WO2020235070A1 - Resin-magnesium metal bonded body and method for manufacturing same - Google Patents

Resin-magnesium metal bonded body and method for manufacturing same Download PDF

Info

Publication number
WO2020235070A1
WO2020235070A1 PCT/JP2019/020368 JP2019020368W WO2020235070A1 WO 2020235070 A1 WO2020235070 A1 WO 2020235070A1 JP 2019020368 W JP2019020368 W JP 2019020368W WO 2020235070 A1 WO2020235070 A1 WO 2020235070A1
Authority
WO
WIPO (PCT)
Prior art keywords
magnesium metal
metal member
resin
less
washing
Prior art date
Application number
PCT/JP2019/020368
Other languages
French (fr)
Japanese (ja)
Inventor
孝 眞 金
修平 三浦
鉄也 藤村
星 衡 李
Original Assignee
ジオネーション株式会社
株式会社東亜電化
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by ジオネーション株式会社, 株式会社東亜電化 filed Critical ジオネーション株式会社
Priority to PCT/JP2019/020368 priority Critical patent/WO2020235070A1/en
Priority to CN201980096719.0A priority patent/CN114207192A/en
Priority to KR1020217042145A priority patent/KR102618505B1/en
Publication of WO2020235070A1 publication Critical patent/WO2020235070A1/en

Links

Images

Classifications

    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
    • B29C45/00—Injection moulding, i.e. forcing the required volume of moulding material through a nozzle into a closed mould; Apparatus therefor
    • B29C45/14—Injection moulding, i.e. forcing the required volume of moulding material through a nozzle into a closed mould; Apparatus therefor incorporating preformed parts or layers, e.g. injection moulding around inserts or for coating articles
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
    • B29C65/00—Joining or sealing of preformed parts, e.g. welding of plastics materials; Apparatus therefor
    • B29C65/70—Joining or sealing of preformed parts, e.g. welding of plastics materials; Apparatus therefor by moulding
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
    • B29C66/00—General aspects of processes or apparatus for joining preformed parts
    • B29C66/70—General aspects of processes or apparatus for joining preformed parts characterised by the composition, physical properties or the structure of the material of the parts to be joined; Joining with non-plastics material
    • B29C66/72—General aspects of processes or apparatus for joining preformed parts characterised by the composition, physical properties or the structure of the material of the parts to be joined; Joining with non-plastics material characterised by the structure of the material of the parts to be joined
    • B29C66/723—General aspects of processes or apparatus for joining preformed parts characterised by the composition, physical properties or the structure of the material of the parts to be joined; Joining with non-plastics material characterised by the structure of the material of the parts to be joined being multi-layered
    • B29C66/7232—General aspects of processes or apparatus for joining preformed parts characterised by the composition, physical properties or the structure of the material of the parts to be joined; Joining with non-plastics material characterised by the structure of the material of the parts to be joined being multi-layered comprising a non-plastics layer
    • B29C66/72321—General aspects of processes or apparatus for joining preformed parts characterised by the composition, physical properties or the structure of the material of the parts to be joined; Joining with non-plastics material characterised by the structure of the material of the parts to be joined being multi-layered comprising a non-plastics layer consisting of metals or their alloys
    • C—CHEMISTRY; METALLURGY
    • C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
    • C25D11/00—Electrolytic coating by surface reaction, i.e. forming conversion layers
    • C25D11/02—Anodisation
    • C25D11/30—Anodisation of magnesium or alloys based thereon

