WO2011104868A1 - Matériau métallique modifié en surface, complexe de matériau métallique modifié en surface, résine, élastomère et film de revêtement, et procédé de fabrication associé - Google Patents

Matériau métallique modifié en surface, complexe de matériau métallique modifié en surface, résine, élastomère et film de revêtement, et procédé de fabrication associé Download PDF

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WO2011104868A1
WO2011104868A1 PCT/JP2010/053115 JP2010053115W WO2011104868A1 WO 2011104868 A1 WO2011104868 A1 WO 2011104868A1 JP 2010053115 W JP2010053115 W JP 2010053115W WO 2011104868 A1 WO2011104868 A1 WO 2011104868A1
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metal
treated
resin
adhesive
metal material
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PCT/JP2010/053115
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English (en)
Japanese (ja)
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都 立原
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株式会社サンベスト
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    • C—CHEMISTRY; METALLURGY
    • C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
    • C25D9/00—Electrolytic coating other than with metals
    • C25D9/04—Electrolytic coating other than with metals with inorganic materials
    • C25D9/06—Electrolytic coating other than with metals with inorganic materials by anodic processes
    • 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
    • C25D11/04—Anodisation of aluminium or alloys based thereon
    • C25D11/06—Anodisation of aluminium or alloys based thereon characterised by the electrolytes used
    • 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
    • C25D11/36—Phosphatising
    • C—CHEMISTRY; METALLURGY
    • C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
    • C25D9/00—Electrolytic coating other than with metals
    • C25D9/04—Electrolytic coating other than with metals with inorganic materials
    • C25D9/08—Electrolytic coating other than with metals with inorganic materials by cathodic processes

Definitions

  • the present invention relates to a surface-modified metal material, a composite of the surface-modified metal material and a resin, an elastomer, and a coating film, and a method for producing the same.
  • an anodic oxide film having a thickness of 0.1 to 1 ⁇ m and a hole having a diameter of 10 nm or more is formed on an aluminum or aluminum alloy plate with an area of 75% or more of the entire area.
  • a method has been proposed in which a thermoplastic resin film is laminated to the surface of aluminum or an aluminum alloy by laminating a thermoplastic resin film by hot pressing or the like (see, for example, Patent Document 1). This is because, when an anodized film is formed so that the diameter of the hole becomes 10 nm or more, when the thermoplastic resin is laminated while being heated and melted from the surface of the film, the molten thermoplastic resin is formed in the hole of the anodized film. It is possible to enter the inside, and the intruding thermoplastic resin is solidified after cooling, and the adhesiveness between the thermoplastic resin film and the anodized film is improved by the anchoring effect.
  • a method has been proposed in which a nonporous anodic oxide film is formed on the surface of aluminum or aluminum alloy to improve the adhesion between the surface of aluminum or aluminum alloy and the resin film (see, for example, Patent Document 2).
  • This nonporous anodic oxide film has a thickness of 5 to 800 nm, a porosity of 20% or less, and at least one of silicon (Si), phosphorus (P), boron (B) or carbon (C) components. It is described that the adhesiveness can be improved when the seeds are contained in a total of 50 ppm or more.
  • the surface has a diameter of 200 mm or more and a depth of 5 ⁇ m or less. It has been proposed to provide fine holes with a hole occupation area ratio of 5 to 60% to improve the adhesion of the coating film of aluminum or aluminum alloy material (see, for example, Patent Document 3).
  • the improvement in the adhesion of the coating film on the aluminum surface described in Patent Document 3 is to improve the adhesion by the anchoring effect of the paint entering into the holes of 200 mm or more, as in Patent Document 1 described above.
  • a metal plate such as aluminum is immersed in an aqueous solution in which an alkali salt or amine ammonium salt of a triazine thiol is dissolved, and is subjected to an electrochemical treatment in the same manner as electroplating, and the metal surface is coated with a triazine thiol.
  • a method has been proposed in which a (organic material layer) is generated, and a resin sheet is superimposed on the coating and pressed with a hot plate to firmly bond the metal and the resin (for example, see Patent Document 5).
  • Patent Document 2 The prior art described in Patent Document 2 is, for example, a polyethylene (PE) resin, a polyethylene terephthalate (PET) resin, a polypropylene (PP) resin, a polyamide resin as an organic resin film that can be bonded to aluminum or an aluminum alloy.
  • PE polyethylene
  • PET polyethylene terephthalate
  • PP polypropylene
  • POM polyacetal
  • the type of resin that can be bonded to the surface of aluminum or an aluminum alloy is a polymer containing polybutylene terephthalate (PBT) or polybutylene terephthalate (PBT). Therefore, there is a problem that a general general-purpose resin such as acrylonitrile butadiene styrene resin (ABS) cannot be bonded to an aluminum alloy.
