WO2011021374A1 - Solution de post-traitement pour film de revêtement auto-déposé formé sur une surface métallique, et procédé pour la production d'un matériau métallique comportant un film de revêtement auto-déposé post-traité formé sur celui-ci - Google Patents

Solution de post-traitement pour film de revêtement auto-déposé formé sur une surface métallique, et procédé pour la production d'un matériau métallique comportant un film de revêtement auto-déposé post-traité formé sur celui-ci Download PDF

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WO2011021374A1
WO2011021374A1 PCT/JP2010/005051 JP2010005051W WO2011021374A1 WO 2011021374 A1 WO2011021374 A1 WO 2011021374A1 JP 2010005051 W JP2010005051 W JP 2010005051W WO 2011021374 A1 WO2011021374 A1 WO 2011021374A1
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Prior art keywords
post
treatment liquid
self
coating
metal
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PCT/JP2010/005051
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English (en)
Japanese (ja)
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高▲桑▼英樹
中山隆臣
藤野孝洋
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日本パーカライジング株式会社
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Publication of WO2011021374A1 publication Critical patent/WO2011021374A1/fr

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Classifications

    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C22/00—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals
    • C23C22/05—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals using aqueous solutions
    • C23C22/06—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals using aqueous solutions using aqueous acidic solutions with pH less than 6
    • C23C22/07—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals using aqueous solutions using aqueous acidic solutions with pH less than 6 containing phosphates
    • C23C22/08—Orthophosphates
    • C23C22/18—Orthophosphates containing manganese cations
    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C22/00—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals
    • C23C22/05—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals using aqueous solutions
    • C23C22/06—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals using aqueous solutions using aqueous acidic solutions with pH less than 6
    • C23C22/07—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals using aqueous solutions using aqueous acidic solutions with pH less than 6 containing phosphates
    • C23C22/08—Orthophosphates
    • C23C22/20—Orthophosphates containing aluminium cations
    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C22/00—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals
    • C23C22/05—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals using aqueous solutions
    • C23C22/06—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals using aqueous solutions using aqueous acidic solutions with pH less than 6
    • C23C22/34—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals using aqueous solutions using aqueous acidic solutions with pH less than 6 containing fluorides or complex fluorides

Definitions

  • the present invention is a surface of an iron-based metal material that requires high corrosion resistance and adhesion, such as automobile bodies, automobile parts, steel furniture, and home appliances, and that may be overcoated in accordance with the application. It relates to processing technology.
  • the present invention aims to form an autodeposition composition containing tannin, an acid and an oxidizing agent on the surface of the metal material for the purpose of forming an autodeposition film having excellent corrosion resistance and adhesion on the surface of the iron-based metal material.
  • This is a technique related to chemical treatment (post-treatment) applied to an uncured autodeposition coating formed on the same surface by bringing it into contact.
  • Japanese Patent Publication No. 47-17630, Japanese Patent Publication No. 48-14412 are self-deposition compositions that can form a resin film on the metal surface by contacting the metal surface with an acidic composition containing an organic coating resin.
  • Conventionally known autodeposition compositions are characterized in that by immersing a clean metal surface in the autodeposition composition, an autodeposition coating whose thickness or weight increases with the immersion time can be formed. Furthermore, a part of the metal ions eluted from the metal by the chemical action (etching) of the autodeposition composition on the surface of the metal is taken into the film to form a film. An autodeposited film can be effectively formed on the metal surface without using.
  • U.S. Pat. Nos. 3,647,567, 4,030,945 and JP-A-61-168673 disclose a chromium compound before drying an uncured autodeposition coating formed on a metal surface. It is disclosed that an autodeposition coating excellent in corrosion resistance can be obtained by contacting with an aqueous solution containing. However, at present, it is not preferable to use a treatment liquid containing chromium whose use is restricted from the viewpoint of environmental problems.
  • Patent Documents 1 to 3 have proposed a method that does not use chromium.
