JP6836714B2 - Manufacturing method of metal / resin composite material - Google Patents

Description

The present invention relates to, for example, high-frequency transmission cables, antennas, high-frequency circuit boards, or electrical components such as flexible elliptical waveguides, medical devices such as guide wires having a fluororesin coating, or frying pans having a fluororesin coating. The present invention relates to a method for producing a metal / resin composite material used for a heating cooker or the like.

Fluorine-based resins are known as polymer materials having various properties such as heat resistance, chemical resistance, and electrical properties. By integrating this fluorinated resin and metal parts, high-performance materials that combine the characteristics of fluorinated resins with the excellent workability, conductivity, and strength of metal parts are expected, and some have been released so far. The form of is proposed. (See Patent Documents 1 and 2)

However, since the fluororesin has low adhesion to different materials, many methods for improving the adhesion to metal parts have been studied so far.

Patent Document 1 proposes a method of roughening the surface of a fluororesin surface by sandblasting or wet blasting to improve the adhesion between the fluororesin and a metal part by utilizing the anchor effect.

Patent Document 2 describes a method in which the surface of a fluororesin or a metal surface is roughened by an etching treatment using a chemical solution, and the adhesion between the fluororesin and a metal part is improved by utilizing the anchor effect. Proposed.

Japanese Unexamined Patent Publication No. 11-61054 Japanese Unexamined Patent Publication No. 2013-52671

However, in the roughening treatment by sandblasting or wet blasting, a polishing agent of hard fine particles mainly composed of alumina or the like is used, but a part of the polishing agent wiped at high speed and high pressure is a soft fluororesin. There is a risk that it will be buried or remain in the metal parts and the adhesion of the metal part / fluororesin interface will be reduced.

Further, when a metal part having a rough surface (uneven surface) formed on the surface is used as a member for high-speed transmission in which a large amount of current flows through the surface layer of a conductor due to the skin effect, the rough surface deteriorates transmission characteristics. May cause. Further, even when an uneven surface is formed on the resin surface, the uneven surface is transferred to the metal surface when bonded to a metal (conductor), so that the uneven surface is transferred when used as a member for high-speed transmission. The rough surface may cause deterioration of transmission characteristics.

In addition, the blast method is a large-scale device and a high-cost product. Further, since the blast method is a physical process, it is difficult to uniformly roughen the surface of a large area or roughen a three-dimensional member.

When a chemical etching treatment method using a chemical solution is selected as another means, the fluororesin has excellent chemical resistance and cannot be easily roughened by general chemical treatment. For example, a metallic sodium solution. It is conceivable to use a special method using.

Even if the uneven surface formed by the chemical treatment is formed not only on the surface side of the fluororesin but also on the surface side of the metal member, it may cause deterioration of transmission characteristics in the case of high-speed transmission application as in the above-mentioned blast method. There is.

Therefore, an object of the present invention is to provide a metal / resin composite material having a fluorine-based resin base material having excellent adhesion on the metal base material without forming irregularities on the surface of the metal base material.

The present invention provides the following metal / resin composite materials [1] to [4] in order to achieve the above object.

[1] A metal / resin composite material provided with an intermediate layer made of zinc or an alloy containing zinc between a metal member and a fluororesin base material.

[2] The metal / resin composite material according to [1], wherein a compound composed of zinc and fluorine is formed at the interface between the intermediate layer and the fluorine-based resin base material.

[3] The metal / resin composite material according to [1] or [2], wherein the metal member is copper or a copper alloy.

[4] The metal / resin composite material according to [1] to [3], wherein the thickness of the intermediate layer is 3 nm or more.

According to the present invention, it is possible to provide a metal / resin composite material having a fluorine-based resin base material having excellent adhesion on the metal base material without forming irregularities on the surface of the metal base material.