  • PBT polybutylene terephthalate
  • PBT polybutylene terephthalate
  • the bonding method between the aluminum or aluminum alloy and the resin disclosed in Patent Documents 1 to 5 can be realized by any method, but the bonding can be realized.
  • resins that cannot be used, and there is a problem in that they cannot have adhesiveness to most resins generally used by one method.
  • polyacetal (POM) is widely used for gears and machine parts because its mechanical properties are close to those of metals, but it is registered in any of the conventional techniques described in Patent Documents 1 to 5.
  • the homopolymer of polyacetal (POM), known as the trademark Delrin, and Duracon, which is a copolymer thereof, could not be bonded to metal even by an adhesive.
  • the present invention relates to general-purpose engineering including acrylonitrile butadiene styrene resin (ABS), polymethyl methacrylate (methacrylic resin, acrylic resin, PMMA), and polyacetal (POM), polycarbonate (PC), polybutylene terephthalate (PBT).
  • ABS acrylonitrile butadiene styrene resin
  • methacrylic resin acrylic resin
  • PMMA polymethyl methacrylate
  • POM polyacetal
  • PC polycarbonate
  • PBT polybutylene terephthalate
  • An object of the present invention is to provide a surface-modified metal material having good adhesion to various resins such as plastics and elastomers, varnishes, paints, adhesives and the like.
  • the surface-modified metal material of the present invention is a resin, an elastomer, and a coating film on the surface of the metal to be treated by passing a current between the counter electrode of the non-soluble conductive material and the metal to be treated in an aqueous solution containing nitrate ions.
  • An adhesive surface having adhesiveness with at least one selected from the group consisting of adhesives is formed.
  • the aqueous solution is also preferable as containing phosphate ions simultaneously.
  • the metal to be treated is preferably aluminum, titanium, steel, stainless steel, nickel, copper, zinc, magnesium and their alloys, or a plated surface.
  • a non-soluble conductive material is used.
  • Connect the counter electrode to the cathode connect the metal to be processed to the anode and energize it. If the metal to be processed is zinc or magnesium and their alloys, or a plated surface, connect the counter electrode of the non-soluble conductive material. It is also preferable to connect to the anode and connect the metal to be processed to the cathode for energization.
  • the composite of the surface-modified metal material of the present invention and a resin or elastomer or paint is energized between a counter electrode of a non-soluble conductive material and a metal to be treated in an aqueous solution containing nitrate ions.
  • the aqueous solution is also preferable as containing phosphate ions simultaneously.
  • a resin or elastomer is applied to the surface of the metal to be treated by passing a current between the counter electrode of the non-soluble conductive material and the metal to be treated in an aqueous solution containing nitrate ions.
  • aqueous solution is suitable also as containing a phosphate ion simultaneously.
  • the method for producing a composite of a surface-modified metal material of the present invention and a resin or an elastomer or a paint is conducted by passing an electric current between a counter electrode such as an insoluble conductive material and a metal to be treated in an aqueous solution containing nitrate ions.
  • the aqueous solution contains phosphate ions simultaneously.
  • the present invention relates to general-purpose engineering including acrylonitrile butadiene styrene resin (ABS), polymethyl methacrylate (methacrylic resin, acrylic resin, PMMA), and polyacetal (POM), polycarbonate (PC), polybutylene terephthalate (PBT).
  • ABS acrylonitrile butadiene styrene resin
  • methacrylic resin acrylic resin
  • PMMA polymethyl methacrylate
  • POM polyacetal
  • PC polycarbonate
  • PBT polybutylene terephthalate
  • the nitrate ion is represented by the chemical formula, NO 3
  • the phosphate ion is represented by the chemical formula, PO 4 .
  • the pH of the aqueous solution containing the nitrate ion and phosphate ion at the same time is such that the natural electrode potential of the metal to be treated is slightly less electrochemical than the conductive non-dissolvable counter-polar material. It must be present or hardly dissolved.
  • a carbon electrode or the like can be used as the counter electrode, but when the metal to be treated is an aluminum alloy, nickel-plated surface, stainless steel, titanium alloy, steel, etc., the pH of the liquid is 2, or slightly less than 2 Then, the metal to be treated is connected to the anode side of the external power source and energized. That is, in an aqueous solution containing the nitrate ion or the nitrate ion and phosphate ion at the same time, the carbon electrode is connected to the negative electrode of the power supply device as a cathode, and the metal plate is used as the positive electrode of the power supply device. Connect to the anode.
  • a current is passed between the positive electrode and the negative electrode of the power supply device, and energization is performed for a predetermined time between the carbon electrode and the metal to be processed.