Definitions

  • the present invention relates to a resin-magnesium metal joint and a method for producing the same, and more particularly to a resin-magnesium metal joint capable of strongly bonding a resin member and a magnesium metal member and a method for producing the same.
  • Patent Document 1 discloses an electrochemical surface treatment method for forming a film of triazinethiol (sulfur organic compound) on the surface of a metal member as a technique for joining a resin member and a metal member.
  • the metal include copper, nickel, aluminum, iron, cobalt, tin and stainless steel.
  • An object of the present invention is to provide a resin-magnesium metal joint body capable of improving the joint strength between a resin member and a magnesium metal member, and to provide a method for producing a resin magnesium metal joint body having good joint strength.
  • the resin magnesium metal joint according to the present invention is a resin magnesium metal joint formed by joining a magnesium metal member and a thermoplastic resin member, and the magnesium metal member and the resin member have a thickness of 50. It is characterized in that it is bonded by an anodic oxide film having a diameter of about 3000 nm.
  • the other resin magnesium metal joint according to the present invention is a resin magnesium metal joint formed by joining a magnesium metal member and a thermoplastic resin member, and the magnesium metal member and the thermoplastic resin member have a thickness. Is bonded by an anodic oxide film in which 50 to 3000 nm triazine thiol is present inside and outside.
  • the anodized film is 1 to 60% by weight of O, 1 to 90% of Mg, 3% or less of S, 20% or less of Al, 3% or less of P, 3% or less of Zn, and Cu. It is characterized by having a component composition of 3% or less, Mn of 3% or less, Ni of 3% or less, Si of 20% or less, and F of 3% or less.
  • the method for producing a resin magnesium metal joint according to the present invention is a production method for producing a resin magnesium metal joint, in which a degreasing step of washing a magnesium metal member with an alkaline solution and a degreasing step of cleaning the magnesium metal member are performed.
  • a thermoplastic resin is inserted into the magnesium metal member on which the anodized film is formed after the washing step of washing the magnesium metal member having the film formed with water at 5 ° C. or higher and lower than 60 ° C. and the washing step. It is characterized in that a step of molding is provided, and the magnesium metal member and a resin member molded of a thermoplastic resin are joined.
  • Another method for producing a resin magnesium metal joint according to the present invention is a method for producing a resin magnesium metal joint, which is a degreasing step of washing a magnesium metal member with an alkaline solution, and a magnesium metal after the degreasing step.
  • An anodic oxide film having a thickness of 50 to 3000 nm is formed on the magnesium metal member by applying a current density of 0.5 A / dm2 or more and less than 5 A / dm2 in a solution containing a triazinethiol derivative at ⁇ 90 ° C.
  • a step of insert-molding a thermoplastic resin is provided, and the magnesium metal member and a resin member molded of the thermoplastic resin are joined.
  • the resin member and the magnesium metal member can be bonded well, and the bonding strength is 30 MPa or more. Can be done.
  • the airtightness between the resin member and the magnesium metal member can be reduced to 10-9 Pam 3 / s or less by a leak test using a helium leak. Waterproofness can also be ensured.
  • an anodic oxide film having triazine thiol having a thickness of 50 to 3000 nm present inside and outside was formed on the surface of the magnesium metal member in advance, so that the resin member and the magnesium metal The members can be joined well.
  • the bonding strength is 30 MPa or more, and the airtightness between the resin member and the magnesium metal member can be 10-9 Pam 3 / s or less in a leak test using a helium leak.
  • the anodized film is 1 to 60% O, 1 to 90% Mg, 3% or less S, 20% or less Al, 3% or less P, 3% or less Zn, and Cu in% by weight. Since it contains a component composition of 3% or less, Mn of 3% or less, Ni of 3% or less, Si of 20% or less, and F of 3% or less, the resin member and the magnesium metal member can be satisfactorily bonded.
  • a degreasing step of dipping to remove oil on the surface of a magnesium metal member (b) an acid treatment step of washing with an acidic solution, and (c). ) An activation step of immersing in an alkaline solution and applying a constant voltage, (d) an oxide film forming step of forming an anodic oxide film in an alkaline solution using a magnesium metal member as an anode, and (e) anodization.
  • a washing step of washing the magnesium metal member with water and (f) an insert step of insert-molding the thermoplastic resin and joining the magnesium metal member to the magnesium metal member were provided, so that the resin member and the magnesium metal member are good.
  • the bonding strength can be 30 MPa or more, and the airtightness can be 10-9 Pam 3 / s or less in a leak test using helium leak.
  • a degreasing step of dipping to remove the oil on the surface of the magnesium metal member there are (a) a degreasing step of dipping to remove the oil on the surface of the magnesium metal member, and (b) an acid treatment step of washing with an acidic solution.
  • TRI electrolysis step (Referred to as TRI electrolysis step), (e) a water washing step of washing the magnesium metal member with water after forming an anodized film, and (f) an insert step of insert molding a thermoplastic resin and joining it to the magnesium metal member. Since the above is provided, the bonding strength between the resin member and the magnesium metal member can be 30 MPa or more, and the airtightness can be 10-9 Pam 3 / s or less in the leak test using a helium leak.
  • (A) is a front view
  • (B) is a right side view
  • (C) is a perspective view.
  • FIG. 1 is a flowchart showing a method for producing a resin-magnesium metal joint according to the present invention.
  • the degreasing step (s1) is performed by immersing the magnesium metal member 1 in an aqueous solution prepared by adding a cationic surfactant to NAOH, KOH, or NA 2 CO 3 of the alkaline series for 1 to 10 minutes.
  • the temperature of the solution is in the range of room temperature to 70 ° C. As a result, the oil content on the surface of the magnesium metal member 1 is removed.
  • the acid treatment step (s2) involves adding a magnesium metal member 1 to an acidic aqueous solution of 5 to 50% phosphoric acid, 1 to 20% sulfuric acid or nitric acid, 1 to 5% oxalic acid, and 1 to 5% fluoride in weight%. Is performed by immersing for 1 to 10 minutes. The temperature of the solution is in the range of room temperature to 50 ° C. As a result, the surface of the magnesium metal member 1 is cleaned to remove the oxide film and the like.
  • a small amount of a cationic surfactant is added to an aqueous solution of caustic soda (NaOH) 1 to 30% and sodium carbonate (Na 2 CO 3 ) 1 to 20% by weight, and the solution is added.
  • the magnesium metal member 1 is immersed for 1 to 10 minutes, and a constant voltage of 0.2 to 5 V is applied to the anode or cathode.
  • the temperature of the aqueous solution is room temperature to 50 ° C.
  • a pulse or DC voltage is applied to the electrodes.
  • ultrasonic treatment at 50 Hz and 100 to 2000 watts is also performed for 1 to 10 minutes.
  • the oxide film forming step (s4) is referred to as a TRI electrolysis step.
  • the magnesium metal member 1 is connected as an anode.
  • the temperature of the solution is normal temperature to 90 ° C.
  • a voltage of 4 to 40 V may be applied between the anode and the cathode.
  • Magnesium metal member by electrolysis for 1 to 40 minutes.
  • An anodic oxide film 4 of triazinethiol having a thickness of 50 to 3000 nm is formed on the surface of the anodized film 4.
  • the anodic oxide film 4 is 10 to 60% by weight, O is 10 to 90%, Mg is 10 to 90%, and S is 3%.
  • Al is 20% or less
  • P is 3% or less
  • Zn is 3% or less
  • Cu is 3% or less
  • Mn is 3% or less
  • Ni is 3% or less
  • Si 3% or less
  • F is 3% or less. It has a component composition.
  • the water washing step (s5) is a step of washing the magnesium metal member 1 having an anodized film formed on its surface with water having a water temperature of 5 ° C. to 60 ° C.
  • the insert molding step (s6) after the washing step (s5), the magnesium metal member 1 on which the anodic oxide film is formed is loaded into the mold, the thermoplastic resin to be the resin member 2 is injected, and the resin member 2 and magnesium are injected. The metal member 1 is joined to form a resin magnesium metal joint 3.
  • FIG. 1 is a flowchart showing a method for producing a resin-magnesium metal joint according to the present invention.
  • the degreasing step (s1) is performed by immersing the magnesium metal member 1 in an aqueous solution prepared by adding a cationic surfactant to NAOH, KOH, or NA 2 CO 3 of the alkaline series for 1 to 10 minutes.
  • the temperature of the solution is in the range of room temperature to 70 ° C. As a result, the oil content on the surface of the magnesium metal member 1 is removed.
  • the acid treatment step (s2) involves adding a magnesium metal member 1 to an acidic aqueous solution of 5 to 50% phosphoric acid, 1 to 20% sulfuric acid or nitric acid, 1 to 5% oxalic acid, and 1 to 5% fluoride in weight%. Is performed by immersing for 1 to 10 minutes. The temperature of the solution is in the range of room temperature to 50 ° C. As a result, the surface of the magnesium metal member 1 is cleaned to remove the oxide film and the like.
  • a small amount of a cationic surfactant is added to an aqueous solution of caustic soda (NaOH) 1 to 30% and sodium carbonate (Na 2 CO 3 ) 1 to 20% by weight, and the solution is added.
  • the magnesium metal member 1 is immersed for 1 to 10 minutes, and a constant voltage of 0.2 to 5 V is applied to the anode or cathode.
  • the temperature of the aqueous solution is room temperature to 50 ° C.
  • a pulse or DC voltage is applied to the electrodes.
  • ultrasonic treatment at 50 Hz and 100 to 2000 watts is also performed for 1 to 10 minutes.
  • the oxide film forming step (s4) is referred to as a TRI electrolysis step.
  • the magnesium metal member 1 is connected as an anode.
  • the triazine-thiol (triazine thiols) derivatives traces added magnesium metal member 1 into the solution Immersion is performed by applying a constant current density of 1 to 20 A / dm 2 between the anode and the cathode.
  • the temperature of the solution is normal temperature to 90 ° C.
  • a voltage of 4 to 40 V is applied between the anode and the cathode.
  • an anodic oxide film 4 of triazinethiol having a thickness of 50 to 3000 nm is formed on the surface of the magnesium metal member.
  • the anodic oxide film 4 is by weight% and O is 10-60%, Mg 10-90%, S 3% or less, Al 20% or less, P 3% or less, Zn 3% or less, Cu 3% or less, Mn 3% or less, Ni It has a component composition of 3% or less, Si of 3% or less, and F of 3% or less.
  • the washing step (s5) is a step of washing the magnesium metal member 1 having a triazine thiol anodized film formed on its surface with water having a water temperature of 5 ° C. to 60 ° C.
  • the insert molding step (s6) after the washing step (s5), the magnesium metal member 1 on which the anodic oxide film is formed is loaded into the mold, the thermoplastic resin to be the resin member 2 is injected, and the resin member 2 and magnesium are injected. The metal member 1 is joined to form a resin magnesium metal joint 3.
  • triazine thiol is not added to the solution of the TRI electrolysis step.
  • triazine thiol is added to the solution of the TRI electrolysis step.
  • FIG. 2 is a diagram showing the shape of the magnesium metal member 1.
  • A is a front view
  • B is a right side view
  • C is a perspective view.
  • a is a hole having a diameter of 4 mm.
  • f is a plate thickness of 3 mm.
  • the length x width is a plate of 40 mm x 12 mm, and b is 12 mm and e is 40 mm.
  • c is 6 mm and d is 5 mm.
  • FIG. 3 is a table showing the types and components of the magnesium alloy used as the magnesium metal member 1.
  • AZ91 is a magnesium alloy having a high content of aluminum (Al) and improved corrosion resistance.
  • AZ31 is a magnesium alloy with improved extensibility by reducing aluminum (Al) to 3.5%.
  • FIG. 4 is a photograph of a hanging jig 7 to which a plurality of magnesium metal members 1 can be attached.
  • the hanging jig 7 has hooks at two upper positions and can be hung.
  • Ten magnesium metal members 1 can be attached.
  • FIG. 5 is a photograph of the hanging jig 7 suspended in the degreasing tank.
  • the degreasing tank is filled with an aqueous solution of NAOH, KOH, or NA 2 CO 3 plus a cationic surfactant.
  • FIG. 6 is a photograph of the hanging jig 7 suspended in an acid treatment tank.
  • the acid treatment tank is filled with an acidic aqueous solution of 5 to 50% phosphoric acid, 1 to 20% sulfuric acid or nitric acid, 1 to 5% oxalic acid, and 1 to 5% fluoride.
  • FIG. 7 is a photograph of the TRI electrolysis treatment tank. A plurality of electrodes are prepared in the tank.
  • FIG. 8 is a photograph showing the surface roughness of the magnesium metal member 1.
  • (A) is the untreated surface
  • (B) is the surface after degreasing
  • (C) is the surface after acid treatment
  • (D) is the surface after activation
  • (E) is the surface after TRI electrolysis treatment. is there.
  • the surface roughness is shown by the central average roughness Ra along three straight lines (three lines running from left to right), in units of ⁇ m.
  • Ra of the three straight lines was (0.5, 0.6, 0.6).
  • (B) Ra of the three straight lines was (0.7, 0.8, 1.0).
  • In (C) Ra of the three straight lines was (1.6, 0.7.0.8).
  • (D) Ra of the three straight lines was (0.6, 0.6, 0.6).
  • the black fine powder adhering to the surface is removed by the acid treatment.
  • Ra of the three straight lines was (0.3, 0.4, 0.4).
  • FIG. 9 is a photograph showing a cross section of the anodized film. Film thicknesses of 300 nm and 1.5 ⁇ m are formed on the surface of the anodized film 4. The thickness of the coating can be 50 nm to 3000 nm (3.0 ⁇ m).
  • FIG. 10 is a photograph of the test piece (left side) and a photograph of a test piece for a tensile test manufactured by the manufacturing method shown in FIG. 1 (right side).
  • Specimens are indicated by reference numeral 3 (3a). That is, the test body is a test body 3a for a tensile test.
  • the resin-magnesium metal joint 3 is formed by integrally molding a resin member 2 with a magnesium metal member 1 by insert molding.
  • the magnesium metal member 1 is loaded in the mold, and the thermoplastic resin is press-fitted to integrally mold the magnesium metal member 1 and the resin member 2.
  • the thermoplastic resin polybutylene terephthalate (PBT) and polyphenylene sulfide (PPS) can be used.
  • FIG. 11 is a diagram showing the tensile strength of the test piece.
  • (A) is a bar graph, and (B) is a list. It was measured with 8 test pieces of Nos. 1 to 8. Nos. 1 to 4 are manufactured in Example 1, and Nos. 5 to 8 are manufactured in Example 1.
  • the tensile strength of the resin member 2 and the magnesium metal member 1 can be set to 30 MPa or more from each numerical value of the test piece.
  • FIG. 12 is a photograph showing a test body for an airtightness test. Specimens are indicated by reference numeral 3 (3b). That is, the test body is the test body 3b for the airtightness test of the resin magnesium metal joint 3. In the test body 3b for the airtightness test, the magnesium metal member 1 penetrates the disk-shaped resin member 2 and is integrally joined. A test piece 3b for an airtightness test is loaded in a tubular container, helium gas is sprayed on one side on which the magnesium metal member 1 protrudes, and the other side on which the magnesium metal member 1 protrudes is evacuated to release helium gas. Check for leaks. Test bodies 1-1 to 1-4 were produced in Example 1, and test bodies 2-1 to 2-4 were produced in Example 2.
  • FIG. 13 is a table showing the results of the airtightness test. If the amount of vacuum exhaust is increased or decreased, the amount of leaked helium (He) also increases or decreases, but from the numerical values in the table of FIG. 13, the test bodies 1-1 to 1-4 of Example 1 and the test of Example 2 Any of the bodies 2-1 to 2-4 can be 1 ⁇ 10 -9 Pam 3 / s or less.
  • FIG. 14 is a diagram showing the tensile strength of the test piece manufactured in Example 1 before and after the thermal shock test.
  • the temperature was changed between -40 ° C and 80 ° C every 30 minutes, and 150 cycles were repeated.
  • the column of MPa is the value when the joint cross section is 36 mm 2
  • the column of N is the value obtained by multiplying the value of MPa by 36.
  • the tensile strength avg was 41.84 MPa before the thermal shock test, but increased to 50.12 MPa after the thermal shock test.
  • FIG. 15 is a diagram showing the tensile strength of the test piece manufactured in Example 2 before and after the thermal shock test.
  • the temperature was changed between -40 ° C and 80 ° C every 30 minutes, and 150 cycles were repeated.
  • the column of MPa is the value when the joint cross section is 36 mm 2
  • the column of N is the value obtained by multiplying the value of MPa by 36.
  • the tensile strength avg was 45.60 MPa before the thermal shock test, but increased to 51.32 MPa after the thermal shock test.
  • FIG. 16 is a diagram showing the tensile strength of the test piece produced in Example 1 before and after the high temperature and high humidity test.
  • the high temperature and high humidity test was carried out at a temperature of 80 ° C., a humidity of 95%, and a test time of 200 hours.
  • the tensile strength after this test was lower than the tensile strength of the test piece not subjected to the load test.
  • the tensile strength avg was 42.82 MPa before the test, but decreased to 30.39 MPa after the test.
  • FIG. 17 is a diagram showing the tensile strength of the test piece produced in Example 2 before and after the high temperature and high humidity test.
  • the high temperature and high humidity test was carried out at a temperature of 80 ° C., a humidity of 95%, and a test time of 200 hours.
  • the tensile strength after this test was lower than the tensile strength of the test piece not subjected to the load test.
  • the tensile strength avg was 42.82 MPa before the test, but decreased to 30.39 MPa after the test.
  • FIG. 18 is a surface photograph and a component analysis table of the Mg material (AZ91) after the TRI electrolysis treatment.
  • the surface has an uneven shape.
  • magnesium oxide (MgO) is formed because Mg is 32.33% and O is 39.59% in weight%.
  • FIG. 19 is a surface photograph and a component analysis table of the Mg material (AZ31) after the TRI electrolysis treatment.
  • the surface has an uneven shape, and a large number of holes are formed.
  • magnesium oxide (MgO) is formed because Mg is 64.32% and O is 31.98% by weight.
  • the resin-magnesium metal joint of the present invention and the method for manufacturing the same are for integrally joining the metal member and the resin member, and are suitable for reducing the weight of the parts.

