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WO2015098623A1 - Agent de traitement de conversion chimique aqueux pour l'aluminium ou un alliage d'aluminium, procédé de traitement de conversion chimique et aluminium et alliage d'aluminium ayant subi un traitement de conversion chimique - Google Patents

Agent de traitement de conversion chimique aqueux pour l'aluminium ou un alliage d'aluminium, procédé de traitement de conversion chimique et aluminium et alliage d'aluminium ayant subi un traitement de conversion chimique Download PDF

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Publication number
WO2015098623A1
WO2015098623A1 PCT/JP2014/083274 JP2014083274W WO2015098623A1 WO 2015098623 A1 WO2015098623 A1 WO 2015098623A1 JP 2014083274 W JP2014083274 W JP 2014083274W WO 2015098623 A1 WO2015098623 A1 WO 2015098623A1
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Prior art keywords
chemical conversion
aluminum
conversion treatment
water
soluble
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English (en)
Japanese (ja)
Inventor
悠 久冨
一博 前田
賢一郎 大下
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Nihon Parkerizing Co Ltd
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Nihon Parkerizing Co Ltd
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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
    • C23C22/34—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
    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C22/00—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals
    • C23C22/78—Pretreatment of the material to be coated
    • 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
    • C23C2222/00—Aspects relating to chemical surface treatment of metallic material by reaction of the surface with a reactive medium
    • C23C2222/10—Use of solutions containing trivalent chromium but free of hexavalent chromium

Definitions

  • the present invention forms a conversion film that imparts excellent corrosion resistance to the surface of aluminum or an aluminum alloy, including aluminum die-cast materials, which are difficult to impart sufficient corrosion resistance with the prior art, without using hexavalent chromium. Related to technology.
  • the chemical conversion film formed with such a hexavalent chromium-containing chemical conversion treatment agent exhibits very excellent corrosion resistance.
  • hexavalent chromium is a harmful chemical substance
  • the performance difference (coating adhesion in addition to corrosion resistance) between the hexavalent chromium-containing chemical conversion treatment agent and the hexavalent chromium-free chemical conversion treatment agent is significant. This is because a thick oxide film is often formed on the surface of the aluminum die-cast material, and a mold release agent used during molding also remains, so that a dense and uniform chemical conversion film is formed. The difficulty is one cause.
  • copper is added to the aluminum die-cast material as an alloy component for the purpose of increasing mechanical strength. Since copper is electrochemically noble with respect to aluminum, it easily induces contact corrosion of different metals and lowers the corrosion resistance of the material itself.
  • copper may be segregated at a high concentration on the surface of the material and may appear more prominently. Therefore, it is difficult for an aluminum die-cast material to obtain a highly corrosion-resistant hexavalent chromium-free chemical conversion film stably as compared with a rolled material.
  • a surface treatment method using a trivalent chromium-containing type chemical conversion treatment agent has been industrialized as a chemical conversion treatment method having performance next to a hexavalent chromium-containing chemical conversion treatment agent.
  • Patent Document 1 As a trivalent chromium-containing type for aluminum and aluminum alloys, a metal component containing trivalent chromium is controlled by controlling the fluorine concentration in the chemical conversion treatment agent. Some have formed a composite film.
  • JP 2006-316334 A includes a chemical conversion treatment agent characterized by containing a trivalent chromium compound, a zirconium compound, and a dicarboxylic acid compound.
  • Patent Documents 3 to 5 various chromium-free chemical conversion treatment agents have been devised, and these form oxides such as zirconium, titanium and vanadium as a film.
  • Patent Document 6 discloses an aqueous ground treatment agent characterized by containing chitosan and a metal compound, and describes that it can also be applied as a reactive chemical conversion treatment agent. ing.
  • Patent Documents 1 to 5 it is difficult to stably impart high corrosion resistance to an aluminum material having a poor surface state such as an aluminum die cast. Furthermore, even when the technique according to Patent Document 6 is applied to aluminum as a metal material, the chemical conversion reaction is difficult to proceed, and a highly corrosion-resistant chemical film cannot be obtained.
  • this invention aims at providing the hexavalent chromium free chemical conversion treatment technology which shows the stable high corrosion resistance with respect to aluminum and aluminum alloys which exhibit various surface states, especially aluminum die-cast material. .