  • energization is performed for a predetermined time between the carbon electrode and the metal to be processed.
  • zinc alloys, galvanized products, magnesium alloys, copper, etc. reduce the concentration of the treatment solution, or at the same time, neutralize the pH, or add alkali to make the treatment solution neutral or slightly alkaline. Then, energize for several minutes while suppressing surface dissolution of the untreated metal.
  • the carbon electrode is connected to the anode and the metal to be processed is connected to the cathode side to be processed. It is good also as making it react with the ion in aqueous solution, suppressing melt
  • the above energization is performed by maintaining the voltage between the counter electrode carbon electrode and the metal to be treated at a constant voltage, and by applying a constant current value flowing between the carbon electrode and the metal to be treated.
  • Two types of energization methods, the constant current method can be applied.
  • Example 1-1 Aluminum plate JIS5052 is attached to a titanium holding jig by a conventional surface treatment method, degreased, washed, neutralized, washed with water, and then at 20 ° C. and 0.5 A / dm 2 in an aqueous solution containing nitrate ions 0.6 mol / L. After anodic electrolytic treatment for 10 minutes, it was washed with water and dried. On the aluminum plate, a 10% organic solvent suspension of polyacetal (POM) powder is sprayed with a coating gun, and then heated gradually to evaporate the solvent, and then heated to polyacetal (POM). ) After melting the powder, it was cooled. The surface of the aluminum alloy plate was firmly coated with a polyacetal (POM) thin film.
  • POM polyacetal
  • Example 1-2 An aluminum plate JIS 5052 similar to Example 1-1 was attached to a titanium holding jig by a conventional surface treatment method, and after degreasing, water washing, neutralization, and water washing, nitrate ions 0.6 mol / L and phosphate ions 0.
  • anodic electrolytic treatment was performed at 20 ° C. and 0.5 A / dm 2 for 10 minutes, followed by washing with water and drying.
  • a 10% organic solvent suspension of polyacetal (POM) powder is sprayed with a coating gun, and then heated gradually to evaporate the solvent, and then heated to polyacetal (POM). ) After melting the powder, it was cooled.
  • POM polyacetal
  • the surface of the aluminum alloy plate was firmly coated with a polyacetal (POM) thin film.
  • POM polyacetal
  • the coating film adhesion of the aluminum alloy plate treated in an aqueous solution in which nitrate ions and phosphate ions coexisted was aluminum treated in an aqueous solution containing only nitrate ions as in Example 1-1. It was judged to be slightly better than the coating film adhesion of the alloy plate.
  • Example 2-1 An aluminum alloy plate similar to Example 1-1 was cut into a width of 25 mm and a length of 75 mm to obtain a test piece, which was degreased, washed, neutralized, washed with water, and then graphite in an aqueous solution containing 1 mol / L of nitrate ions.
  • the electrode was used as a counter electrode and anodized for 5 minutes.
  • the current density was 0.5A / dm 2.
  • the two test pieces are overlapped by 10 mm in the length direction, and a 0.1 mm-thick sheet of polyacetal (POM) (hereinafter referred to as POM sheet) is sandwiched between them. Pressed and welded.
  • POM sheet polyacetal
  • test piece A Five sets of the test pieces were made to make a test piece A for a tensile test. When the tensile test specimen A was applied to a tensile tester and the strength until cutting was measured, all had a strength of 1 KN / cm 2 or more.
  • Example 2-2 Aluminum having the same size as that of Example 2-1, which was electrolytically treated in the same conditions as in Example 2-1, washed with water, and dried in an electrolytic solution containing 1 mol / L of nitric acid and 1.5 mol / L of phosphoric acid.
  • Ten test pieces of alloy were prepared, and cut pieces of a polyacetal (POM) sheet were sandwiched and welded in the same manner as in Example 2-1, and five tensile test pieces B were prepared. Each tensile test specimen B was subjected to a tensile tester and the strength until cutting was measured. As a result, the strength was 1 KN / cm 2 or more.
  • Example 2-3 Anodized in a 15 wt% phosphoric acid aqueous solution for 20 minutes in advance, washed with water, and then electrolytically treated in an aqueous solution containing nitric acid 1 mol / L and phosphoric acid 1.5 mol / L in the same manner as in Example 2-2.
  • the same number of tensile test pieces C as those of Example 2-1 were prepared by combining aluminum alloy test pieces having the same size as that of Example 2-2. When the tensile test specimen C was applied to a tensile tester and the strength until cutting was measured, all had a strength of 1 KN / cm 2 or more.
  • Example 2-1 and Example 2-2 the ranking of the average value of the tensile strength of each of the tensile test pieces A, B, and C is as follows: Tensile test piece C> Tensile test piece B> Tensile test piece A Met.