Landscapes

  • Engineering & Computer Science (AREA)
  • Mechanical Engineering (AREA)
  • Chemical & Material Sciences (AREA)
  • Manufacturing & Machinery (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Electrochemistry (AREA)
  • Materials Engineering (AREA)
  • Metallurgy (AREA)
  • Organic Chemistry (AREA)
  • Laminated Bodies (AREA)
  • Injection Moulding Of Plastics Or The Like (AREA)

Abstract

Provided are: a resin-magnesium metal bonded body having bonding strength; and a method for manufacturing the resin-magnesium metal bonded body. A method for manufacturing a resin-magnesium metal bonded body comprises: a defatting step of washing a magnesium metal member with an alkaline solution; an acid treatment step of washing the magnesium metal member with an acidic solution; an activation treatment step of immersing the magnesium metal member in an alkaline solution and applying a constant voltage to an electrode; a step of applying a predetermined current density in an alkaline solution using the magnesium metal member as a positive electrode to form a positive electrode oxide coating film on the magnesium metal member; a water washing step of washing the magnesium metal member having the positive electrode oxide coating film formed thereon with water; and a step of forming a thermoplastic resin by insert molding on the magnesium metal member having the positive electrode oxide coating film formed thereon.

Description

樹脂マグネシウム金属接合体及びその製造法Resin magnesium metal joint and its manufacturing method
　本発明は、樹脂マグネシウム金属接合体及びその製造方法に係り、より詳しくは、樹脂部材とマグネシウム金属部材を強力に接合できる樹脂マグネシウム金属接合体及びその製造法に関する。 The present invention relates to a resin-magnesium metal joint and a method for producing the same, and more particularly to a resin-magnesium metal joint capable of strongly bonding a resin member and a magnesium metal member and a method for producing the same.
　一般に自動車部品の軽量化は、例えば金属部材で形成されていた部材を金属部材と樹脂部材の接合体とすることで行われる。特許文献１には、樹脂部材と金属部材を接合する技術として、トリアジンチオール（硫黄有機化合物）の被膜を金属部材表面上に形成する電気・化学的な表面処理法が開示されている。金属としては、銅、ニッケル、アルミニウム、鉄、コバルト、錫、ステンレスがあげられている。 Generally, the weight reduction of automobile parts is performed, for example, by making a member formed of a metal member a joint body of a metal member and a resin member. Patent Document 1 discloses an electrochemical surface treatment method for forming a film of triazinethiol (sulfur organic compound) on the surface of a metal member as a technique for joining a resin member and a metal member. Examples of the metal include copper, nickel, aluminum, iron, cobalt, tin and stainless steel.
　しかしながら、マグネシウム金属部材にトリアジンチオールの被膜を形成し、マグネシウム金属部材に樹脂部材を接合して、十分な接合強度を得ることについては具体的な開示がない。 However, there is no specific disclosure about forming a triazine thiol film on the magnesium metal member and joining the resin member to the magnesium metal member to obtain sufficient bonding strength.
特公平５－５１６７１号公報Special Fair No. 5-51671
　本発明の目的は、樹脂部材とマグネシウム金属部材の接合強度が向上できる樹脂マグネシウム金属接合体を提供すること及び接合強度が良好な樹脂マグネシウム金属接合体の製造方法を提供することにある。 An object of the present invention is to provide a resin-magnesium metal joint body capable of improving the joint strength between a resin member and a magnesium metal member, and to provide a method for producing a resin magnesium metal joint body having good joint strength.
　本発明による樹脂マグネシウム金属接合体は、マグネシウム金属部材と、熱可塑性の樹脂部材とを接合してなる樹脂マグネシウム金属接合体であって、前記マグネシウム金属部材と前記樹脂部材とが、膜厚が５０～３０００ｎｍの陽極酸化被膜により接合されていることを特徴とする。 The resin magnesium metal joint according to the present invention is a resin magnesium metal joint formed by joining a magnesium metal member and a thermoplastic resin member, and the magnesium metal member and the resin member have a thickness of 50. It is characterized in that it is bonded by an anodic oxide film having a diameter of about 3000 nm.
　本発明による他の樹脂マグネシウム金属接合体は、マグネシウム金属部材と熱可塑性樹脂部材とを接合してなる樹脂マグネシウム金属接合体であって、前記マグネシウム金属部材と前記熱可塑性樹脂部材とが、膜厚が５０～３０００ｎｍのトリアジンチオールを内部及び外部に存在させた陽極酸化被膜により接合されていることを特徴とする。 The other resin magnesium metal joint according to the present invention is a resin magnesium metal joint formed by joining a magnesium metal member and a thermoplastic resin member, and the magnesium metal member and the thermoplastic resin member have a thickness. Is bonded by an anodic oxide film in which 50 to 3000 nm triazine thiol is present inside and outside.
　前記陽極酸化被膜は、重量％で、Ｏが１～６０％、Ｍｇが１～９０％、Ｓが３％以下、Ａｌが２０％以下、Ｐが３％以下、Ｚｎが３％以下、Ｃｕが３％以下、Ｍｎが３％以下、Ｎｉが３％以下、Ｓｉが２０％以下、Ｆが３％以下の成分構成を有することを特徴とする。 The anodized film is 1 to 60% by weight of O, 1 to 90% of Mg, 3% or less of S, 20% or less of Al, 3% or less of P, 3% or less of Zn, and Cu. It is characterized by having a component composition of 3% or less, Mn of 3% or less, Ni of 3% or less, Si of 20% or less, and F of 3% or less.
　本発明による樹脂マグネシウム金属接合体の製造法は、樹脂マグネシウム金属接合体を製造する製造法であって、マグネシウム金属部材をアルカリ性の溶液で洗浄する脱脂工程と、前記脱脂工程後、マグネシウム金属部材を酸性の溶液で洗浄する酸処理工程と、前記酸処理工程後、マグネシウム金属部材をアルカリ性の溶液に浸漬して電極に定電圧をかける活性化処理工程と、前記マグネシウム金属部材を陽極とし、２０～９０℃の溶液中で、０．５Ａ／ｄｍ２以上５Ａ／ｄｍ２未満の電流密度を印加して、前記マグネシウム金属部材上に膜厚が５０～３０００ｎｍの陽極酸化被膜を形成する工程と、前記陽極酸化被膜が形成されたマグネシウム金属部材を、５℃以上、６０℃未満の水で洗浄する水洗い工程と、前記水洗い工程後の、前記陽極酸化被膜が形成されたマグネシウム金属部材に、熱可塑性樹脂をインサート成形する工程と、が備えられ、前記マグネシウム金属部材と、熱可塑性樹脂で成形された樹脂部材とが接合されることを特徴とする。 The method for producing a resin magnesium metal joint according to the present invention is a production method for producing a resin magnesium metal joint, in which a degreasing step of washing a magnesium metal member with an alkaline solution and a degreasing step of cleaning the magnesium metal member are performed. An acid treatment step of washing with an acidic solution, an activation treatment step of immersing the magnesium metal member in an alkaline solution to apply a constant voltage to the electrode after the acid treatment step, and using the magnesium metal member as an anode, 20 to 20 to A step of forming an anodic oxide film having a film thickness of 50 to 3000 nm on the magnesium metal member by applying a current density of 0.5 A / dm2 or more and less than 5 A / dm2 in a solution at 90 ° C. A thermoplastic resin is inserted into the magnesium metal member on which the anodized film is formed after the washing step of washing the magnesium metal member having the film formed with water at 5 ° C. or higher and lower than 60 ° C. and the washing step. It is characterized in that a step of molding is provided, and the magnesium metal member and a resin member molded of a thermoplastic resin are joined.
　本発明による他の樹脂マグネシウム金属接合体の製造法は、樹脂マグネシウム金属接合体を製造する製造法であって、マグネシウム金属部材をアルカリ性の溶液で洗浄する脱脂工程と、前記脱脂工程後、マグネシウム金属部材を酸性の溶液で洗浄する酸処理工程と、前記酸処理工程後、マグネシウム金属部材をアルカリ性の溶液に浸漬し電極に定電圧をかける活性化処理工程と、前記マグネシウム金属部材を陽極とし、２０～９０℃のトリアジンチオール誘導体を含む溶液中で、０．５Ａ／ｄｍ２以上５Ａ／ｄｍ２未満の電流密度を印加して、前記マグネシウム金属部材上に膜厚が５０～３０００ｎｍの陽極酸化被膜を形成する工程と、前記陽極酸化被膜が形成されたマグネシウム金属部材を、５℃以上、６０℃未満の水で洗浄する水洗い工程と、前記水洗い工程後の、前記陽極酸化被膜が形成されたマグネシウム金属部材に、熱可塑性樹脂をインサート成形する工程と、が備えられ、前記マグネシウム金属部材と、熱可塑性樹脂で成形された樹脂部材とが接合されることを特徴とする。 Another method for producing a resin magnesium metal joint according to the present invention is a method for producing a resin magnesium metal joint, which is a degreasing step of washing a magnesium metal member with an alkaline solution, and a magnesium metal after the degreasing step. An acid treatment step of washing the members with an acidic solution, an activation treatment step of immersing the magnesium metal member in an alkaline solution and applying a constant voltage to the electrodes after the acid treatment step, and using the magnesium metal member as an anode, 20 An anodic oxide film having a thickness of 50 to 3000 nm is formed on the magnesium metal member by applying a current density of 0.5 A / dm2 or more and less than 5 A / dm2 in a solution containing a triazinethiol derivative at ~ 90 ° C. The step, the washing step of washing the magnesium metal member on which the anodized film is formed with water at 5 ° C. or higher and lower than 60 ° C., and the magnesium metal member on which the anodized film is formed after the washing step. A step of insert-molding a thermoplastic resin is provided, and the magnesium metal member and a resin member molded of the thermoplastic resin are joined.
　本発明による樹脂マグネシウム金属接合体は、あらかじめマグネシウム金属部材の表面に、膜厚が５０～３０００ｎｍの陽極酸化被膜を形成したので、樹脂部材とマグネシウム金属部材が良好に接合でき、接合強度を３０ＭＰａ以上にできる。また、樹脂部材とマグネシウム金属部材の間の気密性は、ヘリウムリークを使用したリークテストで、１０－９Ｐａｍ３／ｓ以下にできる。防水性も確保できる。 In the resin-magnesium metal bonded body according to the present invention, since an anodic oxide film having a film thickness of 50 to 3000 nm is formed in advance on the surface of the magnesium metal member, the resin member and the magnesium metal member can be bonded well, and the bonding strength is 30 MPa or more. Can be done. The airtightness between the resin member and the magnesium metal member can be reduced to 10-9 Pam 3 / s or less by a leak test using a helium leak. Waterproofness can also be ensured.