  • Patent Document 2 discloses a self-deposited coating film in which a metal to be coated is coated with an aqueous coating composition and then baked and coated. It is disclosed to wash with an aqueous solution or an aqueous dispersion mainly containing at least one selected from the group of salts, borofluoride, titanium fluoride, aluminum fluoride and nitrite.
  • Patent Document 3 discloses that an autodeposition coating deposited on a metal substrate is brought into contact with an aqueous solution containing a Group II A or Group II B metal cation and a phosphate anion before curing. It is disclosed that a phosphate compound is generated at the interface of the coating and the corrosion resistance is improved.
  • the autodeposition coating using tannin as the resin component gives good results in many test items. be able to.
  • the conventional post-treatment agent is used for the autodeposition coating using tannin as the resin component, the present inventors have tested all the test items required by the present inventors, specifically, the salt warm water test, the salt spray It was confirmed that a high level of corrosion resistance and adhesion satisfying all the test items of the test, the combined environmental cycle test and the adhesion test could not be obtained. Accordingly, the present invention provides a post-treatment technique that imparts a high level of corrosion resistance and adhesion to an autodeposition coating using tannin as a resin component, without using harmful components such as chromium. With the goal.
  • the present invention (1) is an aqueous solution containing at least one metal component selected from the group consisting of lithium, manganese, iron, cobalt, nickel, copper and aluminum and phosphoric acid. It is a post-treatment liquid for autodeposition coating on the metal surface as a resin component.
  • K A / B which is the ratio of the total molar concentration A of the metal components to the molar concentration B of the phosphoric acid is represented by the formula (1): (Formula 2)
  • the molar concentration A in the aqueous solution is in the range of 0.1 to 500 mmol / L as the concentration in the aqueous solution.
  • the present invention (3) is the post-treatment liquid of the invention (1) or (2), wherein the post-treatment liquid for autodeposition coating on the metal surface has a pH of 2 to 6.
  • the post-treatment liquid for autodeposition coating on the metal surface is selected from the group consisting of nitrite, hydroxylamine, hydroxylamine sulfate, hydroxylamine phosphate, hydroxylamine hydrochloride, hydroxylammonium and hydrogen peroxide. Any one of the post-treatment liquids according to any one of the inventions (1) to (3).
  • the present invention (5) is the post-treatment liquid according to any one of the inventions (1) to (4), wherein the self-deposited film contains at least one selected from the group consisting of cerium, yttrium, aluminum and strontium. is there.
  • the present invention (6) is the post-treatment liquid of the invention (5), wherein cerium, yttrium, aluminum and strontium are fluoride particles.
  • At least one crosslinking agent having a phenolic hydroxyl group and / or a crosslinking group capable of thermosetting reaction with a phenol nucleus is used.
  • the present invention (8) is the post-treatment liquid according to the invention (7), wherein the crosslinking group capable of thermosetting reaction in the at least one crosslinking agent is an isocyanate group.
  • the present invention (9) is the post-treatment liquid of the invention (8), wherein the at least one crosslinking agent is a polyfunctional blocked isocyanate blocked with a blocking agent.
  • the at least one crosslinking agent is at least one selected from block isocyanates having at least one molecule of bisphenol A structure and / or self-emulsifying type blocked isocyanates using polyether polyol. This is a post-treatment liquid of the invention (9).
  • an uncured self-deposited film is formed on a metal surface by bringing a self-deposited composition containing tannin as a resin component into contact with a metal material whose surface has been cleaned in advance by degreasing and washing with water.
  • a metal material comprising: a precipitation coating step; a contact step of bringing the post-treatment liquid according to any one of the inventions (1) to (10) into contact with the uncured self-deposition coating; and a baking step This is a surface treatment method.
  • the post-treatment liquid for self-deposition of a metal surface according to the present invention is for an auto-deposition film containing tannin as a resin component, and is at least one selected from the group consisting of lithium, manganese, iron, cobalt, nickel, copper and aluminum It is the aqueous solution containing the metal component and phosphoric acid.
  • aqueous solution containing the metal component and phosphoric acid.