It is a schematic diagram which shows the cross-sectional structure of the metal-resin composite material which concerns on 1st Embodiment of this invention. It is a schematic diagram which shows the cross-sectional structure of the metal-resin composite material which concerns on 2nd Embodiment of this invention. It is a schematic diagram which shows the cross-sectional structure of the metal-resin composite material which concerns on 3rd Embodiment of this invention. It is a schematic diagram which shows the cross-sectional structure of the metal-resin composite material which concerns on 4th Embodiment of this invention. It is a schematic diagram which shows the cross-sectional structure of the metal-resin composite material which concerns on 5th Embodiment of this invention. It is a graph which shows the Auger analysis result of the metal-resin composite material which concerns on the 9th Example of this invention. It is a conceptual diagram of a wire rod adhesion evaluation test.

(First Embodiment)
Hereinafter, the first embodiment of the present invention will be described with reference to FIG. The embodiments shown below are shown as suitable specific examples for carrying out the present invention, and there are some parts that specifically exemplify various technically preferable technical matters. The technical scope of the present invention is not limited to this specific aspect.

FIG. 1 is a schematic view showing a cross-sectional structure of the metal / resin composite material 1 according to the first embodiment of the present invention. As shown in FIG. 1, the metal / resin composite material 1 has a structure in which an intermediate layer 3 made of zinc or an alloy containing zinc is provided between the metal member 4 and the fluororesin base material 2. ..

(Fluorine-based resin base material)
A fluororesin is a polymer compound having a fluorine atom in its molecule, and is a polyvinylidene fluoride (PVF) resin, an ethylene / tetrafluoroethylene copolymer (ETFE) resin, or a tetrafluoride ethylene / perfluoroalkoxyethylene coweight. Combined (PFA) resins, ethylene tetrafluoride / propylene hexafluoride copolymer (FEP) resins, polyvinylidene fluoride (PVDF) resins and the like are known. These fluorine-based resins or a fluorine-based resin obtained by cross-linking these can be used as the fluorine-based resin base material 2.

(Metal member)
An example of the metal member 4 to be integrated with the fluororesin base material 2 is copper, but the copper does not necessarily have to be oxygen-free copper, tough pitch copper, and pure copper, and a copper alloy can also be used. For example, a dilute copper alloy containing 3 to 15 mass ppm of sulfur (S), 2 to 30 mass ppm of oxygen (O) and titanium (Ti) at 5 to 55 mass ppm can be used.

The metal member 4 is not limited to copper, and aluminum, iron, stainless steel, titanium, magnesium, and alloys containing them as main components can be used as long as the effects of the present invention are exhibited.

(Middle layer)
Examples of the intermediate layer 3 include pure zinc and a Zn-based alloy composed of Zn—Ni, Zn—Al, Zn—Cu, Zn—Sn and the like.

The upper limit of the thickness of the intermediate layer 3 is not particularly limited in order to ensure the adhesion, and it is sufficient that the surface of the metal member 4 is coated, and the practical lower limit of the coating thickness is 3 nm. Degree. However, when used for high-speed transmission, if a Zn-based intermediate layer having low conductivity is thickly present on the surface layer of the metal member 4, transmission characteristics will be deteriorated. Therefore, the thickness of the intermediate layer 3 is preferably 1 μm or less, more preferably. It is preferably 0.8 μm or less.

(Manufacturing method of metal / resin composite material)
In the production of the metal / resin composite material 1 of the present invention, for example, first, an intermediate layer 3 made of zinc or an alloy containing zinc is formed on the surface of the metal member 4 by a plating method, a sputtering method, a vacuum vapor deposition method, a clad method or the like. Form. Next, the metal member 4 on which the intermediate layer 3 is formed and the fluororesin base material 2 are integrated to manufacture the metal / resin composite material 1.

This integration can be performed by, for example, pressing if the metal member 4 on which the intermediate layer 3 is formed and the fluororesin base material 2 have a sheet shape or a plate shape. In order to further enhance the adhesion, a method such as maintaining an isothermal temperature at 50 ° C. to 350 ° C. after a low temperature press at 100 ° C. or lower can be applied in addition to a high temperature press at 100 ° C. to 350 ° C.

When the metal member 4 has a sheet (foil) shape, the structure is not limited to the configuration in which the intermediate layer 3 is formed only on one side surface in contact with the fluororesin base material 2. When the intermediate layer 3 is formed by a plating method or the like, the intermediate layer 3 may be formed on both sides of the sheet (foil) from the viewpoint of workability.