　本発明による他の樹脂マグネシウム金属接合体は、あらかじめマグネシウム金属部材の表面に、膜厚が５０～３０００ｎｍのトリアジンチオールを内部及び外部に存在させた陽極酸化被膜を形成したので、樹脂部材とマグネシウム金属部材が良好に接合できる。その接合強度は３０ＭＰａ以上で、樹脂部材とマグネシウム金属部材の間の気密性は、ヘリウムリークを使用したリークテストで、１０－９Ｐａｍ３／ｓ以下にできる。 In the other resin-magnesium metal joint according to the present invention, an anodic oxide film having triazine thiol having a thickness of 50 to 3000 nm present inside and outside was formed on the surface of the magnesium metal member in advance, so that the resin member and the magnesium metal The members can be joined well. The bonding strength is 30 MPa or more, and the airtightness between the resin member and the magnesium metal member can be 10-9 Pam 3 / s or less in a leak test using a helium leak.
　前記陽極酸化被膜は、重量％で、Ｏが１～６０％、Ｍｇが１～９０％、Ｓが３％以下、Ａｌが２０％以下、Ｐが３％以下、Ｚｎが３％以下、Ｃｕが３％以下、Ｍｎが３％以下、Ｎｉが３％以下、Ｓｉが２０％以下、Ｆが３％以下の成分構成を含むので、樹脂部材とマグネシウム金属部材を良好に接合できる。 The anodized film is 1 to 60% O, 1 to 90% Mg, 3% or less S, 20% or less Al, 3% or less P, 3% or less Zn, and Cu in% by weight. Since it contains a component composition of 3% or less, Mn of 3% or less, Ni of 3% or less, Si of 20% or less, and F of 3% or less, the resin member and the magnesium metal member can be satisfactorily bonded.
　本発明による樹脂マグネシウム金属接合体の製造法によれば、（ａ）浸漬してマグネシウム金属部材表面の脂分を除く脱脂工程と、（ｂ）酸性の溶液で洗浄する酸処理工程と、（ｃ）アルカリ性の溶液に浸漬して定電圧をかける活性化工程と、（ｄ）マグネシウム金属部材を陽極とし、アルカリ性の溶液中で、陽極酸化被膜を形成する酸化被膜形成工程と、（ｅ）陽極酸化被膜形成後、マグネシウム金属部材を水で洗う水洗工程と、（ｆ）熱可塑性樹脂をインサート成形して、マグネシウム金属部材に接合するインサート工程と、を設けたので、樹脂部材とマグネシウム金属部材を良好に接合でき、接合強度が３０ＭＰａ以上にでき、気密性はヘリウムリークを使用したリークテストで１０－９Ｐａｍ３／ｓ以下にできる。 According to the method for producing a resin-magnesium metal joint according to the present invention, (a) a degreasing step of dipping to remove oil on the surface of a magnesium metal member, (b) an acid treatment step of washing with an acidic solution, and (c). ) An activation step of immersing in an alkaline solution and applying a constant voltage, (d) an oxide film forming step of forming an anodic oxide film in an alkaline solution using a magnesium metal member as an anode, and (e) anodization. After forming the film, a washing step of washing the magnesium metal member with water and (f) an insert step of insert-molding the thermoplastic resin and joining the magnesium metal member to the magnesium metal member were provided, so that the resin member and the magnesium metal member are good. The bonding strength can be 30 MPa or more, and the airtightness can be 10-9 Pam 3 / s or less in a leak test using helium leak.
　本発明による他の樹脂マグネシウム金属接合体の製造法によれば、（ａ）浸漬してマグネシウム金属部材表面の脂分を除く脱脂工程と、（ｂ）酸性の溶液で洗浄する酸処理工程と、（ｃ）アルカリ性の溶液に浸漬して定電圧をかける活性化工程と、（ｄ）マグネシウム金属部材を陽極とし、トリアジンチオール誘導体を含むアルカリ性の溶液中で、陽極酸化被膜を形成する酸化被膜形成工程（ＴＲＩ電解工程と称す）と、（ｅ）陽極酸化被膜形成後、マグネシウム金属部材を水で洗う水洗工程と、（ｆ）熱可塑性樹脂をインサート成形して、マグネシウム金属部材に接合するインサート工程と、を設けたので、樹脂部材とマグネシウム金属部材の接合強度を３０ＭＰａ以上にでき、気密性は、ヘリウムリークを使用したリークテストで１０－９Ｐａｍ３／ｓ以下にできる。 According to another method for producing a resin-magnesium metal joint according to the present invention, there are (a) a degreasing step of dipping to remove the oil on the surface of the magnesium metal member, and (b) an acid treatment step of washing with an acidic solution. (C) Activation step of immersing in an alkaline solution and applying a constant voltage, and (d) Oxide film forming step of forming an anodized film in an alkaline solution containing a triazinethiol derivative with a magnesium metal member as an anode. (Referred to as TRI electrolysis step), (e) a water washing step of washing the magnesium metal member with water after forming an anodized film, and (f) an insert step of insert molding a thermoplastic resin and joining it to the magnesium metal member. Since the above is provided, the bonding strength between the resin member and the magnesium metal member can be 30 MPa or more, and the airtightness can be 10-9 Pam 3 / s or less in the leak test using a helium leak.
本発明による樹脂マグネシウム金属接合体の製造法を示すフローチャートである。It is a flowchart which shows the manufacturing method of the resin magnesium metal bonded body by this invention. 試験片としたマグネシウム金属部材の形状を示す図である。（Ａ）は正面図、（Ｂ）は右側面図、（Ｃ）は斜視図である。It is a figure which shows the shape of the magnesium metal member used as a test piece. (A) is a front view, (B) is a right side view, and (C) is a perspective view. マグネシウム金属部材として使用するマグネシウム合金の種類と成分を示す表である。It is a table which shows the type and composition of the magnesium alloy used as a magnesium metal member. 複数のマグネシウム金属部材が取り付けできる吊下げ冶具の写真である。It is a photograph of a hanging jig to which multiple magnesium metal members can be attached. 吊下げ冶具が脱脂槽に吊り降ろされた写真である。This is a photograph of a hanging jig suspended in a degreasing tank. 吊下げ冶具が酸処理槽に吊り降ろされた写真である。This is a photograph of a hanging jig suspended in an acid treatment tank. ＴＲＩ電解処理槽の写真である。It is a photograph of a TRI electrolysis treatment tank. マグネシウム金属部材の表面粗さを示す写真である。（Ａ）は未処理状態の表面、（Ｂ）は脱脂後の表面、（Ｃ）は酸処理後の表面、（Ｄ）は活性化後の表面、（Ｅ）はＴＲＩ電解処理後の表面である。It is a photograph which shows the surface roughness of a magnesium metal member. (A) is the untreated surface, (B) is the surface after degreasing, (C) is the surface after acid treatment, (D) is the surface after activation, and (E) is the surface after TRI electrolysis treatment. is there. 陽極酸化被膜の断面を示す写真である。It is a photograph which shows the cross section of the anodized film. マグネシウム金属部材の写真（左側）と、図１に示す製造法で製作した引張試験用の試験体の写真（右側）である。It is a photograph (left side) of a magnesium metal member and a photograph (right side) of a test piece for a tensile test manufactured by the manufacturing method shown in FIG. 引張試験用の試験体の引張強度を示す図である。（Ａ）は棒グラフ、（Ｂ）は一覧表である。It is a figure which shows the tensile strength of the test piece for a tensile test. (A) is a bar graph, and (B) is a list. 気密試験用の試験体を示す写真である。It is a photograph which shows the specimen for the airtightness test. 気密試験の結果を示す表である。It is a table which shows the result of the airtightness test. 実施例１で製作した試験体の熱衝撃テスト前後の引張強度を示す図である。It is a figure which shows the tensile strength before and after the thermal shock test of the test piece manufactured in Example 1. 実施例２で製作した試験体の熱衝撃テスト前後の引張強度を示す図である。It is a figure which shows the tensile strength before and after the thermal shock test of the test piece manufactured in Example 2. 実施例１で製作した試験体の高温高湿テスト前後の引張強度を示す図である。It is a figure which shows the tensile strength before and after the high temperature and high humidity test of the test piece manufactured in Example 1. 実施例２で製作した試験体の高温高湿テスト前後の引張強度を示す図である。It is a figure which shows the tensile strength before and after the high temperature and high humidity test of the test piece manufactured in Example 2. Ｍｇ素材（ＡＺ９１）のＴＲＩ電解処理後の表面写真及び成分分析表である。It is the surface photograph and the component analysis table after the TRI electrolysis treatment of the Mg material (AZ91). Ｍｇ素材（ＡＺ３１）のＴＲＩ電解処理後の表面写真及び成分分析表である。It is a surface photograph and a component analysis table after TRI electrolysis treatment of Mg material (AZ31).
　以下、図面を参照して、本発明による樹脂マグネシウム金属接合体及びその製造法を詳しく説明する。 Hereinafter, the resin-magnesium metal joint according to the present invention and a method for producing the same will be described in detail with reference to the drawings.
　図１は、本発明による樹脂マグネシウム金属接合体の製造法を示すフローチャートである。脱脂工程（ｓ１）は、アルカリ系列のＮＡＯＨ、ＫＯＨ、又はＮＡ２ＣＯ３に陽イオン界面活性剤を加えた水溶液に、マグネシウム金属部材１を１～１０分間浸漬することで行なう。溶液の温度は、常温～７０℃の範囲とする。これにより、マグネシウム金属部材１の表面の脂分を除去する。酸処理工程（ｓ２）は、重量％で、リン酸５～５０％、硫酸又は硝酸１～２０％、シユウ酸１～５％、フッ化物１～５％の酸性の水溶液に、マグネシウム金属部材１を１～１０分間浸漬することで行なう。溶液の温度は、常温～５０℃の範囲とする。これにより、マグネシウム金属部材１の表面を洗浄し、酸化膜等を除去する。 FIG. 1 is a flowchart showing a method for producing a resin-magnesium metal joint according to the present invention. The degreasing step (s1) is performed by immersing the magnesium metal member 1 in an aqueous solution prepared by adding a cationic surfactant to NAOH, KOH, or NA 2 CO 3 of the alkaline series for 1 to 10 minutes. The temperature of the solution is in the range of room temperature to 70 ° C. As a result, the oil content on the surface of the magnesium metal member 1 is removed. The acid treatment step (s2) involves adding a magnesium metal member 1 to an acidic aqueous solution of 5 to 50% phosphoric acid, 1 to 20% sulfuric acid or nitric acid, 1 to 5% oxalic acid, and 1 to 5% fluoride in weight%. Is performed by immersing for 1 to 10 minutes. The temperature of the solution is in the range of room temperature to 50 ° C. As a result, the surface of the magnesium metal member 1 is cleaned to remove the oxide film and the like.
　活性化工程（ｓ３）は、重量％で、苛性ソーダ（ＮａＯＨ）１～３０％、炭酸ナトリウム（Ｎａ２ＣＯ３）１～２０％の水溶液に、陽イオン界面活性剤を微量加え、該溶液中にマグネシウム金属部材１を１～１０分浸漬し、陽極または陰極には、０．２～５Ｖの定電圧を与える。水溶液の温度は常温～５０℃とする。電極には、パルス又は直流電圧が与えられる。同時に１～１０分間、５０Ｈｚ、１００～２０００ワットの超音波処理も行なう。 In the activation step (s3), a small amount of a cationic surfactant is added to an aqueous solution of caustic soda (NaOH) 1 to 30% and sodium carbonate (Na 2 CO 3 ) 1 to 20% by weight, and the solution is added. The magnesium metal member 1 is immersed for 1 to 10 minutes, and a constant voltage of 0.2 to 5 V is applied to the anode or cathode. The temperature of the aqueous solution is room temperature to 50 ° C. A pulse or DC voltage is applied to the electrodes. At the same time, ultrasonic treatment at 50 Hz and 100 to 2000 watts is also performed for 1 to 10 minutes.