  • the present invention relates to an aqueous chemical conversion treatment agent for surface-treating aluminum or an aluminum alloy
  • the aqueous chemical conversion treatment agent is a chitosan (A), at least one component (B) selected from the group consisting of a water-soluble trivalent chromium compound, a water-soluble titanium compound and a water-soluble zirconium compound, and a nitrate radical (C) is an aqueous chemical conversion treatment agent that is used as it is or diluted as it is, which is an agent that contains a dissolved fluorine component (D).
  • the “aqueous chemical conversion treatment agent” in the claims and the specification is a concept including both a stock solution and a diluted solution, and further includes a concept including both a new solution and an old solution.
  • the ratio (X / Y) of the addition amount (X) of the chitosans (A) and the total addition amount (Y) of the metal components (Cr, Ti, Zr) in the component (B) is a mass ratio. It may be 0.02 to 100. Further, the ratio (Y / Z) between the (Y) and the amount of free fluorine (Z) in the agent for the chemical conversion treatment may be 0.07 to 200 in mass ratio.
  • the ratio is in the aqueous chemical conversion treatment agent (raw solution).
  • the diluted raw solution is used for the chemical conversion treatment, It is a ratio in a chemical conversion treatment agent (dilution liquid).
  • the said component (B) may be a water-soluble trivalent chromium compound and a water-soluble zirconium compound.
  • the aqueous chemical conversion treatment agent may contain an alkaline earth metal (E). Further, the pH of the agent when performing the chemical conversion treatment may be 2.3 to 5.0.
  • the aqueous chemical conversion treatment agent (stock solution) when used as it is for the chemical conversion treatment, it is the pH in the aqueous chemical conversion treatment agent (stock solution).
  • the diluted raw solution when used for the chemical conversion treatment, It is pH in a chemical conversion treatment agent (diluent).
  • the concentration of free fluorine of the agent when performing the chemical conversion treatment may be 5 to 150 mg / L.
  • the aqueous chemical conversion treatment agent (stock solution) is used as it is for the chemical conversion treatment, it is the free fluorine concentration in the aqueous chemical conversion treatment agent (stock solution).
  • the present invention is a surface treatment method for aluminum or an aluminum alloy, comprising the step of subjecting the aluminum or aluminum alloy to a chemical conversion treatment using the aqueous chemical conversion treatment agent as it is or diluted.
  • a step of pickling the aluminum or aluminum alloy using the washing treatment liquid may be further included.
  • the ratio (M / N) of the total organic carbon amount (M) in the chemical conversion film formed on the surface-treated aluminum or aluminum alloy and the total amount (N) of Cr, Ti and Zr is mass.
  • the ratio may be 0.05 to 0.95.
  • this invention is a manufacturing method of the surface-treated aluminum or aluminum alloy which includes the said surface treatment method as a process.
  • the present invention relates to an aluminum or aluminum alloy on which a chemical conversion film is formed,
  • the ratio (M / N) of the total organic carbon amount (M) in the chemical conversion film to the total amount (N) of Cr, Ti and Zr is 0.05 to 0.95 in mass ratio.
  • the aluminum or aluminum alloy on which the chemical conversion film is formed may be an aluminum die-cast material.
  • a hexavalent chromium-free chemical conversion technology that stably exhibits excellent corrosion resistance for aluminum and aluminum alloys exhibiting various surface states, particularly aluminum die-cast materials.
  • Water-based chemical conversion treatment agent (2) Method for producing water-based chemical conversion treatment agent (3) Method for using water-based chemical conversion treatment agent (Method for producing aluminum material with chemical conversion film) (4) Aluminum material with chemical coating
  • the water-based chemical conversion treatment agent for surface treatment of aluminum or an aluminum alloy according to the present invention includes chitosans (A), a water-soluble trivalent chromium compound, a water-soluble titanium compound, and a water-soluble zirconium compound.
  • a component comprising at least one component (B) selected from the group consisting of: and a nitrate radical (C), and an agent containing a soluble fluorine component (D) It is a water-based chemical conversion treatment agent used as it is or diluted.
  • each component, composition (blending amount, blending ratio) and liquid property will be described in detail.