  • Lithium, manganese, iron, cobalt, nickel, copper, and aluminum used in the present invention are metal parts in forming a phosphate compound that provides excellent corrosion resistance and adhesion to an autodeposition coating containing tannin as a resin component. It becomes.
  • an aqueous solution containing these metal components and phosphoric acid is applied to an autodeposition coating containing tannin as a resin component, the interface between the metal surface and the autodeposition coating is different from the case of using a post-treatment agent in the prior art.
  • the phosphate compound is not unevenly distributed, but is uniformly dispersed and deposited in the autodeposition coating.
  • the phosphate compound which not only improves the corrosion resistance and adhesion at the interface between the metal surface and the self-deposited coating but also has an effect as a rust preventive pigment is uniformly dispersed in the coating, Corrosion resistance can be remarkably improved over the entire coating.
  • Preferred metal components are manganese, cobalt and nickel.
  • the supply source of the metal component is not particularly limited, and for example, oxides, hydroxides, fluorides, complex fluorides, chlorides, nitrates, oxynitrates, sulfates, oxysulfates of these metal elements , Carbonates, oxycarbonates, phosphates, oxyphosphates, oxalates, oxyoxalates, and organometallic compounds can be used, and two or more can be used in combination.
  • the phosphoric acid used in the present invention becomes an anion moiety when forming the phosphate compound.
  • the supply source of phosphoric acid is not specifically limited, For example, orthophosphoric acid, condensed phosphoric acid, etc. can be used and 2 or more types can be used together.
  • an accelerator for producing a phosphate compound it is preferable to add an accelerator for producing a phosphate compound to the post-treatment liquid for autodeposition coating used in the present invention.
  • the accelerator has an effect of increasing the production amount of the phosphate compound by accelerating the etching reaction on the metal surface on which the uncured autodeposited film has been deposited.
  • the accelerator include nitrite, hydroxylamine, hydroxylamine sulfate, hydroxylamine phosphate, hydroxylamine hydrochloride, hydroxylammonium, hydrogen peroxide, etc. Among them, nitrite and hydroxylamine are preferable.
  • K A / B, which is the ratio of the total molar concentration A of metal components to the molar concentration B of phosphoric acid in the treatment liquid of the present invention, is preferably in the range of formula (1), and in the range of formula (2). More preferably it is.
  • K is smaller than 0.001 since the ratio of the metal component is small, it is not possible to obtain a phosphate compound sufficient to obtain corrosion resistance and adhesion.
  • K is larger than 0.5, an excessive metal component may adversely affect the appearance of the autodeposition coating, resulting in appearance defects such as coating cracks and pinholes.
  • the metal component in the post-treatment liquid for autodeposition coating was measured using high frequency inductively coupled plasma optical emission spectrometry (ICP) and represented by the total molar concentration (mol / L) as each metal element in the treatment liquid. Is done.
  • phosphoric acid in the post-treatment liquid for autodeposition coating is measured using ion chromatography (IC) and is expressed as a molar concentration (mol / L) as PO4 in the treatment liquid. (Formula 3)
  • IC ion chromatography
  • the concentration of the metal component in the treatment liquid of the present invention is preferably 0.1 to 500 mmol / L, more preferably 1 to 100 mmol / L.
  • concentration of the metal component is less than 0.1 mmol / L, formation of a phosphate compound sufficient to obtain corrosion resistance and adhesion cannot be obtained.
  • it is higher than 500 mmol / L, the amount of the phosphate compound formed becomes too large, which may cause an abnormality in the appearance of the self-deposited film, and is also disadvantageous economically.
  • concentrations of the metal component in the treatment liquid of the present invention are 20 mmol / L or more for manganese, 5 mmol / L or more for cobalt, 30 mmol / L or more for nickel, and 1 mmol / L or more for lithium, iron, copper, and aluminum.
  • the concentration of the accelerator when it is added is preferably 1 to 1000 mmol / L, more preferably 10 to 300 mmol / L.