　酸化被膜形成工程（ｓ４）は、ＴＲＩ電解工程と称する。マグネシウム金属部材１を陽極として接続する。重量％で、苛性ソーダ（ＮａＯＨ）３～２０％、三リン酸ナトリウム（Ｎａ３ＰＯ４）又はリン酸アンモニウム（（ＮＨ４）３ＰＯ４）１～５％、炭酸ナントリウム（Ｎａ２ＣＯ３）１～３％、クエン酸ナントリウム（ＮａＨ２（Ｃ３Ｈ５Ｏ（ＣＯＯ）３）１～３％の水溶液中にマグネシウム金属部材１を浸漬し、陽極と陰極間に１～２０Ａ／ｄｍ２の定電流電流密度を印加することで行なう。溶液の温度は常温～９０℃とする。陽極と陰極間に、電圧４～４０Ｖを印加してもよい。１～４０分間の電気分解により、マグネシウム金属部材の表面に、膜厚５０～３０００ｎｍのトリアジンチオールの陽極酸化被膜４が形成される。陽極酸化被膜４は、重量％で、Ｏが１０～６０％、Ｍｇが１０～９０％、Ｓが３％以下、Ａｌが２０％以下、Ｐが３％以下、Ｚｎが３％以下、Ｃｕが３％以下、Ｍｎが３％以下、Ｎｉが３％以下、Ｓｉが３％以下、Ｆが３％以下の成分構成を有する。 The oxide film forming step (s4) is referred to as a TRI electrolysis step. The magnesium metal member 1 is connected as an anode. By weight%, caustic soda (NaOH) 3 to 20%, sodium triphosphate (Na 3 PO 4 ) or ammonium phosphate ((NH 4 ) 3 PO 4 ) 1 to 5%, nantrium carbonate (Na 2 CO 3 ) 1 to 3%, Nantoriumu citric acid (NaH 2 (C 3 H 5 O (COO) 3) 1 ~ 3% of immersing the magnesium metal member 1 in an aqueous solution, anode and cathode constant of 1 ~ 20A / dm 2 between Current The current density is applied. The temperature of the solution is normal temperature to 90 ° C. A voltage of 4 to 40 V may be applied between the anode and the cathode. Magnesium metal member by electrolysis for 1 to 40 minutes. An anodic oxide film 4 of triazinethiol having a thickness of 50 to 3000 nm is formed on the surface of the anodized film 4. The anodic oxide film 4 is 10 to 60% by weight, O is 10 to 90%, Mg is 10 to 90%, and S is 3%. Below, Al is 20% or less, P is 3% or less, Zn is 3% or less, Cu is 3% or less, Mn is 3% or less, Ni is 3% or less, Si is 3% or less, F is 3% or less. It has a component composition.
　水洗い工程（ｓ５）は、表面に陽極酸化被膜が形成されたマグネシウム金属部材１を、水温が５℃～６０℃の水で洗浄する工程である。インサート成形工程（ｓ６）は、水洗い工程（ｓ５）後、陽極酸化被膜が形成されたマグネシウム金属部材１を金型に装填し、樹脂部材２となる熱可塑性樹脂を注入し、樹脂部材２とマグネシウム金属部材１を接合して樹脂マグネシウム金属接合体３を形成する。 The water washing step (s5) is a step of washing the magnesium metal member 1 having an anodized film formed on its surface with water having a water temperature of 5 ° C. to 60 ° C. In the insert molding step (s6), after the washing step (s5), the magnesium metal member 1 on which the anodic oxide film is formed is loaded into the mold, the thermoplastic resin to be the resin member 2 is injected, and the resin member 2 and magnesium are injected. The metal member 1 is joined to form a resin magnesium metal joint 3.
　図１は、本発明による樹脂マグネシウム金属接合体の製造法を示すフローチャートである。脱脂工程（ｓ１）は、アルカリ系列のＮＡＯＨ、ＫＯＨ、又はＮＡ２ＣＯ３に陽イオン界面活性剤を加えた水溶液に、マグネシウム金属部材１を１～１０分間浸漬することで行なう。溶液の温度は、常温～７０℃の範囲とする。これにより、マグネシウム金属部材１の表面の脂分を除去する。酸処理工程（ｓ２）は、重量％で、リン酸５～５０％、硫酸又は硝酸１～２０％、シユウ酸１～５％、フッ化物１～５％の酸性の水溶液に、マグネシウム金属部材１を１～１０分間浸漬することで行なう。溶液の温度は、常温～５０℃の範囲とする。これにより、マグネシウム金属部材１の表面を洗浄し、酸化膜等を除去する。 FIG. 1 is a flowchart showing a method for producing a resin-magnesium metal joint according to the present invention. The degreasing step (s1) is performed by immersing the magnesium metal member 1 in an aqueous solution prepared by adding a cationic surfactant to NAOH, KOH, or NA 2 CO 3 of the alkaline series for 1 to 10 minutes. The temperature of the solution is in the range of room temperature to 70 ° C. As a result, the oil content on the surface of the magnesium metal member 1 is removed. The acid treatment step (s2) involves adding a magnesium metal member 1 to an acidic aqueous solution of 5 to 50% phosphoric acid, 1 to 20% sulfuric acid or nitric acid, 1 to 5% oxalic acid, and 1 to 5% fluoride in weight%. Is performed by immersing for 1 to 10 minutes. The temperature of the solution is in the range of room temperature to 50 ° C. As a result, the surface of the magnesium metal member 1 is cleaned to remove the oxide film and the like.
　活性化工程（ｓ３）は、重量％で、苛性ソーダ（ＮａＯＨ）１～３０％、炭酸ナトリウム（Ｎａ２ＣＯ３）１～２０％の水溶液に、陽イオン界面活性剤を微量加え、該溶液中にマグネシウム金属部材１を１～１０分浸漬し、陽極または陰極には、０．２～５Ｖの定電圧を与える。水溶液の温度は常温～５０℃とする。電極には、パルス又は直流電圧が与えられる。同時に１～１０分間、５０Ｈｚ、１００～２０００ワットの超音波処理も行なう。 In the activation step (s3), a small amount of a cationic surfactant is added to an aqueous solution of caustic soda (NaOH) 1 to 30% and sodium carbonate (Na 2 CO 3 ) 1 to 20% by weight, and the solution is added. The magnesium metal member 1 is immersed for 1 to 10 minutes, and a constant voltage of 0.2 to 5 V is applied to the anode or cathode. The temperature of the aqueous solution is room temperature to 50 ° C. A pulse or DC voltage is applied to the electrodes. At the same time, ultrasonic treatment at 50 Hz and 100 to 2000 watts is also performed for 1 to 10 minutes.
　酸化被膜形成工程（ｓ４）は、ＴＲＩ電解工程と称する。マグネシウム金属部材１を陽極として接続する。重量％で、苛性ソーダ（ＮａＯＨ）３～２０％、三リン酸ナトリウム（Ｎａ３ＰＯ４）又はリン酸アンモニウム（（ＮＨ４）３ＰＯ４）１～５％、炭酸ナントリウム（Ｎａ２ＣＯ３）１～３％、クエン酸ナントリウム（ＮａＨ２（Ｃ３Ｈ５Ｏ（ＣＯＯ）３）１～３％の水溶液に、微量のトリアジンチオール（Ｔｒｉａｚｉｎｅ　Ｔｈｉｏｌｓ）誘導体を加え、この溶液中にマグネシウム金属部材１を浸漬し、陽極と陰極間に１～２０Ａ／ｄｍ２の定電流電流密度を印加することで行なう。溶液の温度は常温～９０℃とする。陽極と陰極間に、電圧４～４０Ｖを印加してもよい。１～４０分間の電気分解により、マグネシウム金属部材の表面に、膜厚５０～３０００ｎｍのトリアジンチオールの陽極酸化被膜４が形成される。陽極酸化被膜４は、重量％で、Ｏが１０～６０％、Ｍｇが１０～９０％、Ｓが３％以下、Ａｌが２０％以下、Ｐが３％以下、Ｚｎが３％以下、Ｃｕが３％以下、Ｍｎが３％以下、Ｎｉが３％以下、Ｓｉが３％以下、Ｆが３％以下の成分構成を有する。 The oxide film forming step (s4) is referred to as a TRI electrolysis step. The magnesium metal member 1 is connected as an anode. By weight%, caustic soda (NaOH) 3 to 20%, sodium triphosphate (Na 3 PO 4 ) or ammonium phosphate ((NH 4 ) 3 PO 4 ) 1 to 5%, nantrium carbonate (Na 2 CO 3 ) 1 to 3%, Nantoriumu citric acid (NaH 2 (the C 3 H 5 O (COO) 3) 1 ~ 3% aqueous solution, the triazine-thiol (triazine thiols) derivatives traces added magnesium metal member 1 into the solution Immersion is performed by applying a constant current density of 1 to 20 A / dm 2 between the anode and the cathode. The temperature of the solution is normal temperature to 90 ° C. A voltage of 4 to 40 V is applied between the anode and the cathode. By electrolysis for 1 to 40 minutes, an anodic oxide film 4 of triazinethiol having a thickness of 50 to 3000 nm is formed on the surface of the magnesium metal member. The anodic oxide film 4 is by weight% and O is 10-60%, Mg 10-90%, S 3% or less, Al 20% or less, P 3% or less, Zn 3% or less, Cu 3% or less, Mn 3% or less, Ni It has a component composition of 3% or less, Si of 3% or less, and F of 3% or less.
　水洗い工程（ｓ５）は、表面にトリアジンチオールの陽極酸化被膜が形成されたマグネシウム金属部材１を、水温が５℃～６０℃の水で洗浄する工程である。インサート成形工程（ｓ６）は、水洗い工程（ｓ５）後、陽極酸化被膜が形成されたマグネシウム金属部材１を金型に装填し、樹脂部材２となる熱可塑性樹脂を注入し、樹脂部材２とマグネシウム金属部材１を接合して樹脂マグネシウム金属接合体３を形成する。
　このように、実施例１は、ＴＲＩ電解工程の溶液中にトリアジンチオールを添加しない。実施例２は、ＴＲＩ電解工程の溶液中にトリアジンチオールを添加する。 The washing step (s5) is a step of washing the magnesium metal member 1 having a triazine thiol anodized film formed on its surface with water having a water temperature of 5 ° C. to 60 ° C. In the insert molding step (s6), after the washing step (s5), the magnesium metal member 1 on which the anodic oxide film is formed is loaded into the mold, the thermoplastic resin to be the resin member 2 is injected, and the resin member 2 and magnesium are injected. The metal member 1 is joined to form a resin magnesium metal joint 3.
Thus, in Example 1, triazine thiol is not added to the solution of the TRI electrolysis step. In Example 2, triazine thiol is added to the solution of the TRI electrolysis step.
　図２は、マグネシウム金属部材１の形状を示す図である。（Ａ）は正面図、（Ｂ）は右側面図、（Ｃ）は斜視図である。ａは直径４ｍｍの孔である。ｆは板厚で３ｍｍである。縦×横は４０ｍｍ×１２ｍｍの板であり、ｂが１２ｍｍ、ｅが４０ｍｍとなる。ｃは６ｍｍ、ｄは５ｍｍである。 FIG. 2 is a diagram showing the shape of the magnesium metal member 1. (A) is a front view, (B) is a right side view, and (C) is a perspective view. a is a hole having a diameter of 4 mm. f is a plate thickness of 3 mm. The length x width is a plate of 40 mm x 12 mm, and b is 12 mm and e is 40 mm. c is 6 mm and d is 5 mm.
　図３は、マグネシウム金属部材１として使用するマグネシウム合金の種類と成分を示す表である。ＡＺ９１は、アルミニウム（Ａｌ）の含有量が多く、耐食性を向上させたマグネシウム合金である。ＡＺ３１は、アルミニウム（Ａｌ）を３．５％と少なくして、展伸性を向上させたマグネシウム合金である。 FIG. 3 is a table showing the types and components of the magnesium alloy used as the magnesium metal member 1. AZ91 is a magnesium alloy having a high content of aluminum (Al) and improved corrosion resistance. AZ31 is a magnesium alloy with improved extensibility by reducing aluminum (Al) to 3.5%.
　図４は、複数のマグネシウム金属部材１が取り付けできる吊下げ冶具７の写真である。吊下げ冶具７は、上部の２箇所にフックがあり、吊り下げできる。マグネシウム金属部材１が１０個装着できる。 FIG. 4 is a photograph of a hanging jig 7 to which a plurality of magnesium metal members 1 can be attached. The hanging jig 7 has hooks at two upper positions and can be hung. Ten magnesium metal members 1 can be attached.
　図５は、吊下げ冶具７が脱脂槽に吊り降ろされた写真である。脱脂槽には、ＮＡＯＨ、ＫＯＨ、又はＮＡ２ＣＯ３に陽イオン界面活性剤を加えた水溶液が満たされる。図６は、吊下げ冶具７が酸処理槽に吊り降ろされた写真である。酸処理槽は、リン酸５～５０％、硫酸又は硝酸１～２０％、シユウ酸１～５％、フッ化物１～５％の酸性の水溶液で満たされる。図７は、ＴＲＩ電解処理槽の写真である。槽内には複数の電極が用意される。 FIG. 5 is a photograph of the hanging jig 7 suspended in the degreasing tank. The degreasing tank is filled with an aqueous solution of NAOH, KOH, or NA 2 CO 3 plus a cationic surfactant. FIG. 6 is a photograph of the hanging jig 7 suspended in an acid treatment tank. The acid treatment tank is filled with an acidic aqueous solution of 5 to 50% phosphoric acid, 1 to 20% sulfuric acid or nitric acid, 1 to 5% oxalic acid, and 1 to 5% fluoride. FIG. 7 is a photograph of the TRI electrolysis treatment tank. A plurality of electrodes are prepared in the tank.
