JP3339632B2 - Manufacturing method of laminated metal strip and laminated metal strip - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a method for manufacturing a laminated metal strip which can be firmly joined and a laminated metal strip.

[0002]

2. Description of the Related Art As a first method of manufacturing a laminated metal strip by pressure bonding using rolling in a vacuum chamber, as shown in Japanese Patent Publication No. 7-55384, a vacuum atmosphere at normal temperature is used. There is a method in which the surface of a metal band to be joined is activated by ion etching treatment and then is subjected to pressure bonding with a low rolling reduction using a rolling method. The first advantage is that, since a compression bonding method is used at room temperature, it is difficult to form an alloy (diffusion) layer at the bonding interface, and the formation of the alloy (diffusion) layer significantly deteriorates the properties of the laminated metal band. It is suitable as a production method for ultra-thin plates. Also, as a second advantage, since the layers are pressure-bonded in a vacuum atmosphere, bonding defects due to gas entrainment or metal oxides on the bonding surface are eliminated, and as a result,
Since it is possible to obtain a composite material having a high bonding strength of the laminated metal band after the lamination and pressure bonding, it is excellent in that a laminated metal band having excellent workability can be manufactured. As a second method, there is a hot rolling method disclosed in JP-A-1-133689. This is a method in which a laminated metal strip is manufactured by heating a superposed dissimilar metal to an arbitrary temperature from room temperature to 1400 ° C. in a vacuum or an adjusted atmosphere, and then rolling. This method does not require a welding step, and can be firmly joined at high speed, so that the production efficiency is good. There are also advantages such as relatively simple equipment and low equipment cost.

On the other hand, a low-pressure diffusion bonding method has been proposed as a third method. This is because, for example, in Japanese Patent Application Laid-Open No. 60-27481, as a joint joining method, Al and Ti to be joined are inserted from a material exchange room, conveyed to a clean surface treatment room by a conveyor, and formed on the joint surface. After the oxide layer is sputtered (dry-etched) and the oxide layer is removed, the carrier is moved to the front of the target device by a transporter, and Zn or Mg is coated by sputtering, and the evaporation of the Zn or Mg is further prevented. A bonding method of coating an evaporation-preventing film such as Si by sputtering, further moving the same to a diffusion furnace, and stacking Al and Ti is disclosed. It is suitable as a joining method. Further, as a fourth method, Japanese Patent Application Laid-Open No. 7-214344 discloses that an active metal thin film is formed by simultaneously sputtering a part or all of three or more plate-like materials on a joint surface or an inert gas. Or after irradiating a beam of metal particles to remove the contaminated layer,
An apparatus for obtaining a laminated material by contacting surfaces to be joined is disclosed, and these methods are suitable for joining relatively small plate-like materials.

[0004]

However, the ion etching in the above-mentioned first method has a low etching rate and requires an etching amount larger than the thickness of the oxide layer in order to form a strong bond. Not only is this method bad, but furthermore, this method is limited to a method of manufacturing a two-layer laminated metal band made of the same or different metal or alloy, so that a laminated metal band having a structure of three or more layers at once can be obtained. Not suitable for manufacturing method. In addition, since the above-mentioned second method heats before bonding, for example, the metal to be bonded has a thickness of 10 μm.
In copper foil etc., wrinkles are likely to occur due to softening of the material, differences in expansion coefficient, etc., making it difficult to manufacture with coils,
Poor productivity.

[0005] Furthermore, the third method is suitable for joining relatively small articles such as joints that can be transported by a transporter. However, the oxide layer of the articles to be joined is removed, and the target is further sputtered. The coating layer is formed at least once by exchanging at least once, and is further transported to a diffusion furnace for joining. The productivity is not good, and it is particularly difficult to continuously produce a strip-shaped laminated metal. Furthermore, the fourth method is also suitable for joining relatively small plates, but is unsuitable for joining long materials such as strips.For example, in the fourth method, strip-shaped metal materials are continuously joined together. It is extremely difficult to join. An object of the present invention is to provide a method for continuously producing a laminated metal strip having a structure of three or more layers at the same time even at a low rolling reduction within a range of technologies that can be sufficiently used industrially, and an object of the present invention to provide a laminated metal strip. .