  • concentration of the accelerator is less than 1 mmol / L, it is not possible to obtain a sufficient promoting effect for obtaining corrosion resistance and adhesion.
  • concentration of the accelerator is higher than 1000 mmol / L, as the metal etching reaction is promoted, the amount of the phosphate compound formed becomes excessive, and the appearance of the autodeposition coating may be abnormal.
  • the post-treatment liquid for autodeposition coating used in the present invention is preferably adjusted and maintained within the range of pH 2-6, more preferably pH 3-5.
  • pH 2-6 more preferably pH 3-5.
  • the pH is less than 2
  • the etching reaction of the metal becomes excessive, and abnormalities such as cracking of the film and pinholes occur in the appearance of the film.
  • the pH is higher than 6, a phosphate compound may be formed and precipitated in the post-treatment liquid for the autodeposition coating depending on the kind of the metal component, and the effect is lost.
  • the drug used is not particularly limited.
  • acids such as hydrochloric acid, sulfuric acid, nitric acid, phosphoric acid, boric acid, organic acids; lithium hydroxide, potassium hydroxide, sodium hydroxide, calcium hydroxide, magnesium hydroxide, barium hydroxide, alkali metal salts, ammonia, Examples include alkalis such as ammonium salts and amines.
  • the post-treatment liquid for autodeposition coating of the present invention can be applied to metal materials such as iron-based metal materials and galvanized steel sheets.
  • metal materials such as iron-based metal materials and galvanized steel sheets.
  • the most suitable metal material is an iron-based metal material.
  • the iron-based metal material as used herein refers to steel sheets such as cold-rolled steel sheets and hot-rolled steel sheets, and iron-based materials such as cast iron and sintered materials.
  • the autodeposition coating that is the target of the post-treatment agent of the present invention is a coating that contains at least tannin as a resin component. This autodeposition coating is formed using the autodeposition composition described below.
  • the autodeposition composition is characterized in that an autodeposition coating whose thickness or weight increases with the immersion time can be formed by immersing a clean metal surface in the composition. Furthermore, a part of the metal ions eluted from the metal by the chemical action (etching) of the autodeposition composition on the metal surface is taken into the film, and the film is formed. There is a feature that an autodeposition coating can be effectively formed on the surface of the metal without using a metal.
  • a suitable autodeposition composition contains a tannin component as a resin and a component having a chemical action (etching).
  • a more preferable autodeposition composition is obtained by mixing a tannin component as a resin, an acid, an oxidizing agent, and a compound capable of supplying ferric ions as required, and further adding water as necessary. is there.
  • each component will be described in detail.
  • the resin component of the autodeposition composition to which the post-treatment liquid according to the present invention is applied contains at least tannin.
  • the post-treatment liquid for autodeposition coating of the present invention was used for an autodeposition coating in which tannin is a resin component, the anticorrosion property of the phosphate compound was imparted to the coating, and the corrosion resistance was significantly improved. It has become possible to obtain a high level of corrosion resistance and adhesion satisfying all the test items of the salt warm water test, the salt spray test, the combined environmental cycle test, and the adhesion test required by the inventors.
  • the tannin used is not particularly limited.
  • tannins are hydrolyzed tannins, and more preferred are pentaploids and gallics.
  • the content of tannin is preferably 10 to 90%, more preferably 20 to 50%, based on the total mass (dry) of the autodeposition composition.
  • phenolic hydroxyl group refers to the hydroxyl group of phenols
  • phenol nucleus refers to a carbon in the ortho or para position relative to the hydroxyl group of phenol.
  • crosslinking group of the crosslinking agent a methylol group, a carboxyl group, a glycidyl group, a secondary alcohol group in which a glycidyl group is opened, an isocyanate group, or the like can be used, and among them, an isocyanate group is preferable.
  • a more preferable crosslinking agent is a polyfunctional blocked isocyanate obtained by adding at least 2 mol of polyisocyanate in which one isocyanate group is blocked with a blocking agent to 1 mol of polyol.