　図８は、マグネシウム金属部材１の表面粗さを示す写真である。（Ａ）は未処理状態の表面、（Ｂ）は脱脂後の表面、（Ｃ）は酸処理後の表面、（Ｄ）は活性化後の表面、（Ｅ）はＴＲＩ電解処理後の表面である。表面粗さは、３本の直線（左から右に走る３本の線）に沿った中心平均粗さＲａ、単位：μｍで示す。（Ａ）では、３本の直線のＲａが（０．５、０．６、０．６）であった。（Ｂ）では、３本の直線のＲａが（０．７、０．８、１．０）であった。（Ｃ）では、３本の直線のＲａが（１．６、０．７．０．８）であった。（Ｄ）では、３本の直線のＲａが（０．６、０．６、０．６）であった。ここでは酸処理で表面に付着した黒色微粉末が除去された状態にある。（Ｅ）では、３本の直線のＲａが（０．３、０．４、０．４）であった。 FIG. 8 is a photograph showing the surface roughness of the magnesium metal member 1. (A) is the untreated surface, (B) is the surface after degreasing, (C) is the surface after acid treatment, (D) is the surface after activation, and (E) is the surface after TRI electrolysis treatment. is there. The surface roughness is shown by the central average roughness Ra along three straight lines (three lines running from left to right), in units of μm. In (A), Ra of the three straight lines was (0.5, 0.6, 0.6). In (B), Ra of the three straight lines was (0.7, 0.8, 1.0). In (C), Ra of the three straight lines was (1.6, 0.7.0.8). In (D), Ra of the three straight lines was (0.6, 0.6, 0.6). Here, the black fine powder adhering to the surface is removed by the acid treatment. In (E), Ra of the three straight lines was (0.3, 0.4, 0.4).
　図９は、陽極酸化被膜の断面を示す写真である。陽極酸化被膜４の表面には、３００ｎｍと１．５μｍの膜厚が形成されている。被膜の厚さは、５０ｎｍ～３０００ｎｍ（３．０μｍ）にできる。 FIG. 9 is a photograph showing a cross section of the anodized film. Film thicknesses of 300 nm and 1.5 μm are formed on the surface of the anodized film 4. The thickness of the coating can be 50 nm to 3000 nm (3.0 μm).
　図１０は、試験片の写真（左側）と、図１に示す製造法で製作した引張試験用の試験体の写真（右側）である。図１０に示すように、マグネシウム金属部材１と樹脂部材２は、１２ｍｍ×３ｍｍ（＝３６ｍｍ２）の端面が接合される。試験体は符号３（３ａ）で示す。すなわち、試験体は、引張試験用の試験体３ａである。樹脂マグネシウム金属接合体３は、マグネシウム金属部材１に樹脂部材２がインサート成形により一体化成形されたものである。インサート成形は、金型にマグネシウム金属部材１を装填しておき、熱可塑性樹脂を圧入することで、マグネシウム金属部材１と樹脂部材２を一体化成形する。熱可塑性樹脂としては、ポリブチレンテレフタレート（ＰＢＴ）、ポリフェニレンサルファイド（ＰＰＳ）を使用できる。 FIG. 10 is a photograph of the test piece (left side) and a photograph of a test piece for a tensile test manufactured by the manufacturing method shown in FIG. 1 (right side). As shown in FIG. 10, the end faces of the magnesium metal member 1 and the resin member 2 are joined to each other by 12 mm × 3 mm (= 36 mm 2 ). Specimens are indicated by reference numeral 3 (3a). That is, the test body is a test body 3a for a tensile test. The resin-magnesium metal joint 3 is formed by integrally molding a resin member 2 with a magnesium metal member 1 by insert molding. In the insert molding, the magnesium metal member 1 is loaded in the mold, and the thermoplastic resin is press-fitted to integrally mold the magnesium metal member 1 and the resin member 2. As the thermoplastic resin, polybutylene terephthalate (PBT) and polyphenylene sulfide (PPS) can be used.
　図１１は、試験体の引張強度を示す図である。（Ａ）は棒グラフ、（Ｂ）は一覧表である。Ｎｏ１～８の８個の試験体で測定した。Ｎｏ１～４が実施例１で製作したもの、Ｎｏ５～８が実施例１で製作したものである。図１１に示すように、試験体の各数値から、樹脂部材２とマグネシウム金属部材１の引張強度を３０ＭＰａ以上にできる。 FIG. 11 is a diagram showing the tensile strength of the test piece. (A) is a bar graph, and (B) is a list. It was measured with 8 test pieces of Nos. 1 to 8. Nos. 1 to 4 are manufactured in Example 1, and Nos. 5 to 8 are manufactured in Example 1. As shown in FIG. 11, the tensile strength of the resin member 2 and the magnesium metal member 1 can be set to 30 MPa or more from each numerical value of the test piece.
　図１２は、気密試験用の試験体を示す写真である。試験体は、符号３（３ｂ）で示す。すなわち、試験体は、樹脂マグネシウム金属接合体３の気密試験用の試験体３ｂである。気密試験用の試験体３ｂは、マグネシウム金属部材１が、円板状の樹脂部材２を貫通して一体に接合されている。筒状の容器に気密試験用の試験体３ｂを装填し、マグネシウム金属部材１が突出した一方の側にヘリウムガスを吹き付け、マグネシウム金属部材１が突出した他方の側を真空にして、ヘリウムガスが漏れないか調べる。実施例１で試験体１－１～１－４を製作し、実施例２で試験体２－１～２－４を製作した。 FIG. 12 is a photograph showing a test body for an airtightness test. Specimens are indicated by reference numeral 3 (3b). That is, the test body is the test body 3b for the airtightness test of the resin magnesium metal joint 3. In the test body 3b for the airtightness test, the magnesium metal member 1 penetrates the disk-shaped resin member 2 and is integrally joined. A test piece 3b for an airtightness test is loaded in a tubular container, helium gas is sprayed on one side on which the magnesium metal member 1 protrudes, and the other side on which the magnesium metal member 1 protrudes is evacuated to release helium gas. Check for leaks. Test bodies 1-1 to 1-4 were produced in Example 1, and test bodies 2-1 to 2-4 were produced in Example 2.
　図１３は、気密試験の結果を示す表である。真空排気の量を増減させれば、漏れ出るヘリウム（Ｈｅ）の量も増減するが、図１３の表の数値から、実施例１の試験体１－１～１－４、実施例２の試験体２－１～２－４のいずれも１×１０－９Ｐａｍ３／ｓ以下にできる。 FIG. 13 is a table showing the results of the airtightness test. If the amount of vacuum exhaust is increased or decreased, the amount of leaked helium (He) also increases or decreases, but from the numerical values in the table of FIG. 13, the test bodies 1-1 to 1-4 of Example 1 and the test of Example 2 Any of the bodies 2-1 to 2-4 can be 1 × 10 -9 Pam 3 / s or less.
　図１４は、実施例１で製作した試験体の熱衝撃テスト前後の引張強度を示す図である。熱衝撃テストは、温度をマイナス４０℃～８０℃間で３０分毎に変化させ、１５０サイクルを繰り返した。表において、ＭＰａの欄は、接合断面が３６ｍｍ２での値であり、Ｎと記載された欄は、ＭＰａの値を３６倍した値を記載している。図１４の表によれば、引張強度のａｖｇは、熱衝撃テスト前では４１．８４ＭＰａであったが、熱衝撃テスト後は５０．１２ＭＰａに上昇している。 FIG. 14 is a diagram showing the tensile strength of the test piece manufactured in Example 1 before and after the thermal shock test. In the thermal shock test, the temperature was changed between -40 ° C and 80 ° C every 30 minutes, and 150 cycles were repeated. In the table, the column of MPa is the value when the joint cross section is 36 mm 2 , and the column of N is the value obtained by multiplying the value of MPa by 36. According to the table of FIG. 14, the tensile strength avg was 41.84 MPa before the thermal shock test, but increased to 50.12 MPa after the thermal shock test.
　図１５は、実施例２で製作した試験体の熱衝撃テスト前後の引張強度を示す図である。熱衝撃テストは、温度をマイナス４０℃～８０℃間で３０分毎に変化させ、１５０サイクルを繰り返した。表において、ＭＰａの欄は、接合断面が３６ｍｍ２での値であり、Ｎと記載された欄は、ＭＰａの値を３６倍した値を記載している。図１５の表によれば、引張強度のａｖｇは、熱衝撃テスト前では４５．６０ＭＰａであったが、熱衝撃テスト後は５１．３２ＭＰａに上昇している。 FIG. 15 is a diagram showing the tensile strength of the test piece manufactured in Example 2 before and after the thermal shock test. In the thermal shock test, the temperature was changed between -40 ° C and 80 ° C every 30 minutes, and 150 cycles were repeated. In the table, the column of MPa is the value when the joint cross section is 36 mm 2 , and the column of N is the value obtained by multiplying the value of MPa by 36. According to the table of FIG. 15, the tensile strength avg was 45.60 MPa before the thermal shock test, but increased to 51.32 MPa after the thermal shock test.
　図１６は、実施例１で製作した試験体の高温高湿テスト前後の引張強度を示す図である。高温高湿テストは、温度が８０℃、湿度９５％、テスト時間は２００時間で実施した。この試験後の引張強度は、図１６に示すように、負荷テストをしない試験体の引張強度よりも低下した。表によれば、引張強度のａｖｇは、テスト前では４２．８２ＭＰａであったが、テスト後は、３０．３９ＭＰａに低下した。 FIG. 16 is a diagram showing the tensile strength of the test piece produced in Example 1 before and after the high temperature and high humidity test. The high temperature and high humidity test was carried out at a temperature of 80 ° C., a humidity of 95%, and a test time of 200 hours. As shown in FIG. 16, the tensile strength after this test was lower than the tensile strength of the test piece not subjected to the load test. According to the table, the tensile strength avg was 42.82 MPa before the test, but decreased to 30.39 MPa after the test.
　図１７は、実施例２で製作した試験体の高温高湿テスト前後の引張強度を示す図である。高温高湿テストは、温度が８０℃、湿度９５％、テスト時間は２００時間で実施した。この試験後の引張強度は、図１７に示すように、負荷テストをしない試験体の引張強度よりも低下した。表によれば、引張強度のａｖｇは、テスト前では４２．８２ＭＰａであったが、テスト後は、３０．３９ＭＰａに低下した。 FIG. 17 is a diagram showing the tensile strength of the test piece produced in Example 2 before and after the high temperature and high humidity test. The high temperature and high humidity test was carried out at a temperature of 80 ° C., a humidity of 95%, and a test time of 200 hours. As shown in FIG. 17, the tensile strength after this test was lower than the tensile strength of the test piece not subjected to the load test. According to the table, the tensile strength avg was 42.82 MPa before the test, but decreased to 30.39 MPa after the test.
　図１８は、Ｍｇ素材（ＡＺ９１）のＴＲＩ電解処理後の表面写真及び成分分析表である。表面は凸凹形状をしている。陽極酸化被膜の成分表によれば、重量％で、Ｍｇが３２．３３％、Ｏが３９．５９％であるから、酸化マグネシウム（ＭｇＯ）が形成されている。 FIG. 18 is a surface photograph and a component analysis table of the Mg material (AZ91) after the TRI electrolysis treatment. The surface has an uneven shape. According to the composition table of the anodized film, magnesium oxide (MgO) is formed because Mg is 32.33% and O is 39.59% in weight%.
　図１９は、Ｍｇ素材（ＡＺ３１）のＴＲＩ電解処理後の表面写真及び成分分析表である。表面は凸凹形状をしており、また、多数の孔が形成されている。陽極酸化被膜の成分表によれば、重量％で、Ｍｇが６４．３２％、Ｏが３１．９８％であるから、酸化マグネシウム（ＭｇＯ）が形成されている。 FIG. 19 is a surface photograph and a component analysis table of the Mg material (AZ31) after the TRI electrolysis treatment. The surface has an uneven shape, and a large number of holes are formed. According to the composition table of the anodized film, magnesium oxide (MgO) is formed because Mg is 64.32% and O is 31.98% by weight.
　本発明の樹脂マグネシウム金属接合体及びその製造法は、金属部材と樹脂部材の一体化して接合するもので、部品の軽量化に好適である。 The resin-magnesium metal joint of the present invention and the method for manufacturing the same are for integrally joining the metal member and the resin member, and are suitable for reducing the weight of the parts.
　１　　マグネシウム金属部材
　２　　樹脂部材
　３　　樹脂マグネシウム金属接合体
　３ａ　　引張試験用の試験体
　３ｂ　　気密試験用の試験体
　４　　陽極酸化被膜
　５　　マグネシウム合金
　７　　吊下げ冶具
　ｓ１～ｓ６　　製造法の各工程 1 Magnesium metal member 2 Resin member 3 Resin magnesium metal joint 3a Test body for tensile test 3b Test body for airtightness test 4 Anodized coating 5 Magnesium alloy 7 Suspension jig s1 to s6 Each process of manufacturing method