  • the tensile test piece C is considered to have a large adhesive force as a result of the formation of a phosphoric acid anodic oxide film resulting in a porous film having a size of 300 angstroms on the aluminum surface and an increase in the adhesion area with the resin.
  • Example 2-3 anodization was performed to increase the adhesion area. However, in order to increase the adhesion area, the metal surface was previously roughened by etching or the like, and then the same energization treatment as in Example 2-3 was performed. You may do.
  • Example 3 The tensile test specimens A, B, and C described in Examples 2-1 to 2-3 are mounted on one end of a separately prepared mold, and polyacetal (POM) injection is injected into the space above the aluminum plate. As a result, the polyacetal (POM) portion was firmly welded to the aluminum. The aluminum part was taken out and attached again to a jig, and an anodized film was formed to a thickness of about 10 ⁇ m in a normal sulfuric acid bath. Dyeing and sealing treatment were carried out by ordinary methods, but this process also produced polyacetal (POM). ) Portion was firmly attached to the aluminum surface.
  • the aluminum plate that had been previously anodized with sulfuric acid by a conventional method was washed with water, put into the solutions of Example 1-1 and Example 1-2 without drying, and subjected to weak electrolysis for 10 minutes under the same conditions. .
  • the resin adhesive strength of the test piece after washing and drying was almost the same as in Example 1-1 and Example 1-2.
  • the film hardness was almost the same as when the same material was subjected to a normal sulfuric acid anodizing treatment.
  • Example 4-1 A hot-rolled titanium alloy plate and a 0.5-t test piece were processed in the same manner as in Example 2-1.
  • the plate surface showed a blue-purple interference color.
  • Polyacetal (POM) and acrylonitrile butadiene styrene resin (ABS) were joined to this test piece.
  • the adhesive strength was sufficiently high and there was almost no variation among the plurality of test pieces.
  • Example 4-2 A test piece similar to that in Example 4-1 was treated in the same manner as in Example 2-2. The plate surface showed a blue-purple interference color. Polyacetal (POM) and acrylonitrile butadiene styrene resin (ABS) were joined to this test piece. The adhesive strength was sufficiently high and there was almost no variation among the plurality of test pieces.
  • POM polyacetal
  • ABS acrylonitrile butadiene styrene resin
  • Example 5 First, the surface of a machine part made of SUS304 material is thoroughly degreased in an alkaline degreasing solution, washed with water, neutralized, washed with water in accordance with a normal surface treatment method, and then 5 parts of this machine part is 1.5 mol / L. Is placed in an aqueous solution containing nitrate ions and 1 mol / L phosphate ions, and is placed on the opposite side of the liquid tank as a non-dissolvable cathode as a non-dissolvable cathode.
  • a SUS304 mechanical component was placed on the anode side, a DC voltage was applied, the passing current value was set to about 0.5 A / dm 2, and energization was performed for about 20 minutes.
  • a dense oxide layer was formed by this treatment, and a slightly yellowish white hue was exhibited.
  • the flat surface of this part was coated with a paint mainly composed of polyamide / imide resin (PAI) and dispersed with molybdenum disulfide having solid lubricating performance, and cured by heating at 230 ° C. for 30 minutes.
  • PAI polyamide / imide resin
  • the surface was subjected to a reciprocating sliding wear tester, and a sliding test was performed by a so-called pin-on-disk method in which a bearing steel ball was reciprocated with a point load of 1 kg to evaluate the life of the solid lubricant film.
  • the test machine was set to automatically stop when the dynamic friction coefficient between the steel ball and the test surface reached 0.6, and the change in the dynamic friction coefficient for each reciprocation was recorded.
  • the coating produced in this example holds the solid lubricating layer on the surface of the mechanical part of SUS304 in a very strong contact, so that it is the same directly in the usual manner, that is, without performing the treatment according to this example.
  • the durability time or sliding distance in the sliding test increased 100 times or more for all five tested. It was confirmed that it was a long-term sliding characteristic achieved as a result of greatly increasing the adhesion of the coating film. That is, this treatment method was effective in maintaining strong adhesion of the coating film on the metal.
  • Example 6 As in Example 5, five mechanical parts of SUS304 were treated in the same manner as in Example 5 in a solution containing only 1.5 mol / L of nitrate ions and no phosphate ions. The surface gloss of the machine parts was generally more glossy than in Example 5. Next, coating was applied in the same manner as in Example 5, and the same pin-on-disk test was conducted. The sliding distance was almost the same, but the variation of the sliding distance of each machine part was larger than that of Example 5.