[0006]

SUMMARY OF THE INVENTION The present inventor can improve the productivity while utilizing the advantages of the crimping method performed in a vacuum chamber, and at the same time, can obtain a laminated metal strip having three or more layers. As a result of intensive studies on the manufacturing method, it has been found that productivity can be greatly improved by forming a new metal layer by a dry film formation method, and that further bonding can be firmly performed by heating, and the present invention has been achieved.

Namely this onset bright, in a vacuum chamber, at least on one surface side of the first object to be bonded surface and the bonded surface of the second metal band of the metal strip, the first by a dry film formation method A laminated metal that press-bonds the first metal band and the second metal band after forming a third metal layer serving as an etching barrier layer of the same type or a different type as the metal band or the second metal band. It is a method of manufacturing a belt. In addition, the present invention provides a
And the surface to be bonded of the first metal band and the surface to be bonded of the second metal band
On at least one side of the surface, the dry film forming method
Same as or similar to the first metal band or the second metal band
After depositing a dissimilar third metal layer, the first
Pressure contact between the metal strip and the second metal strip, and then heat diffusion treatment
And a method of manufacturing a laminated metal strip.

[0008] This onset Ming, in a vacuum chamber, at least on one surface side of the first object to be bonded surface and the bonded surface of the second metal band of the metal strip, the first by a dry film formation method Metal strip and
The second metal strip is a different type of etching barrier layer.After the third metal layer is deposited and adhered, the laminated metal that press-bonds the first metal strip and the second metal strip is formed. In the manufacturing method of the belt
is there. Further, the present invention relates to a method for contacting a first metal strip in a vacuum chamber.
At least one of the joining surface and the surface to be joined of the second metal strip.
On the surface side, the first metal strip and the second
The third metal barrier is a different type of etching barrier layer
After depositing a metal layer, the first metal strip and the second
The product that is bonded by pressure bonding to the metal strip and then heat-diffused
It is a manufacturing method of a layer metal strip. Preferably the above-mentioned dry film formation
A method for producing a laminated metal strip performed by a physical vapor deposition method.
You. Further, the present invention relates to a method in which a gap between the first metal strip and the second metal strip is provided.
Is a laminated metal strip having a dry film-forming layer,
Is the dry film forming layer between the dry film forming layer and the first metal strip.
One or both between the and the second metal strip
This is a laminated metal strip on which a diffused layer is formed. Preferably,
The dry film formation layer is different from the first metal band and the second metal band.
It is a laminated metal strip which is a metal layer.

[0009]

DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS An important feature of the present invention resides in that a strip-shaped metal material is pressed in a vacuum chamber via a metal formed by dry film formation, and is combined with a heat diffusion heat treatment. Dry-formed metal is active and can be bonded by pressing. As a method of crimping,
At least it is only necessary to be able to pressurize. For example, rolling with a roll, rolling, or the like can be applied. In addition, the reason why the heat diffusion treatment is combined is that the bonding force may not be sufficient with only the pressure contact force of the dry film formation, so that a stronger bonding may be obtained. When the joining force is increased only by rolling or the like, it is necessary to increase the rolling reduction. However, in this case, wrinkles and deformations are likely to occur. Therefore, it is desirable to combine the heat diffusion treatment.

Hereinafter, the present invention will be described in detail. In the present invention, first, the same or different etching barrier layer as the first metal band or the second metal band by dry film formation method and
Comprising a third metal first, it is deposited on one or both the joining surface of the second metal strip, and the third metal layer. The adhesion formation of the third metal is performed on any one of the surfaces to be bonded of the first metal band and the surface to be bonded of the second metal band, or both surfaces. If it is adhered and formed on any surface of the bonded surface side of the metal band and the bonded surface side of the second metal band, it can be firmly bonded by the subsequent pressure bonding,
For example, in order to strengthen the bonding, a third metal may be attached to the bonding surfaces of both metal strips.

[0011] This and come, only the third metal layer if dissimilar metals or alloys, for example, is suitable as a material for application to selective etching. If the third metal is made of the same metal or alloy as either the first metal band or the second metal band, a laminated metal band made of two kinds of materials can be easily obtained, for example, thermal expansion. The present invention can be applied to a bimetal material made of two kinds of materials having different rates, a lead frame material made of two kinds of materials having different thermal and electrical properties, a battery part, and the like. Further, when the first metal band and the second metal band are different, if the third metal is also a different metal or alloy from the first metal band and the second metal band, three types of metal layers are formed at a time. A laminated metal strip having a structure of three or more layers can be obtained. For example, the present invention can be applied to a battery material or the like composed of three types of materials having different corrosion resistance, electrical characteristics, weather resistance, and the like.

