29-32% hydrogen peroxide (from Alpha Assar) in a 2 L container of deionized water. commercially available) was added.

test panel manufacturing

An aluminum alloy 6061 panel (AC Test Panels LLC) was cut in half to make a panel size of 4" x 6". For each setup, two 6061 aluminum panels were first washed as follows: In a stainless steel spray cabinet using a non-jet nozzle at 10-15 psi, a 10-gallon bath of the standard Ultrax14AWS cleaner described above was applied. All test panels were spray cleaned using a bath temperature of 49° C. for 2 minutes, followed by an immersion rinse in deionized water for 15 seconds, followed by a spray rinse in deionized water for 15 seconds. The panels were then immersed in the aforementioned AMC66AW deoxidizer bath at 49° C. bath temperature for 1 minute, followed by spray cleaning with deionized water for 15 seconds.

The panel was then introduced into the pretreatment bath described above.

Set 1: Panels were immersed in an X-Bond (XB) pretreatment bath for 2 minutes at a bath temperature of 80°F.

Set 2: Panels were immersed in a cerium chloride pretreatment bath for 2 minutes at room temperature.

Set 3: Panels were immersed in a cerium chloride pretreatment bath for 2 minutes at room temperature, followed by immersion in a Chemsil 59 bath for 1 minute at room temperature.

All panels were then spray cleaned with deionized water for 20-30 seconds. A high-velocity handheld hair dryer (model number 078302-300-000) manufactured by Auster® was heated at a temperature of about 50 to 55° C. until the panels were dried (about 1 to 5 minutes). The panel was warm air dried using the setting.

After drying, the conversion coating was subjected to X-ray fluorescence [X-Met 7500, Oxford Instruments; Operating parameters were determined by a 60 second timed assay, 15 Kv, 45 μA, filter 3, T(p) = 1.1 μs for lanthanide). Due to the output profile, the non-lanthanide conversion coating does not have a baseline of zero counts, and thus the difference between the measured counts and the baseline, rather than the absolute value of the counts, is indicative of the composition of the coating. Results are reported in Table 4.1.

[Table 4.1]

The remaining panel was coated with powder-coated Enviracryl (registered trademark) PCC10103 (acrylic coating commercially available from PPG) to a thickness of 2.75 mil.

Scrib creep was measured by testing the coated panels for scribe creep blistering using ASTM-B 368-09 copper acetate salt spray. Scribe creep was measured for each affected paint to the left and right of the scribe. The scribes were placed in the panel and then placed in the cabinet for a length of 10 days or 240 hours. A table of scribe creep measurements from two test panels, measured at 7 equally spaced points along a 4-inch scribe, is presented below. Measurements were recorded using a Polar Sealback digital caliper Model S 235.

The panels were tested for linear corrosion using the SAE J2635 method. The scribe creep is measured for each affected paint to the left or right of the scribe. The scribes were placed on the panel, then initiated, and then placed in a wet cabinet for 28 days. A table of scribe creep from the average of two panels per set, measured at 7 equally spaced points along a 4-inch scribe, is presented below.

A crosshatch adhesion test was performed on the panels after soaking for one day in a water bath heated to 60°C. The panel was allowed to recover at room temperature for 20 minutes. Using a razor blade and Gardco Temper II gauge tool, 11 cuts spaced 1.5 mm apart were made perpendicular to 11 cuts spaced 1.5 mm apart. A fibrous tape was applied to the area and pulled quickly. Paint adhesion was scored on a scale of 1 (no paint adhesion remaining) to 10 (complete adhesion).

[Table 4.2]

The data in Table 4.2 show a reduction of at least 13% as measured by the CASS test in scribe creep on panels treated with the system of the present invention compared to panels treated with either the cerium conversion composition alone or the zirconium composition alone. The data in Table 4.2 also show that in scribe creep on panels treated with the system of the invention (i.e., cerium conversion composition followed by zirconium-containing conversion composition), SAE compared to panels treated with either the cerium conversion composition alone or the zirconium composition alone, showed a reduction of at least 47% as measured by the J2635 test. Finally, the data in Table 4.2 show that the crosshatch adhesion on panels treated with the system of the present invention (i.e., the cerium conversion composition followed by the zirconium-containing conversion composition) compared to panels treated with the cerium conversion composition alone or the zirconium composition alone. shows an increase of more than 42%.

