JP2003112387A - Metallized aramid film and manufacturing method therefor - Google Patents

Abstract

PROBLEM TO BE SOLVED: To increase a jointing strength between an aramid film and a metallic layer. SOLUTION: The metallized aramid film is composed of an aramid film 1 showing that the Ra value of the surface is 2 to 10 nm because the surface of the film l is roughened and an intermediate layer 2 which is formed of one kind or two kinds or more selected from among molybdenum, silicon, silicon monoxide, an Mo-Ta alloy, an Mo-Si alloy, an Mo-W alloy, an Mo-Al alloy and an Mo-Fe alloy, and applied as a coating film to the surface of the aramid film 1 and has an average thickness of 0.1 to 5 nm and a metallic layer 4, formed on the intermediate layer 2, with an average thickness of 10 nm or more.

Description

Detailed Description of the Invention

[0001]

TECHNICAL FIELD The present invention relates to a metallized aramid film in which a metal layer such as copper is formed on the surface of an aramid film, and more particularly to a metallized aramid used as a TAB tape, a flexible circuit board or a flexible wiring board. Regarding film.

[0002]

2. Description of the Related Art In recent years, TAB (Tape Autom) has been used as a circuit board which is advantageous for downsizing, weight reduction and flexibility of electronic equipment.
Demand for circuit boards using ated bonding, FPC (Flexible Prnt Circuit), etc. is increasing. Conventionally, a circuit board of this type has been used in which a copper foil is bonded to an adhesive such as an epoxy adhesive on a flexible plastic substrate.

However, in order to achieve high-density mounting of electronic equipment, it is desired to further thin this type of circuit board, and as described above, the structure in which copper foil is adhered requires a reduction in thickness. I couldn't answer enough.

Further, in the circuit board using the above-mentioned adhesive, the etching liquid for copper foil is likely to soak into the adhesive layer,
When bias is applied under high temperature and high humidity, copper migration may occur and short circuit may occur.In order to speed up, it is necessary to match impedance and reduce crosstalk. Is difficult, the dimensional stability of the adhesive layer is poor, the fine processing of the circuit board is difficult due to the presence of the adhesive layer, it is difficult to cope with high density, and the thermal characteristics of the adhesive layer are Since it is inferior to that, there is a problem in thermal stability, it is difficult to cope with high density, and there is a problem that the product is easily deformed due to the adhesive.

In order to solve these problems, techniques for forming a metallized film without using an adhesive have been investigated. For example, a metal thin film is directly formed on a plastic substrate along a circuit pattern by a thin film forming technique such as vacuum deposition, sputtering, or ion plating, and then a metal plating layer is formed on the metal thin film by electrolytic plating or the like. A method of depositing, a method of forming a metal thin film on the surface of a plastic substrate, depositing a metal on the surface by electrolytic plating or the like, and then etching the metal layer to form a circuit pattern are known.

However, in such a structure, there is a problem that the bonding strength between the plastic substrate and the metal thin film decreases after the subsequent steps such as the circuit pattern forming step and the electrolytic plating step, and the peeling easily occurs.

In order to solve this problem, Japanese Patent Laid-Open No. 1-13
Japanese Patent No. 3729 discloses a structure in which zirconium oxide or silicon oxide is formed on the surface of a polyimide film, and a copper layer is formed thereon. JP-A-3-274
Japanese Patent No. 261 discloses a structure in which nickel, chromium, titanium, vanadium, tungsten, molybdenum, or the like is formed on the surface of a polyimide film, and a copper layer is formed thereon. Japanese Unexamined Patent Publication No. 5-183012 describes a structure in which a thin film of nickel, cobalt, tungsten, molybdenum, or the like is formed on the surface of a polyimide film by electroless plating, and a copper layer is formed thereon by a plating method. There is.