Claims (2)

  1. 　マグネシウム金属部材と熱可塑性樹脂部材とを接合してなる樹脂マグネシウム金属接合体であって、
    　前記マグネシウム金属部材と前記熱可塑性樹脂部材とが、膜厚が５０～３０００ｎｍの陽極酸化被膜により接合され、
    　前記陽極酸化被膜は、トリアジンチオールを内部及び外部に存在させ、重量％で、Ｏが１～６０％、Ｍｇが１～９０％、Ｓが３％以下、Ａｌが２０％以下、Ｐが３％以下、Ｚｎが３％以下、Ｃｕが３％以下、Ｍｎが３％以下、Ｎｉが３％以下、Ｓｉが２０％以下、Ｆが３％以下の成分構成を有することを特徴とする樹脂マグネシウム金属接合体。     A resin-magnesium metal joint formed by joining a magnesium metal member and a thermoplastic resin member.
    And the thermoplastic resin member and the magnesium metal member, the thickness is joined by positive electrode oxide film of 50 ~ 3000 nm,
    The anodic oxide film has triazine thiol present inside and outside, and by weight%, O is 1 to 60%, Mg is 1 to 90%, S is 3% or less, Al is 20% or less, and P is 3%. Hereinafter, a resin magnesium metal having a component composition of Zn of 3% or less, Cu of 3% or less, Mn of 3% or less, Ni of 3% or less, Si of 20% or less, and F of 3% or less. Joined body.
  2. 　請求項１に記載された樹脂マグネシウム金属接合体を製造する製造法であって、
    　マグネシウム金属部材をアルカリ性の溶液で洗浄する脱脂工程と、
    　前記脱脂工程後、マグネシウム金属部材を酸性の溶液で洗浄する酸処理工程と、
    　前記酸処理工程後、マグネシウム金属部材をアルカリ性の溶液に浸漬し電極に定電圧をかける活性化処理工程と、
    　前記マグネシウム金属部材を陽極とし、２０～９０℃のアルカリ性のトリアジンチオール誘導体を含む溶液中で、０．５Ａ／ｄｍ２以上５Ａ／ｄｍ２未満の電流密度を印加して、前記マグネシウム金属部材上に膜厚が５０～３０００ｎｍの陽極酸化被膜を形成する工程と、
    　前記陽極酸化被膜が形成されたマグネシウム金属部材を、５℃以上、６０℃未満の水で洗浄する水洗い工程と、
    　前記水洗い工程後の、前記陽極酸化被膜が形成されたマグネシウム金属部材に、熱可塑性樹脂をインサート成形する工程と、が備えられ、
    　前記マグネシウム金属部材と、熱可塑性樹脂で成形された樹脂部材とが接合されることを特徴とする樹脂マグネシウム金属接合体の製造法。     A production method for producing the resin-magnesium metal joint according to claim 1.
    A degreasing process that cleans magnesium metal parts with an alkaline solution,
    After the degreasing step, an acid treatment step of washing the magnesium metal member with an acidic solution and
    After the acid treatment step, an activation treatment step of immersing the magnesium metal member in an alkaline solution and applying a constant voltage to the electrodes,
    Using the magnesium metal member as an anode, a current density of 0.5 A / dm2 or more and less than 5 A / dm2 is applied in a solution containing an alkaline triazine thiol derivative at 20 to 90 ° C. to form a film on the magnesium metal member. The process of forming an anodic oxide film of 50 to 3000 nm and
    A water washing step of washing the magnesium metal member on which the anodized film is formed with water at 5 ° C. or higher and lower than 60 ° C.
    A step of insert molding a thermoplastic resin into the magnesium metal member on which the anodized film is formed after the washing step is provided.
    A method for producing a resin-magnesium metal bonded body, which comprises joining the magnesium metal member and a resin member molded of a thermoplastic resin.
PCT/JP2019/020368 2019-05-23 2019-05-23 Resin-magnesium metal bonded body and method for manufacturing same WO2020235070A1 (en)

