JP2000025154A - Laminated aluminum panel for drawing/squeezing processing and production thereof - Google Patents

Abstract

PROBLEM TO BE SOLVED: To prevent generation of breaking, cracking and ply separation of a resin layer even if drawing processing and squeezing processing are applied. SOLUTION: An intermediate layer containing a silane coupling agent having an amino group is provided between a base panel comprising aluminum or an aluminum alloy and a resin film. This intermediate layer may comprise the silane coupling agent alone or a mixture of the silane coupling agent and ammonium polyacrylate. The thickness of this intermediate layer is 0.01-2.0 μm. The resin film comprises a polyamide resin or a Teflon resin. This laminated aluminum panel is produced by coating the base panel comprising aluminum or the aluminum alloy with the silane coupling agent having the amino group or a mixed soln. of this silane coupling agent and ammonium polyacrylate and drying the coated panel at a drying temp. of 30 - below 250 deg.C for 5 sec-10 min and subsequently laminating the resin film at a temp. of 30 deg.C - the m.p. of the resin.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a laminated aluminum plate for drawing and ironing which can be applied to an outer case of electronic parts such as a capacitor cap for accommodating an electrolytic capacitor element and a cap of a microphone capacitor, and a method of manufacturing the same. Particularly, in drawing / ironing, etc., a high-strength laminated aluminum plate for drawing / ironing with excellent interlayer adhesion by suppressing delamination between the resin film and the aluminum plate and cracking of the resin layer, and a method for producing the same About. In the present invention, even when only aluminum is described, an aluminum alloy is included in addition to pure aluminum.

[0002]

2. Description of the Related Art A laminated aluminum plate obtained by laminating various resin films on an aluminum or aluminum alloy plate has been used in various fields for the purpose of corrosion resistance, electrical insulation, and design. In particular, a laminated aluminum plate laminated with a polyamide resin having excellent heat resistance and moldability is used as a capacitor cap, and a laminated aluminum plate laminated with a Teflon resin is used as a microphone cap.

[0003] An aluminum electrolytic capacitor is constituted by housing a capacitor element impregnated with an electrolyte in a bottomed cylindrical capacitor cap formed by drawing an aluminum plate by drawing. The portion is sealed with rubber or the like, and a heat-shrinkable tube such as a vinyl chloride resin or a polyolefin resin is coated on the outer peripheral surface for the purpose of electric insulation and display of contents.

[0004] A condenser microphone converts a signal corresponding to a change in capacitance between the diaphragm and a fixed electrode through an impedance conversion element by vibration of the diaphragm due to sound waves from a sound source, and outputs the signal from an output terminal. The structure is described in, for example,
It is covered with a cap as shown in FIG.

[0005] With the spread of mobile phones and the like, miniaturization of electronic components is progressing, and miniaturization of aluminum electrolytic capacitors and condenser microphones is also required. As for aluminum electrolytic capacitors, chip-type aluminum electrolytic capacitors in which lead wires for surface mounting are omitted are being developed. With such a small aluminum electrolytic capacitor cap, it is extremely difficult to cover the above-described heat-shrinkable tube, and the outer container becomes smaller, so that the stored capacitor element comes into contact with the inner surface of the container, and insulation is impaired. Problem.
In addition, vinyl chloride has been promoted as a measure against dioxin associated with recent environmental protection, and it has been desired to omit the vinyl chloride resin covering the capacitor even in a large aluminum electrolytic capacitor. As a countermeasure, a technique has been put to practical use in which the coating of a tube is omitted and the insulating property is improved by drawing and ironing a laminated material in which the surface of an aluminum plate is coated with an insulating resin layer in advance. As a method of coating the insulating resin layer, a method of coating a resin such as an epoxy-based, vinyl chloride-based, or polyester-based resin, and a method of coating the surface by laminating a resin film on the surface of an aluminum material as described above. There is. Also for condenser microphones,
Application of a laminating material is disclosed (for example, JP-A-8-149598).

On the other hand, as a method for improving the interlayer adhesion between the aluminum material and the resin film, the interlayer adhesion can be improved by providing a heat-treated epoxy resin coating between the polyamide resin and the metal material surface. It has been disclosed (Japanese Patent Laid-Open No. 1-238931).

[0007]

However, in the above-mentioned coating material, when the drawing and the ironing are performed, even if the adhesion before the processing and the adhesion after the drawing are good, the resin layer is broken. In addition, there is a problem that cracks and delamination are likely to occur. In addition, in the method of providing a modified epoxy resin between the polyamide resin and the metal material, since the epoxy resin requires a heat treatment of 250 ° C. or more,
There is a problem that the material strength is significantly reduced.

The present invention has been made in view of the above problems, and does not cause breakage, cracking, or delamination of the resin layer even when drawing and ironing are performed, and a high-strength drawing is possible. An object of the present invention is to provide a laminated aluminum plate for ironing and a method for producing the same.