In Japanese Patent Laid-Open No. 7-197239, nickel, chromium, molybdenum,
A structure in which a metal such as tungsten is vacuum-deposited and a copper layer is further formed by electrolytic plating is described. JP-A-8
-330695 gazette, on a polyimide film,
It describes a structure in which a thin film of molybdenum is formed by sputtering, and a copper layer is formed thereon by electrolytic plating. JP-A-6-256960 discloses that the surface of an aramid film is subjected to etching treatment with an aqueous solution containing hydrazine and an alkali metal hydroxide and subjected to a catalyst application treatment, and then a metal thin film is formed by electroless plating. A method of manufacturing a copper-coated aramid substrate for performing a copper coating treatment is described. Japanese Unexamined Patent Publication No. 2000-212315 describes a method of manufacturing a shield material in which a copper layer is formed on both surfaces of an aramid film or the like by a vacuum vapor deposition method.

[0009]

However, even when any of the conventional methods is applied, when the aramid film is used, the phenomenon that the copper layer peels from the aramid film has not been sufficiently prevented. .

The present invention has been made in view of the above circumstances, and an object of the present invention is to provide a metallized aramid film in which the bonding strength between the metal layer and the aramid film is further increased, and a method for producing the same.

[0011]

In order to solve the above problems, the metallized aramid film according to the present invention is subjected to a surface roughening treatment such as a plasma etching treatment so that the surface has a Ra value of 2 to 10 nm. And the aramid film, and the surface of the aramid film, molybdenum,
Average thickness of one or more selected from silicon, silicon monoxide, Mo-Ta alloy, Mo-Si alloy, Mo-W alloy, Mo-Al alloy and Mo-Fe alloy. Of 0.1 to 5 nm, and a metal layer having an average thickness of 10 nm or more formed on the intermediate layer.

On the other hand, in the method for producing a metallized aramid film of the present invention, the Ra value of the surface of the aramid film is 2-10 by subjecting the surface of the aramid film to a plasma etching treatment.
nm step and on the surface of the plasma-etched aramid film, molybdenum, silicon, silicon monoxide, Mo-Ta alloy, Mo-Si alloy,
A step of forming one or two or more kinds selected from Mo-W alloy, Mo-Al alloy and Mo-Fe alloy to form an intermediate layer having an average thickness of 0.1 to 5 nm; And a step of forming a metal layer having an average thickness of 10 nm or more on the layer.

The metallized aramid film of the present invention comprises TA
It may be in the form of a B tape, a flexible circuit board, a flexible wiring board, or the like.

[0014]

BEST MODE FOR CARRYING OUT THE INVENTION FIG. 1 is a schematic view showing an embodiment of a metallized aramid film according to the present invention. This metallized aramid film includes an aramid film 1 that has been subjected to surface roughening treatment such as plasma etching treatment, an intermediate layer 2 formed on the surface of the aramid film 1, and a metal layer formed on the intermediate layer 2. 4 and.

The aramid resin, which is the material of the aramid film 1, is substantially composed of units selected from the group consisting of the following constitutional units. -NH-Ar1-NH- (1) -CO-Ar2-CO- (2) -NH-Ar3-CO- (3) Ar1, Ar2 and Ar3 are each a divalent group containing at least one aromatic ring. When the structural units (1) and (2) are present in the polymer, both are substantially equimolar.

From the viewpoint of enhancing the mechanical performance and dimensional stability of the aramid film 1, Ar 1, Ar 2 and Ar 3 are preferably para-oriented groups. The para orientation type means that the binding direction of the main chain in the aromatic ring is located at the para position, or that in the residue composed of two or more aromatic rings, the binding directions of the main chains at both ends are coaxial or parallel. means. However, the meta orientation type may be used, or the meta orientation type may be mixed. As a material for the aramid film 1, an aramid resin in which 80 mol% or more of all aromatic rings are bound to para is particularly preferable.

A part of hydrogen atoms on the aromatic ring may be replaced with a halogen group, a nitro group, an alkyl group, an alkoxyl group or the like. Ar1, Ar2 and Ar3 may be two or more kinds, and may be the same or different from each other. The aramid resin may be copolymerized with a group other than those described above in an amount of about 10 mol% or less, or may be blended with another polymer. The most typical aromatic polyamide used in the present invention is polyparaphenylene terephthalamide (PPTA).

Further, the aramid film 1 contains additives such as an antioxidant, a delusterant, an ultraviolet stabilizer, an antistatic agent, etc. within a range not impairing the physical properties of the film or contrary to the gist of the present invention. It may be.