  • the chitosan (A) according to the aqueous chemical conversion treatment agent of the present invention is a very important component for enhancing the barrier effect of the chemical conversion film. This is because when the chitosans are effectively incorporated into the chemical conversion film, the barrier property (shielding property) against the external corrosion factor of the chemical conversion film is remarkably improved, and the corrosion resistance is greatly affected.
  • the chitosans used in the present invention can be obtained, for example, by deacetylating chitin, which is a natural polymer extracted from crustaceans such as crabs and shrimps, to 60 to 100 mol%.
  • chitin which is a natural polymer extracted from crustaceans such as crabs and shrimps
  • 100 mol% deacetylated chitosan is a polymer substance in which N-acetyl- ⁇ -D-glucosamine is bonded at the 1-position and 4-position.
  • the chitosan derivative is a reaction product obtained by carboxylation, glycolation, tosylation, sulfation, phosphorylation, etherification and / or alkylation of the hydroxyl group and / or amino group of chitosan.
  • Specific examples include carboxymethyl chitosan, hydroxyethyl chitosan, hydroxypropyl chitosan, hydroxybutyl chitosan, glycerylated chitosan and salts thereof with acids.
  • the weight average molecular weight of the chitosans (A) is preferably from 1,000 to 2,000,000, more preferably from 10,000 to 1,000,000. If it is less than 1,000, a conversion coating with high barrier properties cannot be obtained. On the other hand, when it exceeds 2 million, the viscosity of the treatment liquid is too high, and the chemical conversion film formation reaction hardly occurs.
  • the weight average molecular weight is a polystyrene equivalent value using a calibration curve of standard polystyrene by gel permeation chromatography (GPC) method.
  • chitosan derivatives in which a tertiary or quaternized amino group is newly introduced using a compound having a tertiary or quaternary amino group or both in chitosan, and the amino group of chitosan is directly alkylated with an alkylating agent. It may be a directly tertiaryized or quaternized tertiary or quaternary amino group, or a so-called cationized chitosan having both in the molecule and a salt thereof with an acid.
  • Examples of the compound having a tertiary or quaternary amino group include 2-chloroethyldiethylamine or its hydrochloride, 3-chloro-2-hydroxypropyldiethylamine, 2,3-epoxypropyldimethylamine, trimethyl-3-chloro. Examples include -2-hydroxypropyltrimethylammonium chloride and 2,3-epoxypropyltrimethylammonium chloride. Examples of the alkylating agent that directly alkylates the amino group include methyl iodine and ethyl iodine.
  • chitosans chitosan, hydroxyethyl chitosan and hydroxypropyl chitosan are most suitable. This is because the crosslinkability with the metal component is particularly high when incorporated in the chemical conversion film.
  • Component (B) consisting of at least one selected from the group consisting of a water-soluble trivalent chromium compound, a water-soluble titanium compound and a water-soluble zirconium compound according to the aqueous chemical conversion treatment agent of the present invention greatly affects the corrosion resistance.
  • water-soluble means that the solubility in water at 20 ° C. is 1 g / 100 ml or more.
  • Specific examples include chromium nitrate, chromium sulfate, chromium fluoride, fluorotitanic acid, fluorotitanium complex salt, fluorozirconic acid, and fluorozirconium complex salt.
  • the combination of the water-soluble trivalent chromium compound and the water-soluble zirconium compound is most preferable as the metal combination in the component (B). This is because chitosan is strongly cross-linked by the presence of the two metal components in the film, and the corrosion resistance is particularly good.
  • the nitrate radical (C) in the aqueous chemical conversion treatment agent of the present invention is a component for stabilizing chitosans and the metal component in the treatment liquid and preventing reprecipitation. Furthermore, there is an effect of facilitating the etching reaction with respect to aluminum or aluminum alloy and facilitating film formation. In addition, there is an effect of reducing the segregation of dissimilar metals on the aluminum surface and forming a uniform chemical conversion film.
  • examples of the nitrate radical (C) source include sodium nitrate, potassium nitrate, magnesium nitrate, and ammonium nitrate.