Further, in the above manufacturing method, the intermediate layer 3 is first formed on the surface of the metal member 4, but the same method can be used even if the intermediate layer 3 is formed on the surface of the fluororesin base material 2 by a sputtering method, a plating method, or the like. The metal / resin composite material 1 can also be manufactured. The fluororesin base material 2 on which the intermediate layer 3 is formed and the metal member 4 can be integrated by, for example, a clad method or the like. When the intermediate layer 3 is formed on the surface of the sheet-shaped fluororesin base material 2 by a plating method or the like, the intermediate layers 3 may be formed on both sides of the sheet from the viewpoint of workability.

(Other embodiments)
Next, other embodiments of the present invention will be described with reference to FIGS. 2 to 5.
FIG. 2 is a schematic view showing a cross-sectional structure of the metal / resin composite material 1 according to the second embodiment of the present invention. As shown in FIG. 2, in this metal / resin composite material 1, for example, when heat is applied, zinc and fluorine are formed at the interface between the intermediate layer 3 made of zinc or an alloy containing zinc and the fluorine-based resin base material 2. A compound 5 composed of the above is formed. The present inventors believe that the compound 5 composed of zinc and fluorine further improves the adhesion (bonding strength) between the fluorine-based resin base material 2 and the metal member 4.

FIG. 3 is a schematic view showing a cross-sectional structure of the metal / resin composite material 1 according to the third embodiment of the present invention, and FIG. 4 is a schematic view showing the cross-sectional structure of the metal / resin composite material 1 according to the fourth embodiment of the present invention. It is a schematic diagram which shows the cross-sectional structure of. The shape of the wire rod as shown in FIGS. 3 and 4 is also possible. It is also possible to use a flat lumber shape instead of a wire rod shape.

When the metal member 4 on which the intermediate layer 3 is formed is in the shape of a wire rod or a flat lumber, the intermediate layer 3 is formed by continuously extruding a fluororesin heated to 250 ° C. to 350 ° C. in the longitudinal direction. It is also possible to integrate the metal member 4 and the fluororesin base material 2 through the metal member 4.

Generally, in the case of extrusion molding, it is desired to increase the production speed in order to reduce the cost by improving the productivity. However, if the cooling rate of the fluororesin after extrusion is increased in order to increase the production rate, the stress at the metal-resin interface generated during heat shrinkage of the fluororesin increases, and a gap is created between the metal and the resin. It ends up.
On the other hand, in the method of the present invention, since the intermediate layer 3 made of zinc or an alloy containing zinc is present, the adhesion between the intermediate layer 3 and the fluororesin base material 2 is high, so that voids may be generated. Instead, the cooling rate is increased, that is, the production by high-speed extrusion molding becomes possible.

FIG. 5 is a schematic view showing a cross-sectional structure of the metal / resin composite material 1 according to the fifth embodiment of the present invention. As shown in FIG. 5, a diffusion layer 6 made of the elements constituting the metal member 4 and zinc may be formed between the intermediate layer 3 and the metal member 4. Further, the zinc existing as the intermediate layer 3 is not limited to metallic zinc, and the surface (the surface facing the fluororesin base material 2) may be partially oxidized to become zinc oxide.

The metal / resin composite material 1 shown in FIGS. 1, 2 and 5 has a configuration in which the fluorine-based resin base material 2 is formed on only one side of the metal member 4, but the fluorine-based resin base material 2 is a metal. The structure may be formed on both sides so as to sandwich the member 4. Further, the metal member 4 may be formed on both sides so as to sandwich the fluororesin base material 2.

Hereinafter, the present invention will be described in more detail with reference to Examples, but the present invention is not limited to these Examples.

Table 1 shows the configurations of the evaluation samples of Examples 1 to 7, Comparative Examples 1 to 5, and Conventional Example 1. Table 1 also shows the evaluation results for the evaluation items described later.

Details of Examples 1 to 7, Comparative Examples 1 to 5 and Conventional Example 1 are shown below.