The polymers used for these aramid resins can be produced from a diamine, a dicarboxylic acid or an aminocarboxylic acid corresponding to each unit by a known method. Specifically, the carboxylic acid group is first acid halide,
A method is used in which the compound is introduced into an acid imidazole, an ester or the like and then reacted with an amino group. As the polymerization method, a so-called low temperature solution polymerization method, an interfacial polymerization method, a melt polymerization method, a solid phase polymerization method, or the like can be used.

Although the thickness of the aramid film 1 is not particularly limited, it is preferably 4 to 50 μm. Within this range, it is suitable for applications such as TAB tapes, flexible circuit boards, and flexible wiring boards. The aramid film 1 may be a single layer, or may be a laminated film in which plural kinds of aramid resins are laminated.

The surface of the aramid film 1 on which the intermediate layer 2 and the metal layer 4 are to be formed is subjected to a surface roughening treatment in advance, and the center plane average roughness (Ra) value of the surface is 2 to 2.
It is set to 10 nm. Ra value is more preferably 2 to 5
nm. Within such a range, the bonding strength between the metal layer 4 and the aramid film 1 can be increased. On the other hand, if the Ra value is too large, the surface of the aramid film 1 is rather deteriorated, and the bonding strength of the metal layer 4 decreases. On the other hand, if the Ra value is too small, the brittle layer cannot be sufficiently removed, and the bonding strength of the metal layer 4 decreases.

The center plane average roughness (Ra) is the roughness curve obtained by removing low-frequency components from the cross-section curve. When the roughness curve is represented by y = f (x, y) with the direction of longitudinal magnification as the y-axis, the value obtained by the following formula is represented. The measurement is performed in the contact mode using the probe of the atomic force microscope, and the measurement range is 2 x
2 μm.

[0023]

[Equation 1]

The type of surface roughening treatment is not limited, but plasma etching treatment is preferred. In the plasma etching process, the aramid film 1 is run in a vacuum container, and the surface of the aramid film 1 is irradiated with plasma to remove the brittle layer on the surface of the aramid film 1. For plasma treatment, one or two of argon, oxygen, nitrogen, helium, carbon tetrafluoride, carbon trifluoride, carbon tetrachloride, etc.
Mixtures of more than one gas can be used. Generally, a direct current (D) is used as an energy supply source required for plasma generation.
C), alternating current (AC), high frequency (RF), microwave, etc. are used, and a method of further stabilizing plasma by applying a magnetic field is also applicable. Although processing conditions vary by device configurations, for example, when using a high-frequency power source, processing bath vacuum 10 ^-2 to 10 ⁰ Pa, high frequency applied 0.05~1.0W / cm ^2, the processing time of 30 seconds to 20 minutes It is preferable to set it to a degree.

By carrying out such a plasma etching treatment, the brittle layer existing on the surface of the aramid film 1 can be removed, and the joint interface can be roughened, so that the aramid film 1, the intermediate layer 2 and the metal. Layer 4
It is possible to increase the bonding strength with the.

The intermediate layer 2 is one or more selected from molybdenum, silicon, silicon monoxide, Mo-Ta alloy, Mo-Si alloy, Mo-W alloy, Mo-Al alloy and Mo-Fe alloy. Is formed as a single layer or a plurality of layers, and its average thickness is 0.1 to 5 nm. In the illustrated example, the intermediate layer 2 and the metal layer 4 are formed on only one side of the aramid film 1, but they may be formed on both sides, or the intermediate layer 2 and the metal layer 4 are previously formed.
May be formed to have a constant pattern shape.

If the average thickness of the intermediate layer 2 is less than 0.1 nm, the thickness of the intermediate layer 2 becomes non-uniform, making it difficult to control the film thickness, and the bonding strength of the metal layer 4 to the aramid film 1 becomes difficult. Also decreases. If the intermediate layer 2 is thicker than 5 nm, the intermediate layer 2 will not be formed when the wiring pattern is formed by etching.
Becomes difficult to dissolve and the etching property deteriorates. The more preferable thickness of the intermediate layer 2 is 1 to 5 nm. Within this range, the manufacturing cost is low and the effect of increasing the bonding strength of the metal layer 4 is excellent.

