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WO2017006805A1 - Solution aqueuse de traitement de surface métallique, procédé de traitement de surface métallique et conjugué - Google Patents

Solution aqueuse de traitement de surface métallique, procédé de traitement de surface métallique et conjugué Download PDF

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Publication number
WO2017006805A1
WO2017006805A1 PCT/JP2016/069105 JP2016069105W WO2017006805A1 WO 2017006805 A1 WO2017006805 A1 WO 2017006805A1 JP 2016069105 W JP2016069105 W JP 2016069105W WO 2017006805 A1 WO2017006805 A1 WO 2017006805A1
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Prior art keywords
surface treatment
metal surface
mass
aqueous solution
metal
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PCT/JP2016/069105
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English (en)
Japanese (ja)
Inventor
佑輔 高橋
悟 高田
Original Assignee
株式会社神戸製鋼所
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Priority claimed from JP2016113752A external-priority patent/JP2017203208A/ja
Application filed by 株式会社神戸製鋼所 filed Critical 株式会社神戸製鋼所
Priority to CN201680040146.6A priority Critical patent/CN107849697B/zh
Priority to US15/741,562 priority patent/US20180216235A1/en
Publication of WO2017006805A1 publication Critical patent/WO2017006805A1/fr

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    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B9/00—Layered products comprising a layer of a particular substance not covered by groups B32B11/00 - B32B29/00
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B15/00—Layered products comprising a layer of metal
    • B32B15/04—Layered products comprising a layer of metal comprising metal as the main or only constituent of a layer, which is next to another layer of the same or of a different material
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B15/00—Layered products comprising a layer of metal
    • B32B15/20—Layered products comprising a layer of metal comprising aluminium or copper
    • 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
    • C23C22/60—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 alkaline aqueous solutions with pH greater than 8
    • C23C22/66—Treatment of aluminium or alloys based thereon

Definitions

  • the present invention relates to a metal surface treatment aqueous solution, a metal surface treatment method, and a bonded body using a metal material treated with the metal surface treatment aqueous solution.
  • a surface treatment for improving the corrosion resistance and paint adhesion of a metal surface is known from the viewpoint of corrosion prevention.
  • Patent Document 1 discloses an adhesive formed on a metal such as aluminum by treating it with an aqueous composition containing a tetraalkylsilicate such as tetraethylorthosilicate and a hydrated oxide sol such as silica sol. A method for improving the initial adhesion of the coating film and the long-term stability of the adhesion is described.
  • Patent Document 2 discloses that after treating a metal substrate with a first treatment solution consisting essentially of at least one polyfunctional silane having at least two trisubstituted silyl groups, at least one kind of organo A technique for improving the corrosion resistance of a metal by applying a second coating containing a second treatment solution containing a functional silane is described.
  • Patent Document 3 describes a technique for improving the corrosion resistance of a metal by treating the metal substrate with a solution containing aminosilane and polysilyl functional silane.
  • Patent Document 4 describes a method of improving corrosion resistance by rinsing the surface of a galvanized steel sheet with an aqueous solution containing a silicate compound and then treating it with a silane coupling agent.
  • Patent Document 5 discloses that a solution containing a silicate ester, an aluminum inorganic salt and polyethylene glycol and further containing a silane coupling agent is applied onto a galvanized steel sheet and dried to form a film. Thus, a technique for improving paint adhesion and white rust resistance is described.
  • Patent Document 6 discloses a technique for improving paint adhesion by treating the surface of a metal material such as aluminum or aluminum alloy with an aqueous solution containing water glass such as sodium water glass and silane such as aminosilane. Are listed.
  • Patent Document 7 improves corrosion resistance and paint adhesion by treating a metal sheet with an alkaline solution containing an inorganic silicate, an organofunctional silane, and a crosslinking agent containing two or more trialkoxysilyl groups. The method is described.
  • Patent Documents 4 to 7 are intended only for the purpose of preventing corrosion of metal surfaces and improving the adhesion of paints. Therefore, although the formed film is thick, the mechanical film itself has low mechanical strength and becomes brittle with respect to tension and stress, and high adhesive strength cannot be obtained.
  • the surface-treated aluminum alloy material is coated with oil after the surface treatment to improve workability, and then molded and bonded.
  • oil such as lubricating oil, processing oil, and press oil
  • the adhesiveness of the adhesive is greatly reduced, and high adhesive strength cannot be obtained.
  • the present inventors first performed alkali degreasing and pickling on the aluminum alloy substrate, then treated with an alkali solution containing a silicic acid compound, and further silane coupling.
  • the inventors have found that the treatment with an aqueous solution containing an agent does not decrease the adhesive strength even after long-term wetting with moisture and that high adhesion durability can be obtained, and a patent application has already been filed (Japanese Patent Application No. 2014-228882).
  • a porous and brittle oxide film on the surface of an aluminum alloy substrate is treated with a basic solution containing a silicate compound, so that the oxide film reacts with silicate ions, resulting in a dense, chemical / physical
  • a composite oxide film that is stable and excellent in corrosion resistance is formed on the substrate surface.
  • the present invention can produce a surface-treated metal material that is less likely to have a reduced adhesive strength even when exposed to a high-temperature and humid environment, and that has excellent adhesion durability, in a simplified process.
  • An object of the present invention is to provide a metal surface treatment aqueous solution and a metal surface treatment method capable of reducing production costs, and a joined body using a metal material treated with the metal surface treatment aqueous solution.