(Example 1)
One side surface of the electrolytic copper foil having a thickness of 0.07 mmt was sealed so as not to adhere to the plating, and then an intermediate layer made of Zn having a thickness of 0.003 μm was formed only on one side surface without the seal by electrogalvanization. Then, by laminating with a rolling roll to which heat (300 ° C.) and pressure (2 MPa) were applied, the electrolytic copper foil and the FEP sheet (thickness 0.5 mmt) were integrated via an intermediate layer to prepare a sample.

(Example 2)
One side surface of the electrolytic copper foil having a thickness of 0.07 mmt was sealed so as not to adhere to the plating, and then an intermediate layer made of Zn having a thickness of 0.01 μm was formed only on one side surface without the seal by electrogalvanization. Then, by laminating with a rolling roll to which heat (300 ° C.) and pressure (2 MPa) were applied, the electrolytic copper foil and the FEP sheet (thickness 0.5 mmt) were integrated via an intermediate layer to prepare a sample.

(Example 3)
One side surface of the electrolytic copper foil having a thickness of 0.07 mmt was sealed so as not to adhere to the plating, and then an intermediate layer made of Zn having a thickness of 0.1 μm was formed only on one side surface without the seal by electrogalvanization. Then, by laminating with a rolling roll to which heat (300 ° C.) and pressure (2 MPa) were applied, the electrolytic copper foil and the FEP sheet (thickness 0.5 mmt) were integrated via an intermediate layer to prepare a sample.

(Example 4)
One side surface of the electrolytic copper foil having a thickness of 0.07 mmt was sealed so as not to adhere to the plating, and then an intermediate layer made of Zn having a thickness of 0.5 μm was formed only on one side surface without the seal by electrogalvanization. Then, by laminating with a rolling roll to which heat (300 ° C.) and pressure (2 MPa) were applied, the electrolytic copper foil and the FEP sheet (thickness 0.5 mmt) were integrated via an intermediate layer to prepare a sample.

(Example 5)
One side surface of the electrolytic copper foil having a thickness of 0.07 mmt was sealed so as not to adhere to the plating, and then an intermediate layer made of Zn having a thickness of 0.8 μm was formed only on one side surface without the seal by electrogalvanization. Then, by laminating with a rolling roll to which heat (300 ° C.) and pressure (2 MPa) were applied, the electrolytic copper foil and the FEP sheet (thickness 0.5 mmt) were integrated via an intermediate layer to prepare a sample.

(Example 6)
One side surface of the electrolytic copper foil having a thickness of 0.07 mmt was sealed so as not to adhere to the plating, and then an intermediate layer made of Zn having a thickness of 1.0 μm was formed only on one side surface without the seal by electrogalvanization. Then, by laminating with a rolling roll to which heat (300 ° C.) and pressure (2 MPa) were applied, the electrolytic copper foil and the FEP sheet (thickness 0.5 mmt) were integrated via an intermediate layer to prepare a sample.

In Examples 1 to 6, the Zn thickness was controlled by keeping the plating current density constant and changing the plating time.

(Example 7)
An intermediate layer made of Zn-5 mass% Ni having a thickness of 0.5 μm was formed only on one side surface of an electrolytic copper foil having a thickness of 0.07 mmt by an electroplating method. Then, by laminating with a rolling roll to which heat (300 ° C.) and pressure (2 MPa) were applied, the electrolytic copper foil and the FEP sheet (thickness 0.5 mmt) were integrated via an intermediate layer to prepare a sample.

(Comparative Example 1)
The surface of the electrolytic copper foil with a thickness of 0.07 mmt is only degreased and washed with an organic solvent, and then the electrolytic copper foil is laminated through the degreased and cleaned surface by laminating with a rolling roll to which heat (300 ° C.) and pressure (2 MPa) are applied. And the FEP sheet (thickness 0.5 mmt) were integrated to prepare a sample.

(Comparative Example 2)
One side surface of the electrolytic copper foil having a thickness of 0.07 mmt was sealed so as not to adhere to the plating, and then an intermediate layer made of Sn having a thickness of 0.3 μm was formed only on one side surface without the seal by electrotin plating. Then, by laminating with a rolling roll to which heat (300 ° C.) and pressure (2 MPa) were applied, the electrolytic copper foil and the FEP sheet (thickness 0.5 mmt) were integrated via an intermediate layer to prepare a sample.