Since the intermediate layer 2 is as thin as 0.1 to 5 nm, it is considered that the intermediate layer 2 is not a dense film without pores. For example, a porous film having a large number of pores or an island is formed. It is considered that the film forming material is scattered. In any case, the effect of the present invention is exhibited. When the film-forming material is scattered on the surface of the aramid film 1, the film-forming material may be concentratedly attached to the microscopic projections on the surface of the aramid film 1, or conversely, The aramid film 1 may be concentratedly attached to the recesses on the surface. The average thickness of the intermediate layer 2 in the case of non-uniform adhesion means the thickness (mass film thickness) obtained by averaging the adhesion amount of the intermediate layer 2 by the area of the adhesion region on the aramid film 1. And

According to the experiments conducted by the present inventors, when Mo-Ta, Mo-Si, and Mo-W are used as the material of the intermediate layer 2, particularly high bonding strength is exhibited, and high bonding strength is obtained even after various durability tests. It turned out that can be maintained.
Since the molybdenum alloy is less likely to be oxidized even at high temperatures than the intermediate layer made of only molybdenum, high joint strength can be maintained even after the durability test.

When a molybdenum alloy is used, the atomic percentage of Mo is preferably 70 to 98%. When the atomic percentage of Mo is less than 70% or more than 98%, the bonding strength of the metal layer 4 to the aramid film 1 is reduced. The atomic percentage of Mo is more preferably 80-
95%.

In order to form the intermediate layer 2 on the aramid film 1, the film-forming material is deposited on the aramid film 1 by a dry thin film forming technique such as a vacuum vapor deposition method, a sputtering method or an ion plating method. Good. More preferable film forming methods for forming the material are a sputtering method and an ion plating method. The film forming conditions are not particularly limited, but it is preferable to make the partial pressures of oxygen and water in the film forming tank as low as possible in order to prevent oxidation of the film forming material.

The material of the metal layer 4 is one or more selected from copper, copper alloy, aluminum, aluminum alloy, silver, gold, platinum and the like, and particularly preferably pure copper,
Alternatively, it is a copper alloy containing nickel, zinc, iron, or the like. The thickness of the metal layer 4 is 10 nm or more, and more preferably 30 nm to 500 nm. If the metal layer 4 is too thick, the cost will be too high, and if it is too thin, defects such as burnout will easily occur in the plating process.

To form the metal layer 4, a metal may be formed on the aramid film 1 on which the intermediate layer 2 is formed by a thin film forming technique such as vacuum deposition, sputtering or ion plating, or After forming a thin film to some extent by each of the above methods, a metal plating layer may be deposited on the deposited film by an electrolytic plating method, an electroless plating method, or the like.

According to the metallized aramid film of the above embodiment, the intermediate layer 2 made of a specific film-forming material is formed between the aramid film 1 and the metal layer 4, so that the aramid film 1 and the metal layer 4 are formed. The joint strength with can be increased.

Further, since the aramid film is used as the base material, the film tensile strength is, for example, two times or more that in the case of using polyimide, and the elastic modulus is four times or more that of polyimide. Therefore, it is possible to provide a flexible substrate material having high mechanical resistance (for example, flexibility) as compared with a conventional product using polyimide as a base material. Further, it is possible to obtain the same dimensional stability, chemical characteristics, and electric characteristics as those of a flexible substrate material using a polyimide film.

Further, the aramid film has a thickness of 10 μm.
Since it is easy to form a thin film having a thickness of m or less, it is possible to reduce the weight and density of the flexible substrate material, and to reduce the manufacturing cost.

[0037]

EXAMPLES Next, the effects of the present invention will be demonstrated with reference to examples. (Example 1) As an aramid film, Asahi Kasei Corporation's trade name "Aramica" (thickness 12 µm) was used, and argon gas was used for this film base material, and high frequency 0.2
Plasma etching treatment was performed under the conditions of W and treatment time of 10 minutes. The Ra value of the film base material at this time is 3.23 n
It became m. For measuring the Ra value, "Nanopic S1000" (trade name) manufactured by Seiko Instruments Inc. was used. The surface-treated film was set in a sputtering apparatus, and an intermediate layer and a metal layer were formed on the plasma-etched surface under the following conditions to obtain a metallized aramid film of Example 1. Intermediate layer material: molybdenum Film formation conditions: Argon gas used, DC output 200W Film thickness: 2nm Metal layer material: Copper film formation conditions: Argon gas used, DC output 3kW Film thickness: 300nm