  • the present inventors have included a silicic acid compound and an organosilane compound in a specific concentration range, and a metal surface treatment whose pH is adjusted to a specific range. It has been found that the above-mentioned problems can be solved by an aqueous solution, and the present invention has been completed.
  • the present invention includes 0.001% by mass or more and less than 0.5% by mass of a silicic acid compound and 0.001% by mass or more and less than 0.5% by mass of an organic silane compound, and has a pH of 7 or more and 14 or less.
  • An aqueous solution for metal surface treatment is provided.
  • the concentration of the silicate compound is preferably 0.01% by mass or more and less than 0.3% by mass.
  • the concentration of the silicate compound is more preferably 0.015% by mass or more and less than 0.2% by mass.
  • the silicate compound is a silicate compound represented by mM 2 O ⁇ nSiO 2 , where M is a monovalent cation and the number of moles of M 2 O.
  • the ratio n / m between m and n which is the number of moles of SiO 2 may be 1.5 or more.
  • M may be a sodium ion.
  • the silicate compound may be kanemite.
  • the concentration of the organosilane compound is preferably 0.005% by mass or more and less than 0.4% by mass.
  • the concentration of the organosilane compound is more preferably 0.01% by mass or more and less than 0.3% by mass.
  • the metal surface treatment aqueous solution has a pH of 8 or more.
  • the organosilane compound may contain a silane compound having a plurality of hydrolyzable trialkoxysilyl groups in the molecule, a hydrolyzate thereof, or a polymer thereof.
  • the aqueous solution for metal surface treatment may further contain at least one selected from the group consisting of an alcohol having 1 to 4 carbon atoms and a carboxylic acid having 1 to 4 carbon atoms as a stabilizer.
  • the organosilane compound may contain a silane coupling agent having a reactive functional group capable of chemically bonding with an organic resin component, a hydrolyzate thereof, or a polymer thereof.
  • the present invention is also directed to a method for treating a metal surface using the metal surface treatment aqueous solution, wherein the surface treatment film amount after drying the metal surface treatment aqueous solution is 0.5 mg / m 2 or more and 35 mg / m 2 or less.
  • a method of treating a metal surface comprising applying to the surface of the metal.
  • the metal may be an aluminum alloy.
  • the present invention also provides a joined body in which metal materials treated with the metal surface treatment aqueous solution are joined together via an adhesive resin.
  • the present invention also provides a joined body in which a metal material treated with the metal surface treatment aqueous solution and a resin molded body are joined via an adhesive resin.
  • the surface-treated metal material that is difficult to decrease the adhesive strength and has excellent adhesion durability even when exposed to a high-temperature wet environment has been simplified. It can manufacture in a process and can reduce capital investment cost and manufacturing cost.
  • FIG. 1A is a side view schematically showing a method for measuring the cohesive failure rate.
  • FIG. 1B is a plan view schematically showing a method for measuring the cohesive failure rate.
  • the aqueous solution for metal surface treatment comprises 0.001% by mass or more and less than 0.5% by mass of a silicic acid compound and 0.001% by mass or more and less than 0.5% by mass of an organosilane compound, and has a pH of 7 or more and 14 or less.
  • a silicate compound is introduced to the metal surface to form a composite oxide film of the metal element and silicon in the metal, A surface treatment film made of an organic silane compound in which the silane compound and the composite oxide film are chemically bonded is formed.
  • the surface-treated metal material obtained in this way has excellent bondability to the adhesive and further corrosion resistance, and it is difficult to decrease the adhesive strength even when exposed to high-temperature and humid environments, and has excellent adhesion durability. It is.
  • the surface treatment with a silicate compound and the surface treatment with an organosilane compound can be performed in one step, so that a surface-treated metal material having excellent adhesion durability can be simplified. It is possible to manufacture in a process that is realized, and it is possible to reduce the capital investment cost and the manufacturing cost.
  • the pH of the surface treatment solution of the present invention is 7 or more and 14 or less.
  • the pH of the surface treatment liquid is higher than 14, the organosilane compound is likely to be polymerized and the storage stability of the solution is lowered, which is not preferable. Further, when the polymerization of the organic silane compound proceeds, the generated organic silane treatment layer becomes thick, and when stress is applied, the inside of the treatment layer is broken and high adhesive strength cannot be obtained.
  • the pH of the surface treatment solution is lower than 7, the silicate compound is precipitated. Since the precipitated silicic acid compound forms a thick film as in the case of the organosilane compound, the adhesive strength decreases due to peeling of the film.
  • the pH of the surface treatment liquid needs to be in the range of 7 or more and 14 or less.
  • the pH of the surface treatment solution is preferably 8 or more, more preferably 9 or more, considering reactivity with the metal oxide film.
  • the pH of the surface treatment liquid can be appropriately adjusted by adding a base such as sodium hydroxide, sodium carbonate, or ammonia, or an acid salt such as acetic acid.
  • the concentration of the silicate compound in the surface treatment liquid is 0.001% by mass or more and less than 0.5% by mass.
  • concentration of the silicate compound in the surface treatment liquid is 0.5% by mass or more, the generated surface treatment film becomes thick and the strength is lowered.
  • concentration of the silicate compound in the surface treatment liquid is less than 0.001% by mass, the concentration of the silicate compound is too low, so that a composite oxide film of the metal element in the metal and silicon is sufficiently formed. Cannot be obtained, and sufficient adhesion durability cannot be obtained.