  • the isocyanate group is optimal as a crosslinking agent because it can be inhibited from reaction with water by blocking with a blocking agent, and the blocking agent is dissociated by applying heat to cause a crosslinking reaction.
  • polyether glycol such as polypropylene glycol, polyethylene glycol, polytetramethylene glycol, a copolymer of polyethylene glycol and polypropylene glycol, polyethylene adipate, polydiethylene adipate, polypropylene adipate,
  • polyester polyols such as polytetramethylene adipate and poly- ⁇ -caprolactone, polycarbonate polyols, acrylic polyols, epoxy polyols, trimethylolpropane, bisphenol A, bisphenol F, and bisphenol AD.
  • a preferred first polyol is a polyether polyol.
  • the detailed mechanism that supports the self-emulsifying type blocked isocyanate using such a polyether polyol is not known at this stage, by using the self-emulsifying type blocked isocyanate using the polyether polyol as the polyol, The deposition rate of the autodeposition coating can be significantly improved.
  • the self-emulsifying type blocked isocyanate means that the polymer molecule itself has an affinity for water by adding an anionic, cationic or nonionic hydrophilic group to the blocked isocyanate polymer molecule. What can be emulsified and dispersed is shown.
  • polyethylene glycol is particularly suitable for the balance between its water solubility and the deposition rate of the autodeposition coating.
  • the preferred second polyol is an epoxy polyol or bisphenol A having at least one bisphenol A structure in the molecular structure.
  • “having at least one molecule of bisphenol A structure” means a polymer such as the above-described epoxy polyol, a polymer partially including a repeating unit of bisphenol A, or a homopolymer of bisphenol A. Or bisphenol A itself.
  • Bisphenol A has a benzene ring in the basic skeleton, and since the two benzene rings are connected by a methylene chain with two methyl groups, the resin itself has robustness (rigidity) and high chemical resistance.
  • polyisocyanate a well-known thing can be used as said polyisocyanate.
  • aliphatic diisocyanates such as hexamethylene diisocyanate, 1,3,6-hexamethylene triisocyanate, 1,8-diisocyanate-4-isocyanatomethyloctane, 2-isocyanatoethyl (2,6-diisocyanate) hexanoate
  • a diisocyanate having a cyclic structure such as aliphatic triisocyanate and isophorone diisocyanate, m- or p-phenylene diisocyanate, toluene-2,4- or 2,6
  • preferred polyisocyanates are 1,6-hexamethylene diisocyanate from the viewpoint of the flexibility of the resulting film, and toluene-2,4- or 2,6-diisocyanate from the viewpoint of the reactivity of the isocyanate group.
  • blocking agent known blocking agents for the isocyanate group can be used.
  • alcohol such as methanol, ethanol, n-propyl alcohol, iso-propyl alcohol, n-butyl alcohol, iso-butyl alcohol, tert-butyl alcohol, phenol, methylphenol, chlorophenol, p-iso-butylphenol, p -Phenols such as tert-butylphenol, p-iso-amylphenol, p-octylphenol and p-nonylphenol; active methylene compounds such as malonic acid dimethyl ester, malonic acid diethyl ester, acetylacetone, methyl acetoacetate and ethyl acetoacetate; Formaldoxime, acetoaldoxime, acetone oxime, methyl ethyl ketone oxime, cyclohexanone oxime, acetophenone oxime, benzophenone oxi
  • the acid and / or oxidizing agent for example, at least one selected from zircon hydrofluoric acid, titanium hydrofluoric acid, silicohydrofluoric acid, borohydrofluoric acid, hydrofluoric acid, phosphoric acid, nitric acid and the like can be used. Hydrofluoric acid is preferred.
  • the compound capable of supplying ferric ions is not particularly limited as long as it is stable in the autodeposition composition, and examples thereof include ferric fluoride, ferric nitrate, and ferrous phosphate. Ferric fluoride is preferred.
  • the autodeposition composition that can be used in the present invention may contain a rust preventive pigment selected from the group consisting of cerium, yttrium, aluminum, and strontium.