Example 2 Toray Co., Ltd., trade name “MICTRON” (thickness: 12 μm) was used as an aramid film substrate, and this film substrate was subjected to the same plasma etching treatment as in Example 1. Ra of the film substrate at this time
The value was 2.81 nm. The surface-treated film was set in a sputtering apparatus, and an intermediate layer and a metal layer were formed on the plasma-etched surface under the following conditions to obtain a metallized aramid film of Example 2. Intermediate layer material: molybdenum Film formation conditions: Argon gas used, DC output 200W Film thickness: 2nm Metal layer material: Copper film formation conditions: Argon gas used, DC output 3kW Film thickness: 300nm

(Example 3) As an aramid film, "Aramika" (trade name, Asahi Kasei Kogyo Co., Ltd.) (thickness: 12 μm) was used, and this film substrate was subjected to the same plasma etching treatment as in Example 1. Ra of the film substrate at this time
The value was 3.20 nm. The surface-treated film was set in a sputtering apparatus, and an intermediate layer and a metal layer were formed on the plasma-etched surface under the following conditions to obtain a metallized aramid film. Intermediate layer material: Silicon Film forming condition: Argon gas used, DC output 250W Film thickness: 2nm Metal layer material: Copper film forming condition: Argon gas used, DC output 3kW Film thickness: 300nm

Example 4 Toray Co., Ltd., trade name “Miktron” (thickness: 12 μm) was used as an aramid film substrate, and this film substrate was subjected to the same plasma etching treatment as in Example 1. Ra of the film substrate at this time
The value was 2.90 nm. The surface-treated film was set in a sputtering apparatus, and an intermediate layer and a metal layer were formed on the plasma-etched surface under the following conditions to obtain a metallized aramid film. Intermediate layer material: Silicon Film forming condition: Argon gas used, DC output 250W Film thickness: 2nm Metal layer material: Copper film forming condition: Argon gas used, DC output 3kW Film thickness: 300nm

(Example 5) As the aramid film, "Aramika" (trade name) (thickness 12 µm) of Asahi Kasei Kogyo Co., Ltd. was used, and this film substrate was subjected to the same plasma etching treatment as in Example 1. Ra of the film substrate at this time
The value was 3.39 nm. The surface-treated film was set in a sputtering apparatus, and an intermediate layer and a metal layer were formed on the plasma-etched surface under the following conditions to obtain a metallized aramid film. Intermediate layer material: Silicon monoxide Film formation conditions: Argon gas used, DC output 400W Film thickness: 2nm Metal layer material: Copper film formation conditions: Argon gas used, DC output 3kW Film thickness: 300nm

(Example 6) As the aramid film substrate, Toray Industries, Inc., trade name "MICRON" (thickness: 12 µm) was used, and this film substrate was subjected to the same plasma etching treatment as in Example 1. Ra of the film substrate at this time
The value was 3.10 nm. The surface-treated film was set in a sputtering apparatus, and an intermediate layer and a metal layer were formed on the plasma-etched surface under the following conditions to obtain a metallized aramid film. Intermediate layer material: Silicon monoxide Film formation conditions: Argon gas used, DC output 400W Film thickness: 2nm Metal layer material: Copper film formation conditions: Argon gas used, DC output 3kW Film thickness: 300nm

(Example 7) As an aramid film, "Aramika" (trade name) (thickness: 12 μm) manufactured by Asahi Kasei Corporation was used, and this film substrate was subjected to the same plasma etching treatment as in Example 1. Ra of the film substrate at this time
The value was 3.58 nm. The surface-treated film was set in a sputtering apparatus, and an intermediate layer and a metal layer were formed on the plasma-etched surface under the following conditions to obtain a metallized aramid film. Intermediate layer material: Mo-Ta Film forming condition: Argon gas used, DC output 200W Film thickness: 2nm Metal layer material: Copper film forming condition: Argon gas used, DC output 3kW Film thickness: 300nm