  • the concentration of the silicate compound in the surface treatment liquid is preferably 0.01% by mass or more, more preferably 0.015% by mass or more. Further, the concentration of the silicate compound in the surface treatment liquid is preferably less than 0.3% by mass, more preferably less than 0.2% by mass.
  • the concentration of the organosilane compound in the surface treatment liquid is 0.001% by mass or more and less than 0.5% by mass.
  • the concentration of the organosilane compound in the surface treatment liquid is 0.5% by mass or more, the generated surface treatment film becomes thick and the strength is lowered. Moreover, since the stability of a solution also falls, it is not preferable.
  • the concentration of the organic silane compound in the surface treatment liquid is less than 0.001% by mass, the concentration of the organic silane compound is too low, so that a surface treatment film containing the organic silane compound cannot be sufficiently formed. Thus, sufficient adhesion durability cannot be obtained.
  • the concentration of the organosilane compound in the surface treatment liquid is preferably 0.005% by mass or more, and more preferably 0.01% by mass or more. Moreover, the concentration of the organosilane compound in the surface treatment liquid is preferably less than 0.4% by mass, more preferably less than 0.3% by mass.
  • the type of silicic acid compound contained in the surface treatment liquid is not particularly limited, but considering the water solubility of the silicic acid compound, the monovalent cation (M) silicic acid compound, and further, crystallinity and amorphous Quality silicic acid compound (which can be expressed as mM 2 O ⁇ nSiO 2 , and the ratio n / m of m which is the number of moles of M 2 O and n which is the number of moles of SiO 2 is represented by a mole ratio). Can be mentioned.
  • alkali metal ions such as lithium ions, sodium ions and potassium ions and ammonium ions are preferable, and sodium ions are particularly preferable from the viewpoint of economy.
  • the silicate compound represented by mM 2 O ⁇ nSiO 2 include sodium orthosilicate (n / m: about 0.5), sodium metasilicate (n / m: about 1), water glass (JIS) No. 1, No. 2, No. 3, n / m: a range of about 1.5 to 4, and kanemite (n / m: a range of about 1.5 to 3).
  • a silicate compound having an n / m of 1.5 or more is preferable because good adhesion durability can be obtained. If the n / m ratio is less than 1.5, the corrosion resistance of the film formed by the reaction between the aqueous solution containing the silicic acid compound and the organosilane compound and the aluminum oxide film tends to slightly decrease, and the adhesion durability may decrease. There is. Moreover, although the upper limit of n / m ratio is not defined, 4 or less is preferable from the problem on the production of silicic acid compounds. Specific examples include layered crystal sodium silicate and water glass.
  • a layered silicate compound such as kanemite is particularly preferable from the viewpoint of stabilization of operation because it does not easily react with minerals in water due to its high ion exchange capacity, and the amount of adhering substances to an apparatus or a container decreases.
  • the type of the organic silane compound contained in the surface treatment liquid is not particularly limited, but the organic silane compound includes a silane compound having a plurality of hydrolyzable trialkoxyl groups in the molecule, a hydrolyzate thereof, or a polymer thereof. May be included. Silane compounds having multiple hydrolyzable trialkoxyl groups in the molecule not only form dense siloxane bonds by self-polymerization, but also form highly chemically reactive bonds with metal oxides. Further, the wet durability of the film can be further increased.
  • organosilane-treated films have high mutual solubility with machine oils such as processing oils and press oils and organic compounds such as adhesives, and even if machine oils such as process oils and press oils adhere to the film Therefore, it also plays a role in preventing a decrease in adhesion durability due to oil coating.
  • a silane compound (bissilane compound) having two hydrolyzable trialkoxysilyl groups in the molecule is preferable, and examples thereof include bistrialkoxysilylethane and bistrimethyl.
  • bistriethoxysilylethane (hereinafter referred to as BTSE) is preferable from the viewpoint of versatility and economy.
  • BTSE bistriethoxysilylethane
  • an organosilane compound only 1 type may be used independently and it may be used in combination of 2 or more type.
  • the organic silane compound may contain a silane coupling agent having a reactive functional group capable of chemically bonding with the organic resin component, a hydrolyzate thereof, or a polymer thereof.
  • a silane coupling agent having a reactive functional group such as amino group, epoxy group, methacryl group, vinyl group and mercapto group alone or in combination with the above silane compound, between the film and the resin A chemical bond can be formed to further enhance the adhesion durability.
  • the functional group of a silane coupling agent is not limited to what was mentioned above, The silane coupling agent which has various functional groups can be selected suitably according to the adhesive resin to be used.
  • silane coupling agents include, for example, 3-aminopropyltrimethoxysilane, 3-aminopropyltriethoxysilane, 3- (N-aminoethyl) -aminopropyltrimethoxysilane, 3- (N— Aminoethyl) -aminopropyltriethoxysilane, 3-mercaptopropyltrimethoxysilane, 3-mercaptopropyltriethoxysilane, 3-glycidoxypropyltrimethoxysilane, 3-glycidoxypropyltriethoxysilane, 3-methacryloxy Examples thereof include propyltrimethoxysilane and 3-methacryloxypropyltriethoxysilane.
  • silane coupling agent only 1 type may be used independently and it may be used in combination of 2 or more type.
  • the surface treatment liquid may further contain one or more of a stabilizer, an auxiliary agent and the like, if desired, in addition to the silicate compound and the organic silane compound.