  • Example 7 An electroless nickel plating layer is formed in advance on the surface of a SUS304 material sliding part similar to that in Example 5 to a thickness of about 3 ⁇ m, and the surface of the mechanical part of SUS304 is treated by the same method as in Example 1-1 to form a film. In addition, a solid lubricant film layer similar to that in Example 5 was produced. Next, the surface was subjected to a sliding test by a pin-on-disk method. Compared to the case where the same solid lubricant was directly applied and formed into a film, the test result was even better, about 300 times that without treatment.
  • this example greatly increases the adhesion of the coating film. It turned out to be effective.
  • Example 8 The surface of the SUS304 plate plated with electroless nickel in the same manner as in Example 7 was treated with a liquid containing only 0.6 mol / L of nitrate ions by the same method as in Example 7. The same solid lubricant as in Example 7 was applied to this and tested. The test results were slightly lower than in Example 7.
  • Example 9-1 A normal structural rolled steel SPCC was tested as a test piece under the same current composition and conditions as in Example 1-1.
  • the electrolytic solution composition was the same as in Example 1-1, and the test was performed under the same conditions, and a test piece D having a treatment time of 10 minutes and a test piece E having a treatment time of 30 minutes were produced.
  • the steel surface was slightly yellow. Although the coloration was substantially uniform, the test piece E having a longer treatment time was more colored than the test piece D having a shorter treatment time, and the oxide layer was also densely formed.
  • An epoxy resin adhesive was placed on each of the test piece D and the test piece E, and the same treated SPCC plate was placed thereon, followed by thermocompression bonding.
  • the adhesive strength of the test piece that was not subjected to the treatment of this example was compared, the adhesive strength of the test piece that was subjected to the treatment of this example showed an adhesive strength that was three times or more that of the test piece that was not treated. There was no clear correlation between treatment time and intensity.
  • the same test was performed for a commercially available isocyanate adhesive, and the adhesive strength of the adhesive that was not treated in this example was compared. The adhesive strength was 3 times or more.
  • Example 9-2 A test piece F obtained by treating the structural rolled steel SPCC for 10 minutes and a test piece G treated for 30 minutes were manufactured in the same manner as in Example 9-1 under the same electrolytic solution composition and conditions as in Example 1-2.
  • the steel surface was slightly yellow. Although the coloring was substantially uniform, the test piece G with a longer processing time was more colored than the test piece F with a shorter processing time, and the oxide layer was densely formed.
  • an epoxy resin adhesive was placed on each of the test piece F and the test piece G, and the same treated SPCC plate was placed thereon, followed by thermocompression bonding and bonding.
  • the adhesive strength of the test piece that was not subjected to the treatment of this example was compared, the adhesive strength of the test piece that was subjected to the treatment of this example showed an adhesive strength that was three times or more that of the test piece that was not treated. There was no clear correlation between treatment time and intensity.
  • the same test was performed on a commercially available isocyanate adhesive, and the adhesive strength was compared with that without the treatment of this example. As compared with the epoxy adhesive without the treatment, The adhesive strength was 3 times or more.
  • the variation in the adhesive strength of the test piece prepared in this example in which phosphate ions were allowed to coexist was less stable than that in Example 9-1 in which phosphate ions were not allowed to coexist.
  • Example 10-1 A rectangular pure copper plate having a thickness of 0.5 mm and a size of 25 mm ⁇ 70 mm was used as a test piece. After degreasing, rinsing, neutralizing, and rinsing with a commercially available degreasing solution for plating pretreatment, it was treated with the same electrolytic solution composition and conditions as in Example 1-1. Using this test piece, a Duracon sheet was welded as a polyacetal (POM) film in the same manner as in Example 2-1, and when subjected to a tensile test with a maximum measured value of 300 kg, the welded portion with the polyacetal (POM) film was peeled off. There wasn't.
  • POM polyacetal
  • Example 10-2 A test piece similar to Example 10-1 was degreased, washed, neutralized and washed with a commercially available degreasing solution for plating pretreatment as in Example 10-1, and then the same electrolyte composition as in Example 1-2 And processed with conditions. Using this test piece, a Duracon sheet was welded as a polyacetal (POM) film in the same manner as in Example 2-1, and when subjected to a tensile test with a maximum measured value of 300 kg, the welded portion with the polyacetal (POM) film was peeled off. There wasn't.
  • Example 10-3 An electroless nickel plating layer of about 3 microns was applied to a copper-zinc alloy plate having the same thickness as that of Example 10-1, that is, a brass plate by a conventional method, and then the same electrolytic solution composition and conditions as in Example 1-1. Processed. Using these test pieces, a Duracon sheet was welded as a polyacetal (POM) film in the same manner as in Example 2-1, and subjected to a tensile test with a maximum measured value of 300 kg. Polyacetal (POM) welding was carried out for any of the test pieces. The part did not peel off.