Priority Applications (3)

Application Number Priority Date Filing Date Title
PCT/JP2019/020368 WO2020235070A1 (en) 2019-05-23 2019-05-23 Resin-magnesium metal bonded body and method for manufacturing same
CN201980096719.0A CN114207192A (en) 2019-05-23 2019-05-23 Resin metal magnesium bonded body and method for producing same
KR1020217042145A KR102618505B1 (en) 2019-05-23 2019-05-23 Conjugate of resin and magnesium-based metal and method for producing the same

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
PCT/JP2019/020368 WO2020235070A1 (en) 2019-05-23 2019-05-23 Resin-magnesium metal bonded body and method for manufacturing same

Publications (1)

Publication Number Publication Date
WO2020235070A1 true WO2020235070A1 (en) 2020-11-26

Family

ID=73459354

Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/JP2019/020368 WO2020235070A1 (en) 2019-05-23 2019-05-23 Resin-magnesium metal bonded body and method for manufacturing same

Country Status (3)

Country Link
KR (1) KR102618505B1 (en)
CN (1) CN114207192A (en)
WO (1) WO2020235070A1 (en)

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP7125804B1 (en) * 2021-06-18 2022-08-25 ドングァン ディーエスピー テクノロジー カンパニー リミテッド Magnesium surface treatment method for polymer-magnesium conjugate

Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2000160392A (en) * 1998-11-27 2000-06-13 Kunio Mori Plated body of magnesium of its alloy by means of triazine-thiol derivative, and composite body of the plated body with organic high-molecular material
JP2009114504A (en) * 2007-11-07 2009-05-28 Shingijutsu Kenkyusho:Kk Magnesium alloy article, magnesium alloy member, and method for manufacturing the same
JP2009132092A (en) * 2007-11-30 2009-06-18 Mitsubishi Plastics Inc Manufacturing process of resin coating magnesium alloy plate and resin coating magnesium alloy molded product
JP2009249663A (en) * 2008-04-03 2009-10-29 Shingijutsu Kenkyusho:Kk Magnesium alloy article and magnesium alloy member
JP2010275571A (en) * 2009-05-26 2010-12-09 Okayama Prefecture Molding made of magnesium or magnesium alloy and method of manufacturing the same

Family Cites Families (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP2221398B1 (en) * 2007-12-14 2016-10-19 Toadenka Corporation Resin-metal bonded body and method for producing the same
KR101243901B1 (en) * 2012-03-21 2013-03-20 주식회사 태성포리테크 Aluminium-polymer resin bonded component and method of preparing the component
JP6501841B2 (en) * 2017-09-08 2019-04-17 ジオネーション株式会社 Resin titanium metal bonded body and method for producing the same

Patent Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2000160392A (en) * 1998-11-27 2000-06-13 Kunio Mori Plated body of magnesium of its alloy by means of triazine-thiol derivative, and composite body of the plated body with organic high-molecular material
JP2009114504A (en) * 2007-11-07 2009-05-28 Shingijutsu Kenkyusho:Kk Magnesium alloy article, magnesium alloy member, and method for manufacturing the same
JP2009132092A (en) * 2007-11-30 2009-06-18 Mitsubishi Plastics Inc Manufacturing process of resin coating magnesium alloy plate and resin coating magnesium alloy molded product
JP2009249663A (en) * 2008-04-03 2009-10-29 Shingijutsu Kenkyusho:Kk Magnesium alloy article and magnesium alloy member
JP2010275571A (en) * 2009-05-26 2010-12-09 Okayama Prefecture Molding made of magnesium or magnesium alloy and method of manufacturing the same

Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP7125804B1 (en) * 2021-06-18 2022-08-25 ドングァン ディーエスピー テクノロジー カンパニー リミテッド Magnesium surface treatment method for polymer-magnesium conjugate
US20220403526A1 (en) * 2021-06-18 2022-12-22 Dongguan DSP Technology Co., Ltd. Surface treatment method of magnesium for the assembly of polymer and magnesium
US11618952B2 (en) * 2021-06-18 2023-04-04 Dongguan DSP Technology Co., Ltd. Surface treatment method of magnesium for the assembly of polymer and magnesium

Also Published As

Publication number Publication date
CN114207192A (en) 2022-03-18
KR20220036915A (en) 2022-03-23
KR102618505B1 (en) 2023-12-29

Similar Documents

Publication Publication Date Title
JP6501841B2 (en) Resin titanium metal bonded body and method for producing the same
JP4686728B2 (en) Method for producing magnesium or magnesium alloy product having an anodized film on the surface
US20110297549A1 (en) Aluminum alloy-and-resin composite and method for making the same
US20110305893A1 (en) Aluminum alloy-and-resin composite and method for making the same
JP6655593B2 (en) Resin magnesium metal joined body and manufacturing method thereof
JP5595874B2 (en) Magnesium alloy surface treatment method
WO2020235070A1 (en) Resin-magnesium metal bonded body and method for manufacturing same
JP2019119914A (en) Resin zirconium alloy joined body and production method thereof
JP2012041579A (en) Surface machining method of aluminum or aluminum alloy material, composite material, and surface machining pretreatment liquid
JP7040988B2 (en) Aluminum alloy and resin complex and its manufacturing method
JP4417106B2 (en) Magnesium anodizing system and method
TW201343044A (en) Forming method for a metal housing
WO2014203919A1 (en) Method for manufacturing magnesium alloy product
AU2002334458A1 (en) Magnesium anodisation system and methods
JP6546313B1 (en) Resin carbon steel joined body and method for producing the same
WO2019189773A1 (en) Substrate having surface made entirely or at least partially of metal material wherein surface of said metal material has holes, and substrate-resin cured product composite containing said substrate and resin cured product
JP2006026912A (en) Base material part, metal/resin composite molded product and manufacturing method of metal/resin composite molded product
US3753882A (en) Method for converting aluminum and aluminum base,and copper and copper base material surfaces from a hydrophobic to a hydraphilic state
KR102620567B1 (en) Anodizing method to improve withstand voltage
KR100453994B1 (en) Two layer non-electrolysis nickel coating method by dynamic etching of magnesium and magnesium alloy
RU2349687C2 (en) Method of making objects from aluminium and its alloys before electrolytic coating
KR101701268B1 (en) Electrolyte solution for PEO on magnesium alloy and PEO method using the same
JP2014128939A (en) Method for producing metal-resin composite
JP7489028B2 (en) Integrated structure of copper material and PPS resin composition and its manufacturing method
KR100431125B1 (en) Double electroless nikel plating method by pre-treatment process of magnesium and magnesium alloy

Legal Events

Date Code Title Description
121 Ep: the epo has been informed by wipo that ep was designated in this application

Ref document number: 19929391

Country of ref document: EP

Kind code of ref document: A1

DPE1 Request for preliminary examination filed after expiration of 19th month from priority date (pct application filed from 20040101)
NENP Non-entry into the national phase

Ref country code: DE

122 Ep: pct application non-entry in european phase

Ref document number: 19929391

Country of ref document: EP

Kind code of ref document: A1

NENP Non-entry into the national phase

Ref country code: JP