  • the stabilizer may include organic compounds such as carboxylic acids having 1 to 4 carbon atoms such as formic acid and acetic acid, and alcohols having 1 to 4 carbon atoms such as methanol and ethanol.
  • a preparation method of a surface treatment liquid although the following adjustment methods are mentioned as an example, for example, it is not limited to this.
  • an organic silane compound and a small amount of acetic acid as a catalyst are added to a mixed liquid of alcohol such as ethanol and water to sufficiently hydrolyze the organic silane compound to obtain an organic silane compound aqueous solution.
  • a surface treatment solution is prepared by adding this organic silane compound aqueous solution to a silicic acid compound aqueous solution having a predetermined concentration.
  • the mixed aqueous solution of the organic silane compound and the silicic acid compound is stable in a basic pH range, but is easy to polymerize at a pH near neutral, so that it is basic from the viewpoint of solution stabilization. It is preferable to gradually add an acidic organic silane compound aqueous solution to the silicic acid compound aqueous solution so that the pH of the solution does not become near neutral.
  • the surface treatment liquid of this invention In order to improve the adhesive durability of various metal materials which have an oxide film, for example, metal materials, such as aluminum, copper, steel, and titanium It can be usefully used.
  • the surface treatment liquid of the present invention can be usefully used for improving the adhesion durability of an aluminum alloy.
  • the type of the aluminum alloy is not particularly limited, and is appropriately selected from various non-heat treatment type or heat treatment type aluminum alloys prescribed in JIS or similar to JIS, depending on the use of the processed member. Can be used.
  • the non-heat treatment type aluminum alloy there are pure aluminum (1000 series), Al—Mn series alloy (3000 series), Al—Si series alloy (4000 series), and Al—Mg series alloy (5000 series).
  • the heat-treatable aluminum alloy there are an Al—Cu—Mg alloy (2000 series), an Al—Mg—Si alloy (6000 series), and an Al—Zn—Mg alloy (7000 series).
  • the aluminum alloy material when used for an automobile member, the aluminum alloy material preferably has a 0.2% proof stress of 100 MPa or more from the viewpoint of strength.
  • aluminum alloys that can form aluminum alloy materials that satisfy these characteristics include those containing a relatively large amount of magnesium, such as 2000 series, 5000 series, 6000 series, and 7000 series. You may temper as needed.
  • it is preferable to use a 6000 series aluminum alloy because it has excellent age-hardening ability, has a relatively small amount of alloy elements, and is excellent in scrap recyclability and formability.
  • the aluminum alloy as a treatment target to which the surface treatment liquid of the present invention is applied particularly contains 0.1 atomic% or more and less than 30 atomic% of Mg in at least a part of the surface, and 0.6 atom of Cu. It is preferable that the aluminum alloy has an oxide film regulated to less than%.
  • An aluminum alloy usually contains magnesium as an alloy component, and when an oxide film that is a composite oxide of aluminum and magnesium is formed on the surface of the aluminum alloy, the magnesium oxide film is present in a concentrated state on the surface. It will be. Therefore, in this state, even if the surface treatment with the surface treatment liquid of the present invention is performed, the magnesium oxide film layer is too thick, so that the surface treatment film contains a large amount of magnesium. With the film, the strength of the film itself cannot be obtained, and the initial adhesiveness may be lowered.
  • the Mg content in the oxide film is 30 atomic% or more, the initial adhesiveness and adhesion durability of the aluminum alloy material after the surface treatment tend to decrease. Therefore, the Mg content in the oxide film of the aluminum alloy is preferably less than 30 atomic%. Thereby, initial adhesiveness and adhesion durability can be improved.
  • the Mg content in the oxide film of the aluminum alloy is more preferably less than 25 atomic%, more preferably less than 20 atomic%, and particularly preferably less than 10 atomic% from the viewpoint of improving the initial adhesiveness and adhesion durability.
  • the lower limit of the Mg content in the oxide film of the aluminum alloy is preferably 0.1 atomic% or more from the viewpoint of economy.
  • the Cu content in the oxide film of the aluminum alloy is preferably regulated to less than 0.6 atomic%, and more preferably regulated to less than 0.5 atomic%.
  • Mg content and Cu content in the oxide film of an aluminum alloy appropriately control various conditions (processing time, processing temperature, concentration of chemical solution, pH, etc.) in etching processing such as pickling and alkali cleaning. Can be adjusted or regulated.
  • the Mg content and the Cu content in the oxide film of the aluminum alloy can be measured by a high-frequency glow discharge optical emission spectrometry (GD-OES).
  • the metal surface treatment method using the aqueous solution for metal surface treatment of the present invention is such that the amount of the surface treatment film after drying the aqueous solution for metal surface treatment is 0.5 mg / m 2 or more and 35 mg / m 2 or less. , Including applying to a metal surface.
  • coating a surface treatment liquid to a metal you may apply
  • Examples of the method for applying the surface treatment liquid include immersion treatment, spraying, roll coating, bar coating, electrostatic coating, and the like.
  • Rinse may or may not be carried out after the surface treatment, but it is desirable not to rinse after coating because of the effect of improving the stability and denseness of the film.
  • cleaning liquid used for rinse water, alcohol, etc. are mentioned, for example.
  • the surface treatment liquid is dried by heating as necessary.
  • the heating temperature is preferably 70 ° C. or higher, more preferably 80 ° C. or higher, and still more preferably 90 ° C. or higher.
  • the heating temperature is preferably 200 ° C. or less, more preferably 190 ° C. or less, and further preferably 180 ° C. or less.