[0009]

According to the present invention, there is provided a laminated aluminum plate for drawing and ironing, comprising an aluminum or aluminum alloy substrate and a silane coupling agent having an amino group formed on the surface of the substrate. And a resin film laminated on the surface of the intermediate layer.

In this laminated aluminum plate for drawing and ironing, the intermediate layer may be formed of a mixed solution of the silane cup agent and ammonium polyacrylate. The thickness of the intermediate layer is preferably 0.01 to 2.0 μm. Furthermore,
It is preferable that the resin film is a polyamide resin or a Teflon resin.

The method for producing a laminated aluminum plate for drawing and ironing according to the present invention is directed to a method for producing a silane coupling agent having an amino group or a silane coupling agent having an amino group on a substrate made of aluminum or an aluminum alloy, and a method of preparing a polyammonium acrylate. The method is characterized in that after the mixed solution is applied, drying is performed at a drying temperature of 30 ° C. or more and less than 250 ° C. for 5 seconds to 10 minutes, and then a resin film is laminated at a temperature of 30 ° C. or more and the melting point of the resin or less.

In the present invention, a silane coupling agent having an amino group alone or a silane coupling agent between an aluminum or aluminum alloy substrate and a resin film made of, for example, a polyamide resin or a Teflon resin is used. Since the intermediate layer made of a mixture with ammonium polyacrylate is provided, the decrease in the material strength in the manufacturing process is extremely small.

[0013]

BEST MODE FOR CARRYING OUT THE INVENTION Hereinafter, embodiments of the present invention will be described.
This will be described in detail. In the present invention, a substrate made of an aluminum or aluminum alloy plate, an intermediate layer on the substrate, and a resin film thereon are further provided.

The type of the substrate is arbitrary, for example, pure aluminum such as JIS A1050, A1100 and A1200, or aluminum-manganese alloy such as JIS A3003 and A3004, and the thickness of the substrate is 0.2 to 0. It is preferably about 0.5 mm. Further, in order to improve the adhesion between the aluminum substrate and the intermediate layer formed thereon, as an aluminum substrate, a phosphoric acid chromate treatment film on the surface of the aluminum material,
Form one kind of film selected from the group consisting of a chromate chromate treatment film, a film composed of an organic resin and Cr, and a chemical conversion treatment film containing Zr or Ti, or by etching treatment such as electrolytic etching Surface-treated ones can be used.

The resin film is, for example, a polyamide resin or a Teflon resin. Any polyamide resin can be used, but nylon 6, nylon 66 and their copolymer resins can be used. There is no limitation on the Teflon resin, but a tetrafluoroethylene-6-fluoropropylene copolymer, a tetrafluoroethylene-ethylene copolymer or the like can be used.

The intermediate layer contains a silane coupling agent having an amino group. Then, the silane coupling agent having the amino group alone may be used, or the intermediate layer may be formed by a mixture of the silane coupling agent and ammonium polyacrylate.

The silane coupling agent is an organic silicon monomer having two or more different reactive groups in the molecule. One of the two reactive groups is a reactive group that chemically bonds to an inorganic substance (glass, metal, etc.), and the other reactive group is a reactive group that chemically bonds to an organic material (various synthetic resins).

The reactive group bonded to the inorganic aluminum plate is not particularly limited, but may be, for example, a methoxy group, an ethoxy group. There are silanol groups and the like. The amino group was used as the reactive group that binds to the polyamide resin, which is an organic material, because other reactive groups have insufficient adhesiveness, and delamination and the like will occur when drawing and ironing are performed. is there.

The ammonium polyacrylate is not particularly limited, but for example, those having a molecular weight of 5,000 to 7000 can be used.

The intermediate layer composed of the silane coupling agent alone or a mixture of the silane coupling agent and ammonium polyacrylate has a thickness after drying of 0.01 to 2.0 μm.
m, preferably 0.02 to 1 μm. When the thickness is less than 0.01 μm, sufficient adhesive strength cannot be obtained, and delamination tends to occur after drawing and ironing, and conversely, when the thickness exceeds 2.0 μm, the adhesive strength decreases.

In the production method of the present invention, after a silane coupling agent alone or a mixture of a silane coupling agent and ammonium polyacrylate is applied to an aluminum plate, the coating is carried out at 30 ° C. or more and less than 250 ° C. for 5 seconds to 10 minutes. And dry. This is because if the temperature is lower than 30 ° C. and the time is less than 5 seconds, there is no problem in performance, but sufficient drying may not be performed, and the aluminum material is softened at 250 ° C. or more and 10 minutes or more. Preferably, 100
Drying at a temperature of not less than 200 ° C and not more than 10 seconds and not more than 3 minutes is desirable.