  • a rust preventive pigment selected from the group consisting of cerium, yttrium, aluminum, and strontium.
  • the cerium, yttrium, aluminum, and strontium are preferably fluoride particles.
  • the fluoride particles will be described in detail.
  • the fluoride particles have low solubility in an aqueous hydrofluoric acid solution, the supplied fluoride exists almost as solid particles in the surface treatment liquid of the present invention, and when the organic coating is deposited by an autodeposition reaction. It is incorporated into the film. Corrosion resistance of the autodeposition coating is improved by the incorporated fluoride particles. At the present time, the effect of the fluoride particles is not clear, but the presence of fluoride particles in the coating slows the rate at which the corrosion promoting components that have entered the coating reach the metal interface, and baking. This is considered to have an effect of promoting the crosslinking reaction between the resin component in the autodeposition coating film and the crosslinking agent.
  • the preferable average particle diameter of at least 1 sort (s) chosen from the group which consists of cerium fluoride, yttrium fluoride, aluminum fluoride, and strontium fluoride is 50 micrometers or less, More preferably, it is 10 micrometers or less.
  • grains is 0.1 micrometer from the effect
  • a degreasing step in which the surface is washed in advance by degreasing and water washing treatment, an iron-based metal material after the degreasing step is brought into contact with the autodeposition composition, and the surface of the metal is not deposited
  • An uncured self-deposited film forming step for forming a cured self-deposited film
  • a post-treatment liquid contacting step for bringing the uncured self-deposited film into contact with the post-treatment liquid for self-deposited film
  • a baking step a baking step.
  • ⁇ Degreasing process> For the degreasing treatment, conventionally used solvent degreasing, alkali degreasing and the like can be used, and the construction method is also poured, and there are no restrictions such as spraying, dipping and electrolysis. Moreover, there is no restriction
  • the quality of water used for washing is not particularly limited, but ion-exchanged water is a preferred choice in consideration of bringing in small components into the autodeposition coating treatment bath and remaining in the coating.
  • ⁇ Uncured autodeposition coating formation process> There is no particular limitation on the method of treating the metal surface using the autodeposition composition that can be used in the present invention, and a general application method of a surface treatment agent such as a dipping method, a spray method, or a roll coating method is adopted. A dipping method is preferred.
  • the treatment temperature and treatment time are not particularly limited, but in the case of immersion treatment, it is generally appropriate to immerse in the composition at room temperature, for example, 18 to 25 ° C. for 30 to 600 seconds, preferably 90 to 300 seconds. is there.
  • the amount of the autodeposition composition applied to the metal is not particularly limited, but the film thickness after baking is preferably 5 to 40 ⁇ m.
  • the post-treatment of the present invention may be performed immediately.
  • the post-treatment of the present invention is preferably performed after washing with water. This water washing is usually performed by immersing in normal temperature water for 10 to 180 seconds, preferably 20 to 120 seconds.
  • the treatment time (for example, immersion time) in the post-treatment for the self-deposited film is not particularly limited, but the preferred treatment time for obtaining the effect of the present invention is 10 seconds to 5 minutes, more preferably 30 seconds to 2 minutes. is there. Usually, after the treatment is completed (for example, after the completion of immersion), baking is performed immediately, but washing may be performed before the baking process.
  • a preferable baking temperature in the baking step is 170 to 220 ° C, more preferably 180 to 200 ° C.
  • a preferable baking time in the baking step is 10 to 60 minutes, more preferably 20 to 40 minutes.
  • the post-treatment liquid for autodeposition coating on a metal surface and the post-treatment method for autodeposition coating of the present invention will be specifically described.
  • the to-be-processed material used in the Example, a degreasing agent, and a coating material are arbitrarily selected from commercially available materials, and for the post-treatment liquid for the autodeposition coating on the metal surface of the present invention and for the autodeposition coating It does not limit the actual use of the post-processing method.