  • the drying time is preferably 2 seconds or more, more preferably 5 seconds or more, and further preferably 10 seconds or more, although it depends on the heating temperature. Moreover, the said drying time becomes like this. Preferably it is 20 minutes or less, More preferably, it is 5 minutes or less, More preferably, it is 2 minutes or less.
  • the coating amount of the surface treatment liquid is preferably adjusted so that the coating amount after drying is 1 mg / m 2 or more and 20 mg / m 2 or less from the viewpoint of obtaining a sufficient effect of improving the adhesion durability. More preferably, the coating amount after drying is adjusted to be 1.5 mg / m 2 or more and 12 mg / m 2 or less. If the coating amount of the surface treatment liquid is too small, a film may not be formed and good adhesion durability may not be obtained. Moreover, when the coating amount of the surface treatment liquid is too large, the surface treatment film to be formed becomes too thick, peeling may occur in the surface treatment film, and adhesion durability may be impaired. Further, for example, the surface treatment film may not be removed in a degreasing etching process for painting after an automobile assembly process, which may adversely affect paint adhesion.
  • etching treatment as a pretreatment on the metal to be treated from the viewpoint of ensuring the uniformity of the treatment.
  • the etching treatment at least one of treatment with an acidic solution (pickling) and treatment with an alkaline solution (alkali washing, alkaline degreasing) is performed on part or all of the metal surface.
  • the chemical solution (acid detergent) used in the pickling is not particularly limited, for example, a solution containing one or more selected from the group selected from sulfuric acid, nitric acid and hydrofluoric acid can be used.
  • the acid detergent may contain a surfactant in order to improve the degreasing property.
  • the pickling conditions can be appropriately set in consideration of the composition of the metal material, the thickness of the oxide film, and the like, and are not particularly limited.
  • the pH is 2 or less
  • the processing temperature is 10 to 80 ° C.
  • the processing time is Conditions of 1 to 120 seconds can be applied.
  • the chemical solution used for alkali cleaning is not particularly limited, and for example, a solution containing at least one selected from the group selected from sodium hydroxide and potassium hydroxide can be used.
  • the conditions for the treatment with the alkaline solution can be appropriately set in consideration of the composition of the metal material, the thickness of the oxide film, and the like, and are not particularly limited.
  • the pH is 10 or more
  • the treatment temperature is 10 to 80 ° C.
  • Conditions with a processing time of 1 to 120 seconds can be applied.
  • the rinsing method is not particularly limited, and examples thereof include spraying and dipping.
  • Examples of the cleaning liquid used for rinsing include industrial water, pure water, and ion exchange water.
  • the metal material surface-treated with the aqueous solution for metal surface treatment of the present invention (hereinafter also referred to as a surface-treated metal material) has an excellent adhesion durability even when exposed to a high-temperature and humid environment, and the adhesive strength is not easily lowered. It is.
  • the surface-treated metal material may be bonded to another member via an adhesive resin to form a bonded body.
  • the other members include other surface-treated metal materials, other metal materials that are not surface-treated, resin molded bodies, and the like.
  • the adhesive resin is not particularly limited, and adhesive resins that have been conventionally used for joining aluminum alloy materials, such as epoxy resins, urethane resins, nitrile resins, nylon resins, and acrylic resins, can be used. Can be used.
  • the thickness of the adhesive resin is not particularly limited, but is preferably 10 to 500 ⁇ m, more preferably 50 to 400 ⁇ m from the viewpoint of improving the adhesive strength.
  • the same metal material that is surface-treated can be used as the other metal material that is not surface-treated.
  • Examples of the resin molding include glass fiber reinforced plastic (GFRP), carbon fiber reinforced plastic (CFRP), boron fiber reinforced plastic (BFRP), aramid fiber reinforced plastic (AFRP, KFRP), and polyethylene fiber reinforced plastic (DFRP). ) And various fiber reinforced plastics such as Zylon reinforced plastic (ZFRP) can be used.
  • GFRP glass fiber reinforced plastic
  • CFRP carbon fiber reinforced plastic
  • BFRP boron fiber reinforced plastic
  • AFRP aramid fiber reinforced plastic
  • KFRP polyethylene fiber reinforced plastic
  • DFRP polyethylene fiber reinforced plastic
  • ZFRP Zylon reinforced plastic
  • the resin molded body includes polypropylene (PP), acrylic-butadiene-styrene copolymer (ABS) resin, polyurethane (PU), polyethylene (PE), polyvinyl chloride (PVC), Nylon 6, nylon 6, 6, polystyrene (PS), polyethylene terephthalate (PET), polyamide (PA), polyphenylene sulfide (PPS), polybutylene terephthalate (PBT), polyphthalamide (PPA), etc.
  • PP polypropylene
  • ABS acrylic-butadiene-styrene copolymer
  • PU polyurethane
  • PE polyethylene
  • PVC polyvinyl chloride
  • PS Nylon 6, nylon 6, 6, polystyrene
  • PET polyamide
  • PA polyphenylene sulfide
  • PBT polybutylene terephthalate
  • PPA polyphthalamide
  • Method of manufacturing joined body As the above-described method for manufacturing a joined body, particularly a joining method, a conventionally known joining method can be used.
  • the method for forming the adhesive resin on the aluminum alloy material is not particularly limited.
  • an adhesive sheet prepared in advance using an adhesive resin may be used, or the adhesive resin may be sprayed on the surface of the surface treatment film. Or you may form by apply
  • the manufactured aluminum alloy material may apply
  • press oil one containing an ester component is mainly used.