Example 5

bath composition

Standard ChemClean 2010LP / 181ALP Cleaner : ChemClean 2010LP at a concentration of 1.25% v/v in deionized water (a phosphate-free alkaline cleaner available from sebum) and ChemClean 181 ALP at 0.125% (a phosphate-free blended interface commercially available from sebum) activator additive). For spray washing, a 10-gallon bath was prepared.

ChemDeox 395 : Acidic deoxidizer (pH 2.5) was prepared from hexafluorosilicic acid, ammonium bifluoride and sodium hydroxide.

Control Zircoband 1.5 (commercially available zirconium pretreatment composition) : 19.16 g 45% hexafluorozirconic acid (commercially available from Honeywell International, Inc.), 35.09 g 2 wt % copper solution in 5 gallons of deionized water [Prepared by dissolving copper nitrate hemipentahydrate (commercially available from Fischer Scientific) in deionized water], 14 g of Kempos AFL (commercially available from PG), and 32 g of Kempyl Buffer (commercially available from PEG) middle) was added. The resulting solution had a pH of 4.61 and free fluoride of 91.2 ppm.

standard chemsil 59 : In a 1-gallon sleeve, 1% v/v Chemsil 59 (an acidic sealer commercially available from PPG) was prepared at pH = 4.2.

Cerium Chloride Pretreatment Composition : 3 g of cerium(III) chloride heptahydrate (commercially available from Across Organics) and 6 g of 29-32% hydrogen peroxide (commercially available from Alpha Assar) in a 2-L container of deionized water was added.

test panel manufacturing

An aluminum alloy 6061 panel (AC Test Panels LLC) was cut in half to make a panel size of 4" x 6". For each set, two 6061 aluminum panels were first cleaned as follows: All test panels were cleaned in a stainless steel spray cabinet using non-jet nozzles at 10-15 psi, standard ChemClean 2010LP/181ALP detailed above. The detergent bath was spray washed using a bath temperature of 49° C. for 2 minutes, followed by an immersion rinse in deionized water for 15 seconds, followed by a spray rinse in deionized water for 15 seconds. The panels were then immersed in Chemdeox395 at a bath temperature of 90° F. with rapid shaking for 1 minute followed by spray cleaning with deionized water for 15 seconds.

The panel was then introduced into the pretreatment bath detailed above:

Set 4: Panels were immersed in a Zircoband 1.5 pretreatment bath for 2 minutes at a bath temperature of 80°F.

Set 5: Panels were immersed in a cerium chloride pretreatment bath for 2 minutes at room temperature.

Set 6: Panels were immersed in a cerium chloride pretreatment bath for 2 minutes at room temperature, followed by a Chemsil 59 bath for 1 minute at room temperature.

Then, all pretreated panels were spray cleaned with deionized water for 20 to 30 seconds, and a high-velocity handheld hair dryer manufactured by Oster (Model No. 078302-300-000) was applied to about 50 to 55 At a temperature of °C until the panels dry (approximately 1-5 minutes), use as a high-setting to dry in warm air.

After drying, the conversion coating was analyzed by X-ray fluorescence (X-Met 7500, Oxford Instruments; operating parameters 60 sec timed assay, 15 Kv, 45 μA, filter 3, T(p) = 1.1 μs for lanthanide). measured. Due to the profile of the output, the non-lanthanide conversion coating did not have a baseline of zero counts, and thus the difference between the measured and baseline, rather than the absolute value of the counts, was indicative of the composition of the coating.