  • Test plate Cold rolled steel sheet: JIS-G-3141
  • Examples 1 to 23 and Comparative Examples 1 to 3 A commercially available alkaline degreasing agent, Fine Cleaner L4460 (Nippon Parkerizing Co., Ltd.) was diluted with water to 2% by mass and humidified to 40 ° C., and sprayed on a test plate with a spray device to perform degreasing treatment. The surface of the test plate after the degreasing treatment was washed with ion-exchanged water using a spray device.
  • the test plate whose surface was degreased and washed was prepared by using commercially available tannin (trade name: Tannic acid AL: Fuji Chemical Industry Co., Ltd.) and a commercially available water-soluble blocked isocyanate (trade name: Elastron H38: Daiichi Kogyo Seiyaku Co., Ltd.).
  • Comparative example 4 A commercially available alkaline degreasing agent, Fine Cleaner L4460 (manufactured by Nihon Parkerizing Co., Ltd.) was diluted to 2% by mass with water and moisturized at 40 ° C., and sprayed on a test plate with a spray device for degreasing treatment. The surface of the test plate after the degreasing treatment was washed with ion-exchanged water using a spray device.
  • Fine Cleaner L4460 manufactured by Nihon Parkerizing Co., Ltd.
  • test plate from which the surface was degreased was washed with commercially available tannin (trade name Tannic Acid AL: manufactured by Fuji Chemical Industry Co., Ltd.) and a commercially available water-soluble blocked isocyanate (trade name Elastron H38: Daiichi Kogyo Seiyaku Co., Ltd.).
  • tannin trade name Tannic Acid AL: manufactured by Fuji Chemical Industry Co., Ltd.
  • water-soluble blocked isocyanate trade name Elastron H38: Daiichi Kogyo Seiyaku Co., Ltd.
  • Examples 24 to 26 and Comparative Examples 5 and 6 A commercially available alkaline degreasing agent, Fine Cleaner L4460 (manufactured by Nihon Parkerizing Co., Ltd.) was diluted to 2% by mass with water and moisturized at 40 ° C., and sprayed on a test plate with a spray device for degreasing treatment. The surface of the test plate after the degreasing treatment was washed with ion-exchanged water using a spray device.
  • Fine Cleaner L4460 manufactured by Nihon Parkerizing Co., Ltd.
  • the test plate whose surface was degreased and washed was prepared by using commercially available tannin (trade name: Tannic acid AL: manufactured by Fuji Chemical Industry Co., Ltd.) and a commercially available water-soluble blocked isocyanate (trade name: Elastron H38: Daiichi Kogyo Seiyaku Co., Ltd.).
  • commercially available tannin trade name: Tannic acid AL: manufactured by Fuji Chemical Industry Co., Ltd.
  • a commercially available water-soluble blocked isocyanate trade name: Elastron H38: Daiichi Kogyo Seiyaku Co., Ltd.
  • the self-deposited film after baking is referred to as a self-deposited film, and the coating film that has been subjected to baking after top coating is referred to as a 3 caots coating film.
  • SDT salt warm water test (self-deposited coating)
  • SST Salt spray test (self-deposited coating)
  • DuPont DuPont impact test (self-deposited coating)
  • CCT Combined environmental cycle test (3caots coating)
  • 1STADH Primary adhesion (3coats coating film)
  • 2ndADH Water resistant secondary adhesion (3coats coating film)
  • the maximum swollen width on both sides is less than 2.0 mm
  • B The maximum swollen width on both sides is 2.0 mm or more and less than 4.0 mm ⁇ : The maximum swollen width on both sides is 4.0 mm or more and less than 6.0 mm ⁇ : The maximum swollen width on both sides is 6. 0mm or more
  • A The maximum swollen width on both sides is less than 4.0 mm.
  • ⁇ The maximum swollen width on both sides is 4.0 mm or more and less than 6.0 mm.
  • ⁇ The maximum swollen width on both sides is 4.0 mm or more and less than 8.0 mm. 0mm or more
  • Table 4 shows the evaluation results of the self-deposited films obtained in Examples 1 to 26 and Comparative Examples 1 to 6.