Next, in the present invention, at least 30 ° C.
The resin film is laminated at a temperature equal to or lower than the melting point of the resin. This means that if the lamination temperature is lower than 30 ° C,
This is because the adhesiveness of the film is low, and when the lamination is performed at a temperature exceeding the melting point, the resin film adheres to the heating roll, and a good appearance cannot be obtained.

[0023]

EXAMPLES Next, a description will be given of the results of manufacturing a laminated aluminum plate according to an example of the present invention and comparing its characteristics with those of a comparative example aluminum plate.

As the aluminum substrate, a 0.3 mm thick JIS A1100 pure aluminum plate subjected to a phosphoric acid chromate treatment was used.
C., using a nylon 6 film with a film thickness of 15 .mu.m. Teflon resin has a melting point of 270.degree.
m 4 fluoroethylene-6 fluoropropylene copolymer (FEP) film was used.

As an intermediate layer between the aluminum substrate and the nylon 6 film or the FEP film, an intermediate layer made of a silane coupling agent alone or a mixture of the silane coupling agent and ammonium polyacrylate was provided. Γ-aminopropyltriethoxysilane was used as the silane coupling agent.

A laminated aluminum plate is coated with a silane coupling agent or a mixture of a silane coupling agent and ammonium polyacrylate on the surface of the phosphoric acid chromate treatment layer, dried, and then coated with nylon using a film laminator. 6 film or FEP film, then 240 ° C for nylon 6 film
In the case of an FEP film, it was produced by melting at 290 ° C. for 20 seconds and cooling with dehumidified frozen air.

As a comparative example, a laminated aluminum plate obtained by directly laminating a nylon 6 film on an aluminum substrate and an aluminum plate having an epoxy equivalent of 180 to 20 were used.
0 bisphenol type epoxy resin, 320 ℃
After laminating a nylon 6 film on the material heat-treated for 5 minutes at 240 ° C. and melting at 240 ° C. for 20 seconds, a film laminated material cooled with dehumidified frozen air was used.

The film of the obtained laminated aluminum plate was peeled off, and the tensile strength of the aluminum material was measured. The nylon 6 film laminated material was drawn so that the laminate layer was located outside the cap, and then subjected to an ironing process at an ironing rate of 30%.
The FEP film laminate was subjected to drawing at a drawing ratio of 1.5. Evaluation of drawability and ironing processability, the peeling of the film, visual observation of the state of cracks, etc., ◎ particularly good case, 良好 good case, △ slightly bad case,
Poor cases were marked as x.

The results are shown in Table 1 below. As is clear from Table 1, as the intermediate layer, in the embodiment of the present invention in which a layer made of a silane coupling agent alone or a mixture of a silane coupling agent and ammonium polyacrylate was formed, the strength of the laminate material was low. The state was extremely high, and the resin film on the side surface of the cap was in a good state of peeling and cracking. Therefore, in the case of the example, good film adhesion was obtained. On the other hand, in the case of the comparative example, the tensile strength was low or the adhesion of the film was extremely poor.

[0030]

[Table 1]

[0031]

As described in detail above, the high-strength laminated aluminum plate according to the present invention is excellent in drawability and ironing workability because peeling and cracking of the resin film during drawing and ironing are prevented. Therefore, the present invention can be applied to drawing and ironing of outer cases of electronic components such as condenser caps and condenser microphones of all sizes from small to large. Further, in the production method of the present invention, since the drying temperature of the silane coupling agent alone or the silane coupling agent and the ammonium polyacrylate is relatively low, a furnace having a large heating capacity is not required, and A laminated aluminum plate having an advantageous effect can be manufactured at low cost.

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Claims (5)

[Claims] An aluminum or aluminum alloy substrate, an intermediate layer containing a silane coupling agent having an amino group formed on the surface of the substrate, and a resin film laminated on the surface of the intermediate layer. A laminated aluminum plate for drawing and ironing. 2. The laminated aluminum plate for drawing and ironing according to claim 1, wherein the intermediate layer is formed of a mixed solution of the silane cup agent and ammonium polyacrylate. 3. The intermediate layer has a thickness of 0.01 to 2.0.
The laminated aluminum plate for drawing and ironing according to claim 1 or 2, wherein the thickness is μm. 4. The laminated aluminum sheet for drawing and ironing according to claim 1, wherein the resin film is a polyamide resin or a Teflon resin. 5. After applying a silane coupling agent having an amino group or a mixture of an amino group-containing silane coupling agent and ammonium polyacrylate to an aluminum or aluminum alloy substrate, a drying temperature of 30 ° C. or more and less than 250 ° C. For 5 seconds to 10 minutes, then 30
A method for producing a laminated aluminum plate for drawing and ironing, comprising laminating a resin film at a temperature of not lower than the melting point of the resin and not lower than ℃.