(Comparative Example 3)
One side surface of the electrolytic copper foil having a thickness of 0.07 mmt was sealed so as not to adhere to the plating, and then an intermediate layer made of Sn having a thickness of 1.0 μm was formed only on one side surface without the seal by electrotin plating. Then, by laminating with a rolling roll to which heat (300 ° C.) and pressure (2 MPa) were applied, the electrolytic copper foil and the FEP sheet (thickness 0.5 mmt) were integrated via an intermediate layer to prepare a sample.

(Comparative Example 4)
One side of an electrolytic copper foil with a thickness of 0.07 mmt is sealed so that plating does not adhere, and then only on one side without a seal is electro-Ag plated with a cyanide bath to form an intermediate made of Ag with a thickness of 0.3 μm. A layer was formed. Then, by laminating with a rolling roll to which heat (300 ° C.) and pressure (2 MPa) were applied, the electrolytic copper foil and the FEP sheet (thickness 0.5 mmt) were integrated via an intermediate layer to prepare a sample.

(Comparative Example 5)
One side of an electrolytic copper foil with a thickness of 0.07 mmt is sealed so that plating does not adhere, and then only on one side without a seal is electro-Ag plated with a cyanide bath to form an intermediate of 1.0 μm thick Ag. A layer was formed. Then, by laminating with a rolling roll to which heat (300 ° C.) and pressure (2 MPa) were applied, the electrolytic copper foil and the FEP sheet (thickness 0.5 mmt) were integrated via an intermediate layer to prepare a sample.

(Conventional example 1)
Unevenness was formed on the surface of a FEP sheet having a thickness of 0.5 mmt by a blasting method in which an alumina abrasive having an average particle size of 10 μm was sprayed at high speed. Then, by laminating with a rolling roll to which heat (300 ° C.) and pressure (2 MPa) were applied, a FEP sheet (thickness 0.5 mmt) and a copper foil that had only been degreased and washed with an organic solvent were formed through the uneven forming surface. Was integrated to prepare a sample.

(Adhesion evaluation test)
The adhesion evaluation between the metal and the resin shown in Table 1 was carried out by a tensile test by Autograph (Shimadzu Corporation) in accordance with JIS C6481. When the peeling strength was 0.5 kN / m or more, it was evaluated as ⊚, when it was 0.2 kN / m or more and less than 0.5 kN / m, it was evaluated as ◯, and when it was less than 0.2 kN / m, it was evaluated as x.

(Transmission characteristic evaluation test)
For the evaluation of the transmission characteristics, a network analyzer was used to measure the transmission loss corresponding to the frequency of 10 GHz. The transmission loss of less than 20 dB / m was evaluated as ◯, the transmission loss of 20 dB / m or more and less than 25 dB / m was evaluated as Δ, and the transmission loss of 25 dB / m or more was evaluated as ×.

(Environmental resistance evaluation)
The environmental resistance was evaluated by evaluating the toxicity and handleability of chemicals and materials used in sample preparation to the human body and the environment, as well as the degree of environmental impact when they were stored and discharged.

(Comprehensive evaluation)
The above items were comprehensively evaluated, and those with x in even one item were judged to be x unsuitable, those with all items being ○ were judged to be good, and those with more than that were judged to be ◎ best.

According to Table 1, the metal / resin adhesion of Examples 1 to 6 provided with an intermediate layer made of Zn whose thickness was changed from 0.003 μm to 1.0 μm between the copper foil and the FEP sheet was good. It was. Among them, when the Zn thickness is 0.01 μm to 0.5 μm, particularly excellent adhesion is exhibited, which is preferable.

On the other hand, Comparative Examples 1 having no intermediate layer, Comparative Examples 2 and 3 having an intermediate layer made of Sn, and Comparative Examples 4 and 5 having an intermediate layer made of Ag had poor adhesion. Good results were obtained in Conventional Example 1, in which the adhesion was improved by the anchor effect due to the unevenness formed by blasting.