The laminated metal band (9) of the present invention is sandwiched between a first metal band (4) and a second metal band (5), for example, as shown in FIG. Etch burr
A structure having a third metal layer (dry film formation layer) (11) serving as a layer. Na us, the laminated metal strip in the present invention refers to those having a structure of the third metal layer first metal strip and sandwiched a second metal strip (dry film forming layer), the same kind of metal Alternatively, even a combination of alloys is referred to as a laminated metal strip in the present invention. Further, if a heat diffusion treatment as described later is performed on this, between the metal forming the third metal layer (dry film formation layer) and the first metal band, the dry film formation layer and the second metal band are formed. A diffusion layer is formed in one or both of them. It is needless to say that a diffusion layer is formed on the dry film formation layer or the entire laminated metal strip depending on the heat diffusion treatment conditions.

Further, in the method described so far, the third metal has been described as one kind of adherently formed.
For example, it is also possible to adhere and form different metals or alloys to the first metal band and the second metal band,
The third metal layer (dry film formation layer) may be made of a different metal.

In the present invention, a third metal is deposited and formed into a layer. If the thickness of the layer is excessively increased to 10 μm or more, the time required for dry film formation increases, and productivity is reduced. Less than 10μm, as it may decrease
A thickness of 3 μm or less is sufficient if the productivity and characteristics required for the third metal layer are, for example, an etching barrier at the time of selective etching. If the third metal layer has to be thickened, first laminate either the first metal band or the second metal band with the same metal or alloy as the third metal. After the band has been manufactured, it can also be used as a first or second metal band. Of course, a metal band laminated on the first metal band and the second metal band may be used.

The dry film forming method referred to in the present invention is a general dry film forming method utilizing a gas phase or plasma, such as physical vapor deposition or chemical vapor deposition. Among these, not only the vacuum deposition method, but also the method of ionizing and accelerating the film heated and evaporated in vacuum like ion plating, or the method of hitting desired atoms by hitting gas ions like sputtering, etc. It also includes a method of film formation, a molecular beam evaporation method that uses a special crucible, draws out a specific material in the form of a molecular beam and evaporates it (above, physical vapor deposition method), or a certain kind of chemical vapor deposition method like A film formation method in which a gas is heated and reacted is also included. For deposition of the third metal of the present invention, a physical vapor deposition method such as a vacuum vapor deposition method, a sputtering method, or an ion plating method, which has recently been significantly accelerated in film forming technology, is suitable. The vacuum evaporation method has a high evaporation rate and good productivity. The sputtering method can cope with the case where the third metal is a high melting point metal, and the selection range of the third metal is wide. The ion plating method has the same productivity as the vacuum vapor deposition method, and the bonding between the strip serving as the substrate and the dry film formation layer is strengthened. However, it is necessary to apply a bias voltage to the strip, and the apparatus configuration is reduced. It becomes complicated.

From these facts, in the case of industrial production, a vacuum evaporation method may be used in a vacuum chamber. At this time, a low-pressure atmosphere of 1 × 10 ^-1 Pa or less should be used. Is good. Note that one or both of the first metal band and the second metal band may be subjected to an ion etching treatment in advance so that dry film formation is easy.

Next, the first and second metal strips on which the dry film-forming layers are adhered are pressed by using the above-mentioned dry film-forming method.
At this time, if the crimping is performed by using rolling, the crimping can be continuously performed on the continuous strip, so that the productivity is good. The rolling is preferably performed at a low rolling reduction of 1% or less. Note that, instead of a rolling roll, a roll such as a take-up roll may be used for the press-bonding, and the roll may be wound with tension and pressed. By performing the pressure bonding as described above, it is possible to obtain a laminated metal band having a dry film formation layer between the first metal band and the second metal band, and the laminated metal band is bonded as it is. are doing.

In one aspect of the present invention, the above-mentioned laminated metal strip may be subjected to a heat diffusion treatment. This heat diffusion treatment is suitable for strengthening the bonding strength of the above-mentioned laminated metal band, and for example, forms another circuit pattern on the first metal band and the second metal band by etching. This is suitable for making the barrier layer stronger when so-called selective etching is performed. In addition, by performing this heat diffusion treatment, the dry etching is insufficient due to the insufficient amount of ion etching when performing ion etching in the pretreatment of dry film formation, the insufficient rolling force after dry film formation, and the poor degree of vacuum. A strong bonding force can be obtained when the bonding force after pressure bonding is not sufficient due to impurities adhering to the film formation surface. The operation of the heat diffusion process may be performed in the above-described vacuum chamber, or another heating furnace may be used.