  • the aqueous chemical conversion treatment agent of the present invention contains a soluble fluorine component (D) (particularly free fluorine). This is to stabilize chitosans and metal components in the treatment liquid and prevent reprecipitation, as with the nitrate radical (C). In addition, the amount of free fluorine determines the etching power for the aluminum alloy.
  • soluble fluorine component (D) source include hydrofluoric acid, ammonium fluoride, silicic acid, sodium fluoride, and potassium fluoride.
  • the aqueous chemical conversion treatment agent of the present invention preferably contains an alkaline earth metal component (E). This is to prevent an excessive amount of free fluorine from being supplied to the metal surface in the etching reaction.
  • a particularly preferred alkaline earth metal is Mg.
  • the component may be added as a component independent of other compounds (A) to (C), or may be derived from another compound ⁇ for example, component (C) ⁇ .
  • One component may correspond to component (A) to component (E).
  • the above-mentioned chromium fluoride corresponds to both a chromium compound (A) and a soluble fluorine component (D) source.
  • composition (1-2-1) Blending amount
  • the blending amount (content) of component (A) is preferably 20 to 1000 mg / L, and more preferably 200 to 700 mg.
  • the content of the component (A) is less than 20 mg / L, the barrier effect of the chemical conversion film is insufficient and the corrosion resistance becomes insufficient.
  • the blending amount (content) here refers to the concentration after the dilution ⁇ the same applies to the following components (B) to (D) ⁇ .
  • the blending amount (content) of component (B) is preferably in the range of 10 to 1000 mg / L, more preferably in the range of 200 to 400 mg / L, in terms of chromium, titanium and / or zirconium. It is in. In any case of less than 10 mg / L and more than 1000 mg / L, it is difficult to obtain optimum film performance.
  • the blending amount (content) of the component (C) is preferably in the range of 500 to 10,000 mg / L in terms of total nitric acid equivalent content (CC) including the amount of nitric acid supplied by other components. .
  • CC content is less than 500 mg / L, chemical conversion failure due to insufficient etching occurs, and the stability of the treatment agent also deteriorates.
  • etching with respect to the aluminum alloy becomes excessive, and formation of a chemical conversion film hardly occurs.
  • the free fluorine concentration (CD) is preferably 5 to 150 mg / L, and more preferably 20 to 80 mg / L.
  • CD is less than 5 mg / L, etching becomes insufficient and a predetermined chemical conversion film may not be obtained.
  • the CD exceeds 150 mg / L, etching becomes excessive and formation of a chemical conversion film is difficult to occur.
  • the free fluorine is a value measured by the method described in Japanese Patent Publication No. 06-095086 (Japanese Patent Laid-Open No. 58-21644).
  • the mass ratio is preferably 0.02 to 100, and more preferably 0.5 to 3.5.
  • the ratio is less than 0.02 since the ratio of chitosan taken in in a chemical conversion film is low, high corrosion resistance cannot be obtained and predetermined performance may not be obtained.
  • it exceeds 100 since the ratio of a metal is low, chitosan is not fully bridge
  • the ratio (Y / Z) of (Y) to the amount of free fluorine (Z) in the agent for the chemical conversion treatment is preferably 0.07 to 200 by mass ratio. More preferably, it is 2.5 to 20.
  • capture of the fluorine in a chemical conversion film may become excess, and corrosion resistance may fall.
  • it exceeds 200 the metal component with respect to fluorine in the treatment liquid is excessive, and thus may be reprecipitated.
  • the pH of the agent during the chemical conversion treatment is preferably 2.3 to 5.0, and more preferably 3.0 to 4.5.
  • the pH is less than 2.3, the etching power of the obtained chemical conversion treatment agent becomes strong, and the deposition efficiency of the film is deteriorated.
  • pH exceeds 5.0, generation
  • the measurement of pH is a value measured according to a well-known method. Measurement temperature: A value measured at the processing temperature.
  • the eluted aluminum is considered to react with hydrogen fluoride present in the chemical conversion treating agent of the present invention to become aluminum fluoride.
  • the equilibrium reaction of this complex fluoride is changed due to the consumption of hydrogen ions accompanying the etching reaction, the dissociation of hydrofluoric acid, etc.
  • oxidation of trivalent chromium, titanium and / or zirconium is performed.
  • Substances are deposited on the film surface.