  • POM polyacetal
  • Example 10-4 Using the same test piece as in Example 10-3, after applying an electroless nickel plating layer of about 3 microns by a conventional method, the treatment was performed with the same electrolytic solution composition and conditions as in Example 1-2. Using these test pieces, a Duracon sheet was welded as a polyacetal (POM) film in the same manner as in Example 2-1, and subjected to a tensile test with a maximum measured value of 300 kg. Polyacetal (POM) welding was carried out for any of the test pieces. The part did not peel off.
  • POM polyacetal
  • Example 11 For a pure nickel plate, a test piece having the same shape as in Example 2-1 was prepared and treated under the same electrolytic solution composition and conditions as in Example 2-2. However, the test time was divided into 10 minutes, 20 minutes, and 30 minutes to prepare 10 test pieces each. Two test pieces of each processing time were welded by sandwiching a POM sheet in the same manner as in Example 2-1, to prepare a tensile test piece. Each of the tensile test specimens was subjected to a tensile tester and the strength until cutting was measured. As a result, each had a strength of 1 KN / cm 2 or more. The tensile test results were almost the same for each group regardless of the treatment time.
  • Example 12 For a pure nickel plate, a test piece having the same shape as in Example 2-1 was prepared, and the electrolytic treatment solution composition was only 2 mol / L of nitrate ions, and the treatment was performed under the same conditions as in Example 2-1. As in Example 11, the treatment time was divided into 10 minutes, 20 minutes, and 30 minutes, and ten tensile test specimens were prepared. Each tensile test specimen was applied to a tensile tester and the strength until cutting was measured. As a result, the strength was 1 KN / cm 2 or more, and the test results were not significantly different from Example 11. However, the variation in strength until the cutting of each tensile test specimen was larger than that in Example 11. From this result, it was estimated that the addition of phosphate ions is effective in making the properties of the chemical conversion surface uniform.
  • Example 13 For a pure nickel plate, the same test piece as in Example 12 was used, the nitrate ion concentration of the electrolytic treatment solution was set to 6 mol / L, and the same tensile condition as in Example 12 was applied. A test piece was prepared and a tensile test was performed. The results of the tensile test were not much different from those of Example 12, but it was judged that the practicality was low due to many negative factors such as liquid discharge and gas odor to the working environment.
  • Example 14-1 A commercially available galvanized steel sheet was cut, degreased and washed with water, and the nitrate ion concentration was reduced to 1/3 of Example 1-1. After anodic electrolysis at dm 2 for 3 minutes, it was washed with water and dried. Prepare 0.2 mm thick films of polypropylene (PP) and polyacetal (POM), put the metal plate in an electric furnace, warm it to the softening temperature of the resin, take it out, and immediately press the resin sheet with a roller. Tested. Both polypropylene (PP) and polyacetal (POM) films were firmly bonded and laminated on a metal plate. However, the galvanized surface was slightly unevenly dissolved, which was not preferable in appearance.
  • PP polypropylene
  • POM polyacetal
  • Example 14-2 Similar to Example 14-1, after cutting, degreasing and washing with a commercially available galvanized steel sheet, the nitrate ion concentration was 0.2 mol / L, which was one-third that of Example 1-2, and phosphoric acid. After treatment in an aqueous solution containing 0.5 mol / L of ions under the same conditions as in Example 14-1, it was washed with water and dried. Prepare 0.2 mm thick films of polypropylene (PP) and polyacetal (POM), put the metal plate in an electric furnace, warm it to the softening temperature of the resin, take it out, and immediately press the resin sheet with a roller. Tested. Both polypropylene (PP) and polyacetal (POM) films were firmly bonded and laminated on a metal plate. However, the galvanized surface was slightly unevenly dissolved, which was not preferable in appearance.
  • PP polypropylene
  • POM polyacetal
  • Example 15 The cold rolled steel sheet SPCC was electrogalvanized with a blue bath, and subsequently, as in Example 14-1, caustic soda was added to an acidic aqueous solution containing 0.2 mol / L of nitrate ions to adjust the pH to 8, A test piece energized for 1 minute was prepared. After washing and drying, each test piece was placed on a heating plate, and when the heat softening temperature of polypropylene (PP) was reached as in Example 14-1, a polypropylene (PP) sheet was pressure-bonded and laminated. In the case of a polyacetal (POM) sheet, it was similarly laminated at the heat softening point, and both were laminated firmly and smoothly. The appearance had a loss of gloss.
  • PP polypropylene
  • POM polyacetal
  • Example 16 Cold-rolled steel plate SPCC is electrogalvanized with a bluening bath, followed by treatment in an aqueous solution containing nitrate ions of 0.3 mol / L, which is a nitrate ion concentration half that of Example 1-1.