The heating temperature after pressing is, for example, 150 ° C. or higher to 800 ° C. when Ni is used for the first metal band and Cu is used for the second metal band.
Degree, preferably between 200 ° C and 400 ° C. Heating is preferably performed continuously on the strip being conveyed in the above-described vacuum chamber, but if the rate of temperature rise is not sufficient,
You may take out from a vacuum tank and heat using another heat processing furnace. As a method of heating the strip being transported in the vacuum chamber,
A heating device may be mounted on the transport path, or the temperature of the rolling roll used for pressing may be increased. Further, the strip manufactured in this manner may be conveniently cut into a laminated metal plate.

As described above, according to the present invention, pressure contact is performed with a low load,
Because of the heating, it is suitable for manufacturing a relatively thin laminated metal strip having a thickness of 0.5 mm or less. As a specific example, copper
/ Invar alloy, lead frame material composed of two types of materials, CSP, BGA and other fine wiring application materials, copper / nickel / copper three-layer structure material, etc.

Embodiment 1 Hereinafter, the present invention will be described in detail with reference to embodiments and drawings. FIG. 2 is a schematic view showing an example of the apparatus for manufacturing a laminated metal strip of the present invention. As shown in FIG. 2, a first metal unwinding reel (2) arranged in a vacuum chamber (1) and a first metal strip unwound from a second metal unwinding reel (3). (Four),
When the second metal band (5) passes over a guide roll (7) provided at a position facing the dry film forming apparatus (6), an etching barrier layer is formed on the surface to be joined of the first and second metals. to become the third metal is deposited by dry deposition method, a rolling roll (8)
Thereby, the pressure bonding is completed, and the laminated metal band (9) having the dry film-forming layer is formed between the first and second metal bands. Further, the laminated metal strip is heated by the heating device (12) and wound up by the take-up reel (10).

As an example, the first metal strip (4) has a thickness of 1
0 μm Cu foil as a second metal band (5)
The foils were respectively unwound from the unwinding reels, and the respective joining surfaces were opposed to the Ni dry film forming material of the dry film forming apparatus (6). At this time, as a low-pressure atmosphere of about 5 × 10 ⁻³ Pa in the vacuum chamber (1), Ni was adhered and formed on the surfaces to be joined of the first and second metals, respectively, by a dry film forming method (vacuum vapor deposition method). . The adhered surfaces are pressure-bonded by a rolling roll (8) to form a laminated metal band (9) of Cu / Ni / Cu with Ni as a dry film formation layer,
The laminated metal strip was subjected to heat diffusion treatment at 300 ° C. by a heating device (12), and was taken up by a take-up reel (10).

The sectional form of the Cu / Ni / Cu laminated metal band (9) obtained as described above was observed with an optical microscope. As a result, FIG. 1 (a) shows a photomicrograph at 400 × magnification.
(b) shows a schematic diagram thereof. As a cross-sectional configuration, a third metal layer (dry film formation layer) (11) is formed by dry film formation extremely uniformly between the first metal band (4) and the second metal band (5). You can see that Note that a diffusion layer of Ni constituting the third metal layer (dry film formation layer) and Cu forming the first and second metal bands is a dry film formation layer and the first and second metal layers. The formation between the layers was confirmed with an X-ray analyzer. Also, of the laminated metal strip cut to a width of 10 mm, the first metal strip and the second metal strip were forcibly peeled off at a speed of 50 mm / min. As a result, when not heated, bonding was performed at 0.1 N / mm. When heated to 300 ° C., it was 0.5 N / mm or more, and the bonding was stronger.

(Example 2) A stainless steel foil having a thickness of 60 µm was used as the first metal band (4).
A 10 μm-thick Ni foil was unwound from the unwinding reel as the second metal strip (5), and the respective joining surfaces were opposed to the Ni dry film forming material provided in the dry film forming apparatus (6). . At this time, the inside of the vacuum chamber (1) is set to a vacuum atmosphere of about 1 × 10 ^-2 Pa, and Ni to be an etching barrier layer is dried by a dry film forming method (vacuum deposition method) to form a surface to be joined of the first and second metal bands. Respectively. This adhesion surface is a rolling roll
Bonded by (8), stainless steel foil / Ni dry film layer / N
A laminated metal band (9) of i-foil was formed, and was wound by a take-up reel (10) to obtain a laminated metal band for a battery safety valve having a plurality of through holes on one surface .