[Table 5.1]

After drying, the panel was electrocoated with ED7000Z Electrocoat commercially available from PPG. Electrocoat was applied with a target of 0.60 mil thickness. The rectifier (Zantrex model XFR600-2) was set to the "Coulomb controlled" setting. Conditions were set to 22 coulomb for set 4 (zirconium), and 21 coulomb for set 5 (cerium chloride) and set 6 (cerium chloride and seal), and 0.5 amp limit, a voltage setpoint of 200 V, and a ramp of 30 s. time was set. The electrocoat was maintained at a bath temperature of 90° F. with a stirring speed of 320 rpm. After electrocoat application, the panels were baked in an oven at 177° C. (Despatch model LFD-1-42) for 25 minutes. The coating thickness was measured using a film thickness gauge (Fischer Technology, Inc. model FMP40C).

Scribe creep was measured by testing the coated panels for scribe creep blistering using STM-B 368-09 copper acetate salt spray. Scribe creep was measured for each affected paint to the left and right of the scribe. The scribes were placed in the panel and then placed in the cabinet for a period of 20 days or 480 hours. A table of scribe creep measurements from the average of two test panels per set, measured at 7 equally spaced points along a 4-inch scribe, is presented below. Measurements were recorded using a Polar Sealback digital caliper Model S 235.

The panels were tested for linear corrosion for 6 weeks. Place the panels horizontally at room temperature for 1 hour in a desiccator containing a thin layer of 12 N hydrochloric acid (HCl) so that only HCl vapors come into contact with the sample, and within 5 minutes, place the panels at 40° C. and 80% relative humidity. was placed in a vertical orientation in a wet cabinet maintained for 6 weeks in Scribe creep was measured for each affected paint to the left and right of the scribe. A table of scribe creep measurements from the average of two test panels per set, measured at 7 equally spaced points along a 4-inch scribe, is presented below. Measurements were recorded using a Polar Sealback digital caliper Model S 235.

[Table 5.2]

The data in Table 5.2 show a reduction of at least 39% as measured in the CASS test in scribe creep on electrocoated panels treated with the system of the present invention as compared to panels treated with either the cerium conversion composition alone or the zirconium composition alone. In addition, the data in Table 5.2 show a reduction of at least 10% as measured by the linear corrosion test in scribe creep on electrocoated panels treated with the system of the present invention as compared to panels treated with either the cerium conversion composition alone or the zirconium composition alone. indicates.

Example 6

To a 2 L container of deionized water were added 3 g of cerium(III) chloride heptahydrate (commercially available from Acros Organics) and 5 g of 29-32% hydrogen peroxide (commercially available from Alpha Asar). The temperature of the bath was room temperature and the bath was left standing until the panel was impregnated (ie, not stirred or agitated).

In this example, 6111 aluminum panels (ACT) were evaluated for deposition of cerium or zinc phosphate and coloration of the pretreated panels.

A 4" x 12" panel of 6111 aluminum (commercially available from AC Test Panels LLC, product number 39279) was cut in half to make a 4" x 6" panel.

For each set, wash 1/2 6111 aluminum panels by spray cleaning with Cleaner 2 at 120° F. for 2 minutes in a stainless steel spray cabinet using non-jet nozzles at 10-15 psi, followed by , impregnated in deionized water for 15 seconds, followed by spray cleaning with deionized water for 15 seconds using a Melnor Rear-Trigger 7-Pattern nozzle set to the shower mode described above. The panel was then introduced into one of the aforementioned conversion composition baths as follows:

Set 10 —The bath containing Conversion Composition 4 (room temperature bath) was immersed in the bath for 2 minutes. Then, the Melner rare-trigger 7-pattern panel set to the shower mode described above was spray cleaned with deionized water for 20 to 30 seconds using a nozzle. The panels were warm air dried using a high-velocity handheld hair dryer by Auster, described above, at a high-setting at a temperature of 50-55° C. until the panels were dry (1-5 minutes).

Panel set 12 was a comparative panel aluminum 6111 zinc phosphate treated with panels purchased from AC Test Panels (Product No. 42606, AC Zinc Phosphate 6111AA Panels) and heated as described below for colorimetric data.

X-ray fluorescence (measured using an X-Met 7500, Oxford Instruments; operating parameters for a Cerium 60 sec timed assay, 15 Kv, 45 μA, filter 3, T(p) = 1.1 μs; 60 sec time Operating variable for conditioning assay, 25 Kv, 20 μA, filter 1, T(p) = 1.1 μs; μs) to analyze the panel for deposition of cerium, phosphorus and zinc. Data are reported in Table 5, and each reported value is the average of two measurements taken at different locations on each panel.