  • the method and conditions for applying press oil to the aluminum alloy material are not particularly limited, and methods and conditions for applying ordinary press oil can be widely applied.
  • press oil containing ethyl oleate as an ester component Then, an aluminum alloy material may be dipped.
  • the ester component is not limited to ethyl oleate, and various materials such as butyl stearate and sorbitan monostearate can be used.
  • the joined body may be coated with press oil on the surface thereof before being processed into a member for an automobile.
  • the effects of the present invention will be specifically described with reference to Examples and Comparative Examples of the present invention.
  • the metal surface was treated by the following methods and conditions, and adhesion durability and the like were evaluated.
  • Example 1 Using a 6000 series aluminum alloy of JIS 6016 (Mg: 0.54 mass%, Si: 1.11 mass%, Cu: 0.14 mass%), an aluminum alloy cold-rolled sheet having a thickness of 1 mm was produced. And this cold-rolled board was cut
  • JIS 6016 Mg: 0.54 mass%, Si: 1.11 mass%, Cu: 0.14 mass%
  • bistriethoxysilylethane (BTSE) as an organic silane compound was mixed with 2.0 g of ethanol, 0.001 g of acetic acid and 1 g of water and stirred. Next, the obtained solution was further diluted to 10 mL with water to prepare a BTSE aqueous solution having a concentration of 10% by mass.
  • BTSE bistriethoxysilylethane
  • BTSE aqueous solution is added to an aqueous solution containing 0.008 g of kanemite (trade name: Prefeed, manufactured by Tokuyama Siltec Co., Ltd., the molar ratio of SiO 2 and Na 2 O is about 2) as a silicic acid compound of layered crystals.
  • kanemite trade name: Prefeed, manufactured by Tokuyama Siltec Co., Ltd., the molar ratio of SiO 2 and Na 2 O is about 2
  • a silicic acid compound of layered crystals After adding 0.4 mL, the mixture was further diluted to 100 mL with water to prepare a mixed aqueous solution of silicate compound-BTSE (surface treatment solution).
  • concentration of the kanemite in the obtained surface treatment liquid was 0.008 mass%
  • concentration of BTSE was 0.04 mass%.
  • pH of the obtained surface treatment liquid was 10.5.
  • the surface treatment liquid was uniformly applied to the surface of the substrate with a bar coater, and was heated and dried at 100 ° C. for 1 minute to produce a surface treatment material.
  • the press oil was diluted with toluene to adjust the concentration, it was applied to the surface treatment material so that the coating amount after drying was 1 g / m 2 and dried.
  • Example 2 A surface treatment material of Example 2 was obtained in the same manner as in Example 1 except that a surface treatment liquid having a kanemite concentration of 0.4 mass% and a BTSE concentration of 0.003 mass% was used. The pH of the surface treatment solution was 12.5. Thereafter, press oil was diluted with toluene to adjust the concentration, and then applied to the surface treatment material such that the coating amount after drying was 1 g / m 2 and dried.
  • Example 3 A surface treatment material of Example 3 was obtained in the same manner as in Example 1 except that a surface treatment liquid having a kanemite concentration of 0.25% by mass and a BTSE concentration of 0.01% by mass was used. The pH of the surface treatment solution was 12.2. Thereafter, press oil was diluted with toluene to adjust the concentration, and then applied to the surface treatment material such that the coating amount after drying was 1 g / m 2 and dried.
  • Example 4 A surface-treated material of Example 4 was obtained in the same manner as in Example 1 except that the surface treatment liquid having a kanemite concentration of 0.012% by mass and a BTSE concentration of 0.35% by mass was used. The pH of the surface treatment solution was 11.2. Thereafter, press oil was diluted with toluene to adjust the concentration, and then applied to the surface treatment material such that the coating amount after drying was 1 g / m 2 and dried.
  • Example 5 The concentration of kanemite is 0.02% by mass, the organic silane compound contains 0.15% by mass of BTSE, and further 0.05% by mass of 3-glycidoxypropyltriethoxysilane (GPS).
  • a surface treatment material of Example 5 was obtained in the same manner as Example 1 except that the surface treatment liquid was used. The pH of the surface treatment solution was 11. Thereafter, press oil was diluted with toluene to adjust the concentration, and then applied to the surface treatment material such that the coating amount after drying was 1 g / m 2 and dried.
  • Example 6 A surface treatment material of Example 6 was obtained in the same manner as in Example 1 except that a surface treatment liquid having a kanemite concentration of 0.15% by mass and a BTSE concentration of 0.15% by mass was used. It was. The pH of the surface treatment liquid was 11.8. Thereafter, press oil was diluted with toluene to adjust the concentration, and then applied to the surface treatment material such that the coating amount after drying was 1 g / m 2 and dried.
  • Example 7 Example 1 except that the concentration of kanemite is 0.1% by mass, and the surface treatment solution containing 0.01% by mass of BTSE and 0.01% by mass of GPS is used as the organosilane compound.
  • the surface treatment material of Example 7 was obtained.
  • the pH of the surface treatment solution was 11.5.
  • press oil was diluted with toluene to adjust the concentration, and then applied to the surface treatment material such that the coating amount after drying was 1 g / m 2 and dried.