  • the chemical conversion film of the present invention contains the oxide as a main component and chitosan incorporated when the oxide is formed.
  • the chemical conversion film includes in its structure a form in which chitosan is crosslinked or combined with trivalent chromium oxide, zirconium oxide and / or titanium oxide.
  • the composite of chitosan into the film is considered to have a significant effect on imparting corrosion resistance.
  • the aqueous chemical conversion treatment agent according to the present invention can be obtained by adding an appropriate amount of the above-mentioned production raw material to water and stirring.
  • the solid raw material may be added to water, or the solid raw material may be previously dissolved in water and then added as an aqueous solution.
  • the method for adjusting the pH is not particularly limited, but it is preferably adjusted using nitric acid, hydrofluoric acid, ammonium hydrogen carbonate, aqueous ammonia, or the like.
  • the aqueous chemical conversion treatment agent (stock solution) manufactured by the above-mentioned method is diluted with an appropriate amount of water.
  • the solvent of the water-based chemical conversion treatment agent (stock solution, diluted solution) is mainly water.
  • the water-based chemical conversion treatment agent according to the present invention is particularly effective for aluminum and aluminum alloys, particularly aluminum die-cast materials having a thick oxide film on the surface and segregating alloy components. .
  • (3-2-1) Cleaning step It is preferable that the surface of the material to be brought into contact with the aqueous chemical conversion treatment agent according to the present invention is clean. Therefore, prior to the chemical conversion treatment, it is preferable to perform the chemical conversion treatment after cleaning the surface by solvent degreasing or alkali degreasing.
  • (3-2-2) Pickling Step When the pickling step using a specific pickling solution is applied before the chemical conversion treatment step as the surface treatment method of the present invention, the barrier property of the chemical conversion coating is amplified and the corrosion resistance is large. improves.
  • the pickling solution at least one selected from the group consisting of a water-soluble fluorine compound, a water-soluble sulfuric acid compound, a water-soluble nitric acid compound, a water-soluble phosphoric acid compound and an oxycarboxylic acid compound is added.
  • a water-soluble sulfuric acid compound ( ⁇ ) a water-soluble sulfuric acid compound, a water-soluble nitric acid compound, a water-soluble phosphoric acid compound and / or an oxycarboxylic acid compound, and ( ⁇ ) a water-soluble fluorine compound,
  • the combination of is more preferable.
  • specific examples of the water-soluble fluorine compound, water-soluble sulfuric acid compound, water-soluble nitric acid compound, water-soluble phosphoric acid compound and oxycarboxylic acid compound include hydrofluoric acid, sulfuric acid, nitric acid, phosphoric acid and hydrogen peroxide. be able to.
  • the pH of the liquid is preferably 1 to 5, and more preferably 1 to 3.
  • the substrate is brought into contact with this pickling solution for 30 to 600 seconds, then washed with water, and subsequently subjected to chemical conversion treatment.
  • the degree of etching in the pickling process depends on the surface state of the metal material to be treated, but usually the treatment time and concentration so that the etching weight for the base metal falls within the range of 0.1 to 5.0 g / m 2. To decide.
  • the mechanism by which the corrosion resistance is improved by the pickling method in the surface treatment of the present invention will be outlined.
  • a particularly preferable aluminum die casting material will be described as an example. Since the aluminum die cast material is formed by injecting a molten aluminum alloy at a high speed and a high pressure, a thick oxide film is formed on the surface as compared with a rolled material or the like. Since the oxide film inhibits the chemical conversion reaction, it is considered as a cause of chemical conversion failure. Further, as described above, the aluminum die-cast material includes various alloy components on the surface, and in particular, some alloy components such as copper have a standard electrode potential that is electrochemically noble with respect to aluminum.
  • the chemical conversion treatment step of the present invention is a step in which the aqueous chemical conversion treatment agent is heated to a temperature of 30 to 70 ° C. and brought into contact with the surface of clean aluminum or aluminum alloy for 10 to 600 seconds. is there. In addition, after the said process, it wash
  • the drying temperature is preferably from 50 to 140 ° C.
  • the target chemical conversion film with high barrier property may not be formed, and corrosion resistance may fall.