[Table 6.1]

The panels were also measured for yellowing of the panels according to the conversion composition (measured using an X-Lite Ci7800 colorimeter, 25 mm aperture). Data are reported in Table 6, and each reported value is the average of two measurements taken at the same location on the panel. The reported data is Spectral Component Excluded.

[Table 6.2]

The panels were then baked in an oven at 177° C. (Despatch model LFD-1-42) for 25 minutes (panels not electrocoated). Panels were measured for yellowing of panel heating of pretreated panels (measured using an X-Lite Ci7800 colorimeter, 25 mm aperture). Data are reported in Table 6.3, and each reported value is the average of two measurements taken at the same location on the panel. Reported data exclude spectral components.

[Table 6.3]

The b ^* values and YI-E313 values of the panels pretreated with the cerium-containing composition alone had increased b ^* values compared to the zinc phosphate treated panels, indicating that the cerium-treated panels were colored more yellow. In particular, the b ^* values and YI-E313 values were significantly lower in the heated panels pretreated in the same way compared to the unheated panels pretreated with cerium alone, indicating further reduction of the yellow coloration of the panels. In addition, the b ^* and YI-E313 values of the panels pretreated with the cerium-containing composition were lower after heating the panels, compared to the untreated panels and the heating panels treated with conventional zinc phosphate.

Claims (20)

a first composition comprising a lanthanide-based element cation and an oxidizing agent for contacting at least a portion of the surface of the substrate; and
a second composition comprising a Group IA metal carbonate and containing less than 10 ppm of an oxidizing agent and free fluoride for contacting at least a portion of a surface of a substrate
A system for treating substrates, comprising: According to claim 1,
wherein the oxidizing agent is present in the first composition in an amount of 25 to 25,000 ppm based on the total weight of the first composition. According to claim 1,
wherein the lanthanide series element cation comprises cerium, praseodymium, or a combination thereof. According to claim 1,
wherein the lanthanide series elemental cation is present in the first composition in an amount of from 50 to 200 ppm calculated as cations based on the total weight of the first composition. According to claim 1,
wherein the Group IA metal cation comprises lithium, sodium, potassium, or a combination thereof. According to claim 1,
wherein the Group IA metal cation is present in the second composition in an amount of from 5 to 30,000 ppm as metal cations based on the total weight of the second composition. According to claim 1,
wherein the second composition has a pH between 8 and 13. According to claim 1,
wherein the phosphate is present in each of the first composition and the second composition in an amount of 5 ppm or less. A substrate treated with the system according to claim 1 . contacting at least a portion of the surface of the substrate with a first composition comprising a lanthanide-based element cation and an oxidizing agent; and
contacting at least a portion of the surface of the substrate with a second composition comprising a Group IA metal carbonate and containing less than 10 ppm of an oxidizing agent and free fluoride;
A method of treating a substrate comprising: 11. The method of claim 10,
the substrate surface is contacted with the first composition, resulting in a level of lanthanide series element cations on the contacted substrate surface measured by X-ray fluorescence that is at least 100 counts greater than on the surface of the substrate not contacted with the first composition; , wherein the X-ray fluorescence is measured by an X-Met 7500 from Oxford Instruments (operating parameters 60 sec timed assay, 15 Kv, 45 μA, filter 3, T(p) = 1.5 μs). processing method. 11. The method of claim 10,
wherein the step of contacting with the first composition is performed prior to the step of contacting with the second composition. 11. The method of claim 10,
wherein the step of contacting with the second composition is performed prior to the step of contacting with the first composition. 11. The method of claim 10,
wherein the step of contacting with the first composition is from 15 seconds to 4 minutes. 11. The method of claim 10,
and heating the substrate at a temperature of 110 to 232° C. for 15 to 30 minutes. A substrate treated by the treatment method according to claim 10 , excluding spectral components, having a b ^* value of less than 3.09 measured with a 25 mm aperture. delete delete delete delete

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