  • Example 8 Example 1 except that a surface treatment solution containing 0.018% by mass of kanemite, 0.008% by mass of BTSE, and 0.004% by mass of APS as an organosilane compound was prepared. In the same manner as described above, the surface treatment material of Example 8 was obtained. The pH of the surface treatment solution was 10.8. Thereafter, press oil was diluted with toluene to adjust the concentration, and then applied to the surface treatment material such that the coating amount after drying was 1 g / m 2 and dried.
  • Example 9 A surface-treated material of Example 9 was obtained in the same manner as in Example 1 except that the surface treatment liquid having a kanemite concentration of 0.05% by mass and a BTSE concentration of 0.25% by mass was used.
  • the pH of the surface treatment solution was 10.5.
  • press oil was diluted with toluene to adjust the concentration, and then applied to the surface treatment material such that the coating amount after drying was 1 g / m 2 and dried.
  • Example 10 The surface treatment material of Example 10 is the same as the method of Example 9, except that a surface treatment liquid containing 0.20% by mass of APS instead of 0.25% by mass of BTSE is used as the organosilane compound. Got. The pH of the surface treatment liquid was 11.4. Thereafter, press oil was diluted with toluene to adjust the concentration, and then applied to the surface treatment material such that the coating amount after drying was 1 g / m 2 and dried.
  • Example 11 Example 1 except that the concentration of kanemite was 0.05% by mass and a surface treatment liquid containing 0.08% by mass of bistriethoxysilylbenzene (BTSB) instead of BTSE was used as the organosilane compound. Similarly, the surface treatment material of Example 11 was obtained. The pH of the surface treatment solution was 11. Thereafter, press oil was diluted with toluene to adjust the concentration, and then applied to the surface treatment material such that the coating amount after drying was 1 g / m 2 and dried.
  • BTSB bistriethoxysilylbenzene
  • Example 12 The concentration of kanemite is 0.05% by mass, and the organosilane compound contains 0.14% by mass of bistriethoxysilylpropyltetrasulfide (BTSH) instead of BTSE, and the composition of the solvent is 90% ethanol water.
  • a surface treatment material of Example 12 was obtained in the same manner as in Example 1 except that a certain surface treatment liquid was used. The pH of the surface treatment solution was 11. Thereafter, press oil was diluted with toluene to adjust the concentration, and then applied to the surface treatment material such that the coating amount after drying was 1 g / m 2 and dried.
  • BTSH bistriethoxysilylpropyltetrasulfide
  • Example 13 A surface treatment material of Example 13 was obtained in the same manner as Example 9 except that sodium metasilicate (Molar ratio of SiO 2 and Na 2 O was about 1) was used instead of kanemite.
  • the pH of the surface treatment liquid was 10.7. Thereafter, press oil was diluted with toluene to adjust the concentration, and then applied to the surface treatment material such that the coating amount after drying was 1 g / m 2 and dried.
  • Example 14 A surface treatment material of Example 14 was obtained in the same manner as Example 9 except that water glass (SiO 2: Na 2 O molar ratio: 3 to 3.4) was used instead of kanemite.
  • the pH of the surface treatment solution was 10.2.
  • press oil was diluted with toluene to adjust the concentration, and then applied to the surface treatment material such that the coating amount after drying was 1 g / m 2 and dried.
  • Comparative Example 1 A surface treatment material of Comparative Example 1 was obtained in the same manner as in Example 1 except that a surface treatment liquid having a kanemite concentration of 0.61% by mass and a BTSE concentration of 0.1% by mass was used. The pH of the surface treatment solution was 12.5. Thereafter, press oil was diluted with toluene to adjust the concentration, and then applied to the surface treatment material such that the coating amount after drying was 1 g / m 2 and dried.
  • Example 2 Example 1 except that the concentration of kanemite was 0.061% by mass, and the surface treatment solution containing 0.2% by mass of BTSE and 0.8% by mass of APS was used as the organosilane compound. In the same manner as described above, the surface treatment material of Comparative Example 2 was obtained. The pH of the surface treatment solution was 12.1. Thereafter, press oil was diluted with toluene to adjust the concentration, and then applied to the surface treatment material such that the coating amount after drying was 1 g / m 2 and dried.
  • Comparative Example 3 A surface treatment material of Comparative Example 3 was obtained in the same manner as in Example 1 except that a surface treatment liquid having a kanemite concentration of 0.005 mass% and a BTSE concentration of 1 mass% was used. The pH of the surface treatment solution was 9.5. Thereafter, press oil was diluted with toluene to adjust the concentration, and then applied to the surface treatment material such that the coating amount after drying was 1 g / m 2 and dried.
  • Comparative Example 4 A surface treatment material of Comparative Example 4 was obtained in the same manner as in Example 1 except that the surface treatment liquid having a kanemite concentration of 0.0061 mass% and a BTSE concentration of 0.0009 mass% was used. The pH of the surface treatment solution was 10.3. Thereafter, press oil was diluted with toluene to adjust the concentration, and then applied to the surface treatment material such that the coating amount after drying was 1 g / m 2 and dried.
  • Comparative Example 5 A surface treatment material of Comparative Example 5 was obtained in the same manner as in Example 1 except that the surface treatment liquid having a kanemite concentration of 0.0009 mass% and a BTSE concentration of 0.01 mass% was used. The pH of the surface treatment solution was 8.1. Thereafter, press oil was diluted with toluene to adjust the concentration, and then applied to the surface treatment material such that the coating amount after drying was 1 g / m 2 and dried.