Circular through-holes having a diameter of 3 mm were provided by selective etching in the obtained stainless steel foil of the laminated metal band for a battery safety valve so as to form a grid-like arrangement with a pitch of 10.5 mm. After that, the long side is 10.5m using a punch press
m, a short side of 7.5 mm, and a laminated metal strip for a battery safety valve having one circular hole formed at the center thereof was used as a safety valve chip, and 10 safety valve chips were collected. These safety valve chips were hermetically welded to a pressurizable steel plate pressure vessel, then connected to a compressor at one end of the vessel via a pressure gauge, and the inside of the steel plate pressure vessel was pressurized. In the chip for use, the Ni foil burst in a pressure range of 1.3 to 1.7 MPa. Further, a test piece for observing the cross-sectional morphology was collected from the above-described metal laminate for a safety valve, and the cross-sectional morphology was observed with an electron microscope. According to this observation, a 1 μm-thick metal strip (stainless steel foil) and a second metal strip (Ni foil)
It was confirmed from the cross-sectional morphology that a dry film formation layer of Ni was formed.

[0026]

According to the present invention, a laminated metal strip having a structure of three or more layers, which conventionally required two steps, can be manufactured in one step, and ion etching which is a pretreatment for dry film formation is simplified. As a result, productivity was dramatically improved.

[Brief description of the drawings]

FIG. 1 is a cross-sectional micrograph of a laminated metal strip as an example of the present invention and a schematic view thereof.

FIG. 2 is a schematic view showing a laminated metal strip manufacturing apparatus as an example of the present invention.

[Explanation of symbols]

1. 1. vacuum chamber; 2. First metal unwinding reel; 3. a second metal unwinding reel; 4. first metal band; 5. second metal strip; 6. Dry film forming apparatus, Guide roll,
8. Rolling roll, 9. 9. laminated metal strip; Take-up reel, 11. 11. third metal layer (dry film formation layer); Heating equipment

Claims (8)

(57) [Claims] In a vacuum chamber, the first metal strip or the first metal strip is formed on at least one surface side of the first metal strip and the second metal strip by a dry film forming method. Etching barrier of the same type or different type as the second metal strip
A method for manufacturing a laminated metal strip, comprising: after forming a third metal layer as a layer by adhesion, bonding the first metal strip and the second metal strip by pressure bonding. 2. The method according to claim 1, wherein the first metal band or the first metal band is formed on at least one of the surfaces to be bonded of the first metal band and the surface to be bonded of the second metal band by a dry film forming method. Etching barrier layer of the same or different type as the second metal strip
A method for producing a laminated metal strip, comprising: after adhering and forming a third metal layer, bonding the first metal strip and the second metal strip by pressure bonding, and then performing a heat diffusion treatment. 3. The surface to be joined of the first metal strip in a vacuum chamber.
And at least one side of the joined surface of the second metal strip
The first metal strip and the second metal strip are formed by a dry film forming method.
Metal that is a different type of etching barrier layer from the third metal band
After depositing the metal layer, the first metal strip and the second gold
Manufacture of laminated metal strip characterized by pressure bonding with metal strip
Construction method. 4. A surface to be joined of a first metal strip in a vacuum chamber.
And at least one side of the joined surface of the second metal strip
The first metal strip and the second metal strip are formed by a dry film forming method.
A third metal that is a different type of etching barrier layer from a metal strip
After depositing the layer, the first metal strip and the second metal
Bonding the band with the band, and then performing the heat diffusion process
A method for producing a laminated metal strip, which is characterized by the following. 5. The dry deposition method is a manufacturing method of a laminated metal strip according to any one of claims 1 to 4, characterized in that a physical vapor deposition. 6. d between the first metal strip and the second metal strip
A laminated metal strip having a dry film forming layer serving as a switching barrier layer . 7. A diffusion layer is formed between at least one of the dry film forming layer and the first metal band or between the dry film forming layer and the second metal band. Claims
7. The laminated metal strip according to 6 . 8. The dry film forming layer includes a first metal strip and a second gold band.
Dissimilar metals from genus 7. The layer according to claim 6, wherein the layer is a layer.
Or the laminated metal strip according to 7.