  • Example 20 where the nickel concentration was as low as 0.1 mmol, Example 21 where the cobalt concentration was as low as 0.4 mmol, and Example 22 where the manganese concentration was as low as 0.2 mmol were as in Example Although it is inferior to 1 to 5, the SDT evaluation is ⁇ , and the SST evaluation is ⁇ .
  • a DuPont test result is OK and has favorable adhesiveness.
  • Example 23 which has a higher pH than Examples 1-16, precipitates were generated in the uncured autodeposition coating treatment solution, and the results of the SDT and SST tests were higher than those of Examples 1-16.
  • the evaluation of the inferior one is ⁇ .
  • a DuPont test result is OK and has favorable adhesiveness.
  • Examples 24 to 26 are evaluated as ⁇ in the CCT test results, have extremely excellent corrosion resistance, and also have excellent adhesion.

Abstract

L'invention porte sur une technique de post-traitement pour un film de revêtement auto-déposé qui contient du tannin comme composant de résine, qui ne contient aucun composant dangereux pour l'environnement tel que du chrome, et qui peut communiquer des niveaux élevés de résistance à la corrosion et des propriétés d'adhérence élevées au film de revêtement auto-déposé. Selon l'invention, il est décrit de façon spécifique une solution de post-traitement pour un film de revêtement auto-déposé qui est formé sur une surface métallique et qui contient du tannin comme composant de résine. La solution de post-traitement est caractérisée en ce qu'elle est une solution aqueuse comprenant au moins un composant métallique sélectionné parmi le groupe comprenant le lithium, le manganèse, le fer, le cobalt, le nickel, le cuivre et l'aluminium et de l'acide phosphorique.
PCT/JP2010/005051 2009-08-17 2010-08-12 Solution de post-traitement pour film de revêtement auto-déposé formé sur une surface métallique, et procédé pour la production d'un matériau métallique comportant un film de revêtement auto-déposé post-traité formé sur celui-ci WO2011021374A1 (fr)

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JP2009188564A JP5518398B2 (ja) 2009-08-17 2009-08-17 金属表面の自己析出被膜用後処理液及び後処理された自己析出被膜が形成された金属材料の製造方法

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JP5865619B2 (ja) * 2011-07-15 2016-02-17 日本パーカライジング株式会社 水系金属表面処理剤及びその処理剤で処理してなる金属材料
JP5889561B2 (ja) * 2011-07-15 2016-03-22 日本パーカライジング株式会社 水系金属表面処理剤及び表面皮膜付き金属材料
JP2019173180A (ja) * 2019-07-09 2019-10-10 有限会社昭和ケミカル静岡 塗装下地皮膜付き金属の製造方法および塗装下地皮膜形成用の処理液
CN115463564B (zh) * 2022-09-08 2023-08-15 哈尔滨工业大学水资源国家工程研究中心有限公司 一种基于金属多酚网络的超滤膜表面原位生长二氧化锰改性方法

Citations (3)

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Publication number Priority date Publication date Assignee Title
JPS6191369A (ja) * 1984-10-09 1986-05-09 パーカー・ケミカル・カンパニー クロムを含まない処理液でアルミニウム表面を処理する方法
JP2001192852A (ja) * 1999-10-22 2001-07-17 Kawasaki Steel Corp 金属表面処理組成物
JP2008150542A (ja) * 2006-12-20 2008-07-03 Cadic:Kk コーティング溶液、該溶液を用いた無機−有機ハイブリッド皮膜の形成方法、およびこの形成方法により得られる皮膜

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS6191369A (ja) * 1984-10-09 1986-05-09 パーカー・ケミカル・カンパニー クロムを含まない処理液でアルミニウム表面を処理する方法
JP2001192852A (ja) * 1999-10-22 2001-07-17 Kawasaki Steel Corp 金属表面処理組成物
JP2008150542A (ja) * 2006-12-20 2008-07-03 Cadic:Kk コーティング溶液、該溶液を用いた無機−有機ハイブリッド皮膜の形成方法、およびこの形成方法により得られる皮膜

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