  • the amount of the film formed by the treatment liquid in the present invention was measured by fluorescent X-ray. Specifically, the amount of silicon after film treatment was measured with fluorescent X-rays, and the calculation was performed by converting the intensity of fluorescent X-rays and the amount of film using a calibration curve. The results are shown in Table 1.
  • FIGS. 1A and 1B are diagrams schematically showing a method for measuring the cohesive failure rate
  • FIG. 1A is a side view
  • FIG. 1B is a plan view.
  • the end portions of two test materials 31a and 31b (25 mm width) having the same configuration are wrapped with a thermosetting epoxy resin adhesive resin with a wrap length of 10 mm (adhesion area: 25 mm ⁇ 10 mm).
  • the adhesive resin 35 used here is a thermosetting epoxy resin-based adhesive resin (bisphenol A type epoxy resin amount 40 to 50 mass%).
  • the prepared adhesion test specimen was held in a high temperature and humidity environment of 50 ° C. and a relative humidity of 95% for 30 days, and then pulled at a rate of 50 mm / min with a tensile tester to evaluate the cohesive failure rate of the adhesive resin at the adhesion portion.
  • the cohesive failure rate was calculated based on Equation 1 below.
  • the test specimen a was used as one side after the tension of the adhesion test specimen, and the test specimen b was used as the other side.
  • the evaluation criteria are that the cohesive failure rate is less than 60% defective (x), 60% or more and less than 70% is slightly good ( ⁇ ), 70% or more and less than 90% is good ( ⁇ ), and 90% or more is excellent. ( ⁇ ).
  • the results are shown in Table 1.
  • Comparative Example 1 since the concentration of the silicate compound in the surface treatment liquid was higher than the range specified in the present invention, the adhesion durability was poor. Moreover, in Comparative Example 2 and Comparative Example 3, since the concentration of the organosilane compound in the surface treatment liquid was higher than the range specified in the present invention, the adhesion durability was poor. In Comparative Example 4, the adhesion durability was poor because the concentration of the organosilane compound in the surface treatment liquid was lower than the range specified in the present invention. Further, in Comparative Example 5, since the concentration of the silicate compound in the surface treatment solution was lower than the range specified in the present invention, the adhesion durability was poor.
  • Example 1 to 14 that satisfy each requirement defined in the present invention, the adhesion durability was good.
  • sodium metasilicate SiO 2 and Na 2 O kanemite used in Example 9 (molar ratio of SiO 2 and Na 2 O of about 2) (Tokuyama Siltech made pre feed)
  • the molar ratio of SiO 2 and Na 2 O was used sodium metasilicate less than 1.5 (about 1), although the cohesive failure rate was less than 90% to 70% pass level, SiO 2
  • the cohesive failure rate was slightly inferior to Example 9 using Kanemite in which the molar ratio of Na 2 O was about 2.
  • Example 14 instead of the kanemite used in Example 1 (the molar ratio of SiO 2 and Na 2 O is about 2) (pre-feed made by Tokuyama Siltec), water glass (SiO 2 and Na 2 O This is an example using a molar ratio of 3 to 3.4), and is an example prepared under substantially the same conditions as in Example 9 except that the sodium silicate species was changed.
  • Example 11 using a water glass having a molar ratio of SiO 2 to Na 2 O of 1.5 or more (about 3 to 3.4), kanemite having a molar ratio of SiO 2 to Na 2 O of about 2 was used. The cohesive failure rate equivalent to that of Example 9 was obtained.

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  • 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

La présente invention concerne une solution aqueuse de traitement de surface métallique contenant de 0,001 % en masse à moins de 0,5 % en masse d'un composé de silicate et de 0,001 % en masse à moins de 0,5 % en masse d'un composé de silane organique et ayant un pH de 7 à 14. Ladite solution permet de fabriquer grâce à un processus simplifié un matériau métallique à surface traitée qui n'est pas susceptible de présenter une diminution de la résistance d'adhérence même lorsqu'il est exposé à un environnement chaud et humide et qui présente une excellente durabilité d'adhérence. Par conséquent, les coûts d'investissement en capital et le coût de production peuvent être réduits.
PCT/JP2016/069105 2015-07-09 2016-06-28 Solution aqueuse de traitement de surface métallique, procédé de traitement de surface métallique et conjugué WO2017006805A1 (fr)

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US15/741,562 US20180216235A1 (en) 2015-07-09 2016-06-28 Aqueous solution for metal surface treatment, metal surface treatment method, and bonded article

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WO2021140751A1 (fr) * 2020-01-08 2021-07-15 株式会社デンソー Structure

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JP2006299356A (ja) * 2005-04-21 2006-11-02 Chubu Kiresuto Kk 防錆剤組成物および水性防錆潤滑剤、並びにこれを用いた加工法
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JP2017203186A (ja) * 2016-05-10 2017-11-16 株式会社神戸製鋼所 金属表面処理用水溶液、金属表面の処理方法、及び接合体
WO2017195803A1 (fr) * 2016-05-10 2017-11-16 株式会社神戸製鋼所 Solution aqueuse pour traitement de surface métallique, procédé de traitement de surface métallique, et corps relié
WO2021140751A1 (fr) * 2020-01-08 2021-07-15 株式会社デンソー Structure
JP2021109336A (ja) * 2020-01-08 2021-08-02 株式会社デンソー 構造体
CN114929473A (zh) * 2020-01-08 2022-08-19 株式会社电装 结构体
JP7434901B2 (ja) 2020-01-08 2024-02-21 株式会社デンソー 構造体

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