Regarding the transmission characteristics, good results were obtained in Examples 1 to 5, Comparative Examples 1, 2 and 4, 5. On the other hand, in Example 6 and Comparative Example 3, the transmission loss was slightly larger. It is considered that this is because high-resistance Zn and Sn are present thicker than the samples under other conditions as the physical characteristics of the material, and thus the increase in loss is affected by the skin effect. From this result, from the viewpoint of metal / resin adhesion, the Zn thickness is practically effective from about 3 nm without an upper limit, but the Zn thickness when used for high-speed transmission characteristic applications is 1.0 μm or less. Is more preferable.

Conventional example 1 has a high transmission loss. It is considered that this is because the unevenness of the resin surface formed for improving the metal / resin adhesion is transferred to the metal surface, and the unevenness is also formed on the metal surface.

Regarding the environmental resistance, it can be judged that there is no problem in Examples 1 to 6 and Comparative Examples 1 to 3. Comparative Examples 4 and 5 provided with an intermediate layer made of Ag use a highly toxic cyan bath even if they are used in a work environment or a place where wastewater treatment is well-prepared, and therefore have a high impact on the environment. And said. Conventional Example 1 uses alumina, which has low toxicity, as a material, but since it is a fine powder on the order of several tens of μm, it is set as Δ in consideration of the influence on pneumoconiosis and the like.

It goes without saying that the composite materials according to Examples 1 to 6 are economical as compared with Ag plating and the like shown in Comparative Examples 4 and 5 because inexpensive Zn is used as the material.

Example 7 is the result of a Zn—Ni alloy instead of pure Zn, but it was confirmed that the same result as that of pure Zn can be obtained even when a Zn-based alloy is used.

Comprehensively judging from these results, as a metal-resin composite material having high adhesion between the metal member and the fluororesin base material and having good characteristics in high-speed transmission applications, the composites shown in Examples 1 to 7 are used. Materials can be proposed.

Table 2 shows the configurations of the evaluation samples of Examples 8 to 10 and Comparative Examples 6 and 7. Table 2 also shows the evaluation results for the evaluation items described later.

Details of Examples 8 to 10 and Comparative Examples 6 and 7 are shown below.

(Example 8)
An intermediate layer made of Zn having a thickness of 0.008 μm was formed by electrogalvanizing a pure copper wire having a wire diameter of Φ0.25 mm. A wire rod-shaped sample was prepared by extruding and molding FEP on the pure copper wire on which this intermediate layer was formed and integrating it. In the extrusion molding, the pure copper wire was continuously coated with a resin (thickness 0.5 mmt) at 340 ° C. and cooled by water cooling.

(Example 9)
An intermediate layer made of Zn having a thickness of 0.03 μm was formed by electrogalvanizing a pure copper wire having a wire diameter of Φ0.25 mm. A sample was prepared by extruding and molding FEP on the pure copper wire on which this intermediate layer was formed and integrating it. In the extrusion molding, the pure copper wire was continuously coated with a resin (thickness 0.5 mmt) at 340 ° C. and cooled by water cooling.

(Example 10)
An intermediate layer made of Zn having a thickness of 0.3 μm was formed by electrogalvanizing a pure copper wire having a wire diameter of Φ0.25 mm. A sample was prepared by extruding and molding FEP on the pure copper wire on which this intermediate layer was formed and integrating it. In the extrusion molding, the pure copper wire was continuously coated with a resin (thickness 0.5 mmt) at 340 ° C. and cooled by water cooling.

In Examples 8 to 10, the Zn thickness was controlled by keeping the plating current density constant and changing the plating time.

(Comparative Example 6)
A sample was prepared by only degreasing and cleaning the surface of a pure copper wire having a wire diameter of Φ0.25 mm with an organic solvent, and then extruding and integrating the FEP. In the extrusion molding, the pure copper wire was continuously coated with a resin (thickness 0.5 mmt) at 340 ° C. and cooled by water cooling.

(Comparative Example 7)
An intermediate layer made of Ag having a thickness of 1.0 μm was formed by electro-Ag plating using a cyan bath on a pure copper wire having a wire diameter of Φ0.25 mm. A sample was prepared by extruding and molding FEP on the pure copper wire on which this intermediate layer was formed and integrating it. In the extrusion molding, the pure copper wire was continuously coated with a resin (thickness 0.5 mmt) at 340 ° C. and cooled by water cooling.