  • POM polyacetal
  • the metal to be treated was subjected to cathodic electrolysis by reversing the polarity at the time of energization with that of Example 15, but by applying cathodic electrolysis, the dissolution of zinc was prevented and the gloss remained.
  • Example 17 cold-rolled steel plate SPCC was electrogalvanized with a blue bath, and subsequently nitrate ion concentration of 0.3 mol, which is half the concentration of nitrate ion and phosphate ion of Example 1-2.
  • the cold-rolled steel plate SPCC after electrogalvanization which is the metal to be treated, is connected to the cathode, the counter electrode is connected to the anode, and 20 ° C.
  • Cathodic electrolysis at 0.5 A / dm 2 for 1 minute.
  • a polyacetal (POM) sheet was welded in the same manner as in Example 15, the polyacetal (POM) sheet was firmly laminated with little variation. Further, as in Example 16, the dissolution of zinc was prevented and the gloss remained.
  • the metal to be treated when the galvanized surface is treated, the metal to be treated may be connected to the anode or may be treated by being connected to the cathode. good. However, when the treatment is performed by connecting to the cathode, the surface becomes less rough, and the surface finish becomes glossy.
  • Example 18 Magnesium alloy plate JISAZ31 was degreased, washed with water, neutralized, washed with water, 0.1 mol / L of nitrate ions and 0.1 mol / L of phosphate ions were contained, and PH was adjusted to about 8 as in Example 15. Anodization was conducted for 1 minute in an aqueous solution. Thereafter, it was washed with water and dried, and the magnesium plate was heated in a furnace in the same manner as in Example 16, and a sheet of polyethylene (PE), polypropylene (PP), acrylonitrile butadiene styrene resin (ABS), polyacetal (POM), etc. was laminated. did. In both cases, the adhesive force between the magnesium plate and the resin sheet was sufficient, but roughening due to dissolution of the surface was observed.
  • PE polyethylene
  • PP polypropylene
  • ABS acrylonitrile butadiene styrene resin
  • POM polyacetal
  • Example 19 After degreasing, washing, neutralizing, and washing the magnesium alloy plate JISAZ31, the magnesium alloy plate as the metal to be treated was connected to the cathode in an aqueous solution containing 0.6 mol / L of nitrate ions as in Example 1-1. The counter electrode was connected to the anode, and cathode electrolysis was performed at 20 ° C. and 0.5 A / dm 2 for 1 minute. When a polyacetal (POM) sheet was welded in the same manner as in Example 15, a strong laminate was obtained.
  • POM polyacetal
  • the metal to be treated was subjected to cathodic electrolysis by reversing the polarity at the time of energization with that of Example 18, but by applying cathodic electrolysis, dissolution of magnesium was prevented and the surface remained glossy.
  • Example 20 As in Example 19, magnesium alloy plate JISAZ31 was degreased, washed, neutralized, and washed with water, and as in Example 1-2, nitrate ions 0.6 mol / L and phosphate ions 0.5 mol / L were contained. In an aqueous solution, a magnesium alloy plate as a metal to be treated was connected to the cathode, a counter electrode was connected to the anode, and cathode electrolysis was performed at 20 ° C. and 0.5 A / dm 2 for 1 minute. When a polyacetal (POM) sheet was welded in the same manner as in Example 15, the polyacetal (POM) sheet was firmly laminated with little variation. As in Example 19, dissolution of magnesium was prevented and the surface remained glossy.
  • POM polyacetal
  • the metal to be processed may be connected to the anode or may be connected to the cathode.
  • the treatment is performed by connecting to the cathode, the surface becomes less rough, and the surface finish becomes glossy.
  • Example 1-2 the production of a composite material of an aluminum plate and resin on which adhesiveness has been formed by the method of Example 1-2 will be described.
  • FIG. 1 is a perspective view of a composite 11 in which a resin is integrated with an aluminum alloy plate 13, and FIG. 2 is a cross-sectional view thereof.
  • the composite 11 is formed with a resin mold 15 that encloses the outer peripheral edge of the aluminum alloy plate 13. Further, one surface of the aluminum alloy plate 13 is provided with ribs 17 whose both ends are integrated with the mold 15 at the periphery of the aluminum alloy plate 13 and bonded to the surface of the aluminum alloy plate 13.
  • FIG. 3 shows a cross-sectional view of the state in which the aluminum alloy plate 13 is set in a molding die for producing the composite 11 of the resin and the aluminum alloy plate 13 described in FIGS.
  • the mold has an upper mold 25 having an injection port 27 for injecting molten resin, and a resin injection path 29 and ribs for introducing the molten resin injected from the injection port 27 into each mold 15 and rib 17.