  • the method for bringing the chemical conversion treatment agent into contact with the metal material include an immersion method, a spray method, and a flow coating method.
  • the amount of chemical coating deposited on the aluminum material with chemical coating according to the present invention is 1 to 1000 mg / m 2 of total organic carbon (M), the total amount of Cr, Ti and Zr (N ) Is preferably 1 to 1000 mg / m 2 . Furthermore, the ratio (M / N) of the total organic carbon amount (M) to the total amount (N) of Cr, Ti and Zr is preferably 0.05 to 0.95. When the mass ratio is less than 0.05, the corrosion resistance is not sufficient because the incorporation of chitosan into the chemical conversion film is insufficient. On the other hand, when the mass ratio is more than 0.95, the metal component acting as a crosslinking agent is not sufficiently taken in, the barrier property of the chemical conversion film is lowered, and the corrosion resistance is not sufficient.
  • the weight average molecular weights of chitosan, hydroxyethyl chitosan, hydroxypropyl chitosan, carboxymethylpropane and 2-chloroethyldiethylamine used for the O-3 tertiary aminated chitosan used were 150,000, 170,000, 190,000, 140,000 and 180,000.
  • ⁇ Pickling Solution (Pretreatment Solution)> (A): Sulfuric acid: 5 g / L
  • test metal material was immersed in the cleaning agent at 65 ° C. for 2 minutes, and then the surface was rinsed and cleaned with tap water.
  • the sample metal material was immersed in the pickling solution at room temperature for 2 minutes, and then the surface was rinsed and cleaned with tap water (Table 2).
  • the said test metal material was immersed in the chemical conversion treatment agent which concerns on an Example and a comparative example (The undiluted
  • a solvent-based paint (amino alkyd) is applied to the surface of the test material that has been subjected to chemical conversion treatment to a thickness of 20 ⁇ m, and then separated from the edge by 15 mm using an acrylic cutter, and two diagonal lines intersecting to reach the substrate. Pull.
  • the specimen was subjected to a salt spray test (JIS-Z2371), and after 168 hours, the tape was peeled off, and the peel width of the coating film from the cut portion was measured.

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  • Chemical & Material Sciences (AREA)
  • General Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Mechanical Engineering (AREA)
  • Metallurgy (AREA)
  • Organic Chemistry (AREA)
  • Chemical Treatment Of Metals (AREA)

Abstract

Le problème à résoudre dans le cadre de l'invention consiste à fournir une technique de traitement de conversion chimique dépourvue de chrome hexavalent qui peut transmettre régulièrement une excellente résistance à la corrosion à l'aluminium ou à des alliages d'aluminium, en particulier un matériau moulé sous pression en aluminium, qui présentent divers états de surface. La solution proposée consiste en un agent de traitement de conversion chimique aqueux destiné à traiter la surface de l'aluminium ou d'un alliage d'aluminium, ledit agent de traitement de conversion chimique aqueux étant caractérisé par le fait qu'il est préparé par ajout d'un composé chitosane (A), d'au moins un composant (B) sélectionné dans le groupe constitué par un composé de chrome trivalent soluble dans l'eau, un composé de titane soluble dans l'eau et un composé de zirconium soluble dans l'eau et d'un ion nitrate (C) ensemble, et est également caractérisé par le fait qu'il contient en outre un composant de fluor soluble (D).
PCT/JP2014/083274 2013-12-25 2014-12-16 Agent de traitement de conversion chimique aqueux pour l'aluminium ou un alliage d'aluminium, procédé de traitement de conversion chimique et aluminium et alliage d'aluminium ayant subi un traitement de conversion chimique Ceased WO2015098623A1 (fr)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
JP2013267873A JP6395376B2 (ja) 2013-12-25 2013-12-25 アルミニウム又はアルミニウム合金用水系化成処理剤、化成処理方法及び化成処理されたアルミニウム及びアルミニウム合金
JP2013-267873 2013-12-25

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CN105463432A (zh) * 2015-12-31 2016-04-06 芜湖市金宇石化设备有限公司 一种铝合金表面磷化处理用处理液的制备方法
CN105543833A (zh) * 2015-12-31 2016-05-04 芜湖市金宇石化设备有限公司 一种铝合金表面磷化处理方法
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