(Wire rod adhesion evaluation test)
In the evaluation of the adhesion between the metal and the resin shown in Table 2, as shown in FIG. 7, a weight 7 having a weight of 20 g was hung from the lower end of the sample, and the sample was formed at a rate of 10 times / minute along a roll 8 having a diameter of 20 mm. After repeated bending at 90 ° 10 times, the presence or absence of a gap between the metal wire and the resin was confirmed by observing the cross section of the bent portion (magnification: 500 times). Of the n = 10 samples, those in which two or more voids were found were marked with x, and those with less than two voids or no voids were marked with ◯.

(Environmental resistance evaluation and comprehensive evaluation)
The environmental resistance evaluation and the comprehensive evaluation were based on the same criteria as those shown in Table 1.

According to Table 2, even in a cable in which various copper wires are extruded and coated with a fluororesin, an intermediate layer made of Zn whose thickness is changed from 0.008 μm to 0.3 μm between the copper wire and the fluororesin. The metal / resin adhesion of Examples 8 to 10 provided with the above was good. On the other hand, Comparative Example 6 having no intermediate layer and Comparative Example 7 having an intermediate layer made of Ag had poor adhesion.

FIG. 6 shows the results of elemental analysis of the conductor surface of the sample of Example 9 after peeling the FEP coated on the pure copper wire (conductor) by Auger electron spectroscopy while repeating sputtering. The horizontal axis of FIG. 6 is the sputtering time. It should be _{noted that the sputter rate (11 nm / min) of SiO 2} can be converted into a thickness unit, and a guideline for the depth from the surface layer can be grasped.

From the result of Auger analysis, it can be seen that Zn on the conductor surface exists up to a depth of about 30 nm. Fluorine (F) is detected from the surface layer up to about 6 nm.

Table 3 shows the results of analyzing the surface of the same sample (Example 9) as in FIG. 6 by X-ray photoelectron spectroscopy (XPS) in order to analyze the bonding state of the elements detected by these Auger analyzes. The analysis points of XPS are (1) the outermost surface (no sputtering (sputtering time 0 min)), (2) sputtering time 0.1 min, and (3) sputtering time 1 min. As a result of XPS analysis, it was found that _{Zn exists as a zinc fluoride (ZnF 2} ) in addition to a metallic state, an oxide, or a Cu-Zn compound. _{The inventors believe that the formation of this ZnF 2} composed of the mutual components of the metal member and the resin can improve the adhesion between the metal and the fluororesin interface shown in the present invention.

Regarding the environmental resistance, as in Table 1, Zn plating Examples 8 to 10 capable of forming a non-cyanide film are superior to Ag plating of Comparative Example 7 in which a cyanide bath is used for surface treatment. There is.

Although the embodiments of the present invention have been described above, the embodiments described above do not limit the invention according to the claims. It should also be noted that not all combinations of features described in the embodiments are essential to the means for solving the problems of the invention. In addition, the present invention can be appropriately modified and implemented without departing from the spirit of the present invention.

For example, in a signal transmission cable having a central conductor, an insulator, an outer conductor, and a sheath in sequence, a fluororesin is used as an insulator, and a copper foil having a Zn plating layer or a Zn alloy plating layer is wound and integrated as the outer conductor. It is also possible to improve the adhesion between the insulator (fluorine-based resin) and the outer conductor (Zn plating layer or Zn alloy plating layer) so that a sufficient shielding effect can be obtained.

1 Metal / resin composite material 2 Fluorine-based resin base material 3 Intermediate layer 4 Metal member 5 Compound composed of zinc and fluorine 6 Diffusion layer composed of elements and zinc constituting the metal member

Claims (3)

Forming an intermediate layer made of an alloy containing zinc or zinc to the outer periphery of the metallic member the form of a wire, method of manufacturing a metal-resin composite material to extrude a full Tsu Motokei resin substrate on the outer periphery thereof. The method for producing a metal / resin composite material according to claim 1, wherein zinc fluoride is formed at the interface between the intermediate layer and the fluorine-based resin base material. The method for producing a metal / resin composite material according to claim 1 or 2 , wherein the thickness of the intermediate layer is 3 nm or more.

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