  • a middle mold 21 having a resin injection space 33 in the form of 17 and a lower mold 23 having a resin injection space 31 in the form of a mold 15 and supporting the aluminum alloy plate 13 are provided.
  • FIG. 3 shows a cross-sectional view of the state in which the aluminum alloy plate 13 is set in a molding die for producing the composite 11 of the resin and the aluminum alloy plate 13 described in FIGS.
  • the mold has an upper mold 25 having an injection port 27 for injecting molten resin, and a resin injection path 29 and ribs for introducing the molten resin injected from the injection port 27 into each mold 15 and
  • the upper mold 25, the middle mold 21, and the lower mold 23 are assembled so that the resin injection port 27, the resin injection passage 29, and the resin injection space 31 communicate with each other.
  • the aluminum alloy plate 13 that is energized and has an adhesive surface is set at a predetermined position on the lower mold 23.
  • the resin When the molten resin is press-fitted from the injection port 27, the resin is filled into the resin injection space 31 through the resin injection path 29. Then, it is pressed onto the adhesive surface of the aluminum alloy plate 13. After cooling, when the mold is removed and the aluminum alloy plate 13 is taken out, a mold 15 is formed around the aluminum alloy plate 13, and ribs 17 are formed on the surface of the aluminum alloy plate 13. Since the surface of the aluminum alloy plate 13 is subjected to the above-described energization treatment and has adhesiveness, the mold 15 and the rib 17 can be bonded to the surface of the aluminum alloy plate 13 to form a composite 11. it can.
  • the resin-metal composite may be integrally formed by other methods such as the outsert method, not by the insertion method by injection as described above, or by heating and pressing a film-like resin or the like. It is also possible to coat a resin-based paint to form a coating film, or apply an adhesive to a metal-adhesive surface and bond the metal to each other or the metal and the resin via the adhesive. May be joined together.

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  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Electrochemistry (AREA)
  • Materials Engineering (AREA)
  • Metallurgy (AREA)
  • Organic Chemistry (AREA)
  • Inorganic Chemistry (AREA)
  • Laminated Bodies (AREA)

Abstract

Un courant électrique est distribué entre une contre-électrode comprenant un matériau conducteur insoluble et un métal d'intérêt dans une solution aqueuse contenant des ions nitrate, mieux des ions phosphate et des ions nitrate, pour former une surface adhésive sur la surface du métal. Si le métal est l'aluminium, le titane, un acier, un acier inoxydable, le nickel, le cuivre, un alliage de l'un quelconque des métaux susmentionnés, ou une surface recouverte de l'un quelconque des matériaux susmentionnés, la distribution de courant est réalisée en reliant le métal à une anode. Si le métal est le zinc, le magnésium, un alliage de l'un quelconque des métaux susmentionnés, ou une surface recouverte de l'un quelconque des matériaux susmentionnés, la distribution de courant est réalisée en reliant le métal à une cathode. De cette manière, un matériau métallique modifié en surface présentant une bonne adhérence aux articles en plastique, aux matières plastiques industrielles, aux élastomères, aux films de revêtement et aux agents adhésifs peut être fabriqué.
PCT/JP2010/053115 2010-02-26 2010-02-26 Matériau métallique modifié en surface, complexe de matériau métallique modifié en surface, résine, élastomère et film de revêtement, et procédé de fabrication associé WO2011104868A1 (fr)

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Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS50108138A (fr) * 1974-02-01 1975-08-26
JPS591699A (ja) * 1982-06-26 1984-01-07 Mitsubishi Alum Co Ltd アルミニウム又はアルミニウム合金の皮膜生成法
JPH0813154A (ja) * 1994-06-27 1996-01-16 Nippon Parkerizing Co Ltd 塗装性に優れた亜鉛含有金属めっき鋼板複合体、およびその製造方法
JP2010053392A (ja) * 2008-08-27 2010-03-11 Sanbesuto:Kk 表面改質金属材料及び表面改質金属材料と樹脂、エラストマー、塗膜との複合体並びにその製造方法

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS50108138A (fr) * 1974-02-01 1975-08-26
JPS591699A (ja) * 1982-06-26 1984-01-07 Mitsubishi Alum Co Ltd アルミニウム又はアルミニウム合金の皮膜生成法
JPH0813154A (ja) * 1994-06-27 1996-01-16 Nippon Parkerizing Co Ltd 塗装性に優れた亜鉛含有金属めっき鋼板複合体、およびその製造方法
JP2010053392A (ja) * 2008-08-27 2010-03-11 Sanbesuto:Kk 表面改質金属材料及び表面改質金属材料と樹脂、エラストマー、塗膜との複合体並びにその製造方法

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