(Example 8) Toray Co., Ltd., trade name "Miktron" (thickness: 12 μm) was used as an aramid film substrate, and this film substrate was subjected to the same plasma etching treatment as in Example 1. Ra of the film substrate at this time
The value was 2.71 nm. The surface-treated film was set in a sputtering apparatus, and an intermediate layer and a metal layer were formed on the plasma-etched surface under the following conditions to obtain a metallized aramid film. Intermediate layer material: Mo-Ta Film forming condition: Argon gas used, DC output 200W Film thickness: 2nm Metal layer material: Copper film forming condition: Argon gas used, DC output 3kW Film thickness: 300nm

(Example 9) As an aramid film, "Aramika" (trade name) (thickness: 12 μm) manufactured by Asahi Kasei Corporation was used, and this film substrate was subjected to the same plasma etching treatment as in Example 1. Ra of the film substrate at this time
The value was 3.62 nm. The surface-treated film was set in a sputtering apparatus, and an intermediate layer and a metal layer were formed on the plasma-etched surface under the following conditions to obtain a metallized aramid film. Intermediate layer material: Mo-Si Film forming condition: Argon gas used, DC output 200W Film thickness: 2nm Metal layer material: Copper film forming condition: Argon gas used, DC output 3kW Film thickness: 300nm

(Example 10) As an aramid film base material, Toray Industries, Inc., trade name "MICTRON" (thickness 12 μm)
And the same plasma etching treatment as in Example 1 was applied to this film substrate. R of the film substrate at this time
The a value was 2.91 nm. The surface-treated film was set in a sputtering apparatus, and an intermediate layer and a metal layer were formed on the plasma-etched surface under the following conditions to obtain a metallized aramid film. Intermediate layer material: Mo-Si Film forming condition: Argon gas used, DC output 200W Film thickness: 2nm Metal layer material: Copper film forming condition: Argon gas used, DC output 3kW Film thickness: 300nm

(Example 11) As an aramid film, Asahi Kasei Co., Ltd., trade name "Aramica" (thickness: 12 μm)
And the same plasma etching treatment as in Example 1 was applied to this film substrate. R of the film substrate at this time
The a value was 3.10 nm. The surface-treated film was set in a sputtering apparatus, and an intermediate layer and a metal layer were formed on the plasma-etched surface under the following conditions to obtain a metallized aramid film. Intermediate layer material: Mo-W Film forming condition: Argon gas used, DC output 200W Film thickness: 2nm Metal layer material: Copper film forming condition: Argon gas used, DC output 3kW Film thickness: 300nm

Example 12 Toray Co., Ltd., trade name “MICTRON” (thickness: 12 μm) as an aramid film base material
And the same plasma etching treatment as in Example 1 was applied to this film substrate. R of the film substrate at this time
The a value was 2.85 nm. The surface-treated film was set in a sputtering apparatus, and an intermediate layer and a metal layer were formed on the plasma-etched surface under the following conditions to obtain a metallized aramid film. Intermediate layer material: Mo-W Film forming condition: Argon gas used, DC output 200W Film thickness: 2nm Metal layer material: Copper film forming condition: Argon gas used, DC output 3kW Film thickness: 300nm

(Example 13) As an aramid film, Asahi Chemical Industry Co., Ltd., trade name "Aramica" (thickness: 12 μm)
And the same plasma etching treatment as in Example 1 was applied to this film substrate. R of the film substrate at this time
The a value was 3.09 nm. The surface-treated film was set in a sputtering apparatus, and an intermediate layer and a metal layer were formed on the plasma-etched surface under the following conditions to obtain a metallized aramid film. Intermediate layer material: Mo-Al Film forming condition: Argon gas used, DC output 200W Film thickness: 2nm Metal layer material: Copper film forming condition: Argon gas used, DC output 3kW Film thickness: 300nm

Example 14 Toray Co., Ltd., trade name “MICTRON” (thickness: 12 μm) as an aramid film substrate
And the same plasma etching treatment as in Example 1 was applied to this film substrate. R of the film substrate at this time
The a value was 2.90 nm. The surface-treated film was set in a sputtering apparatus, and an intermediate layer and a metal layer were formed on the plasma-etched surface under the following conditions to obtain a metallized aramid film. Intermediate layer material: Mo-Al Film forming condition: Argon gas used, DC output 200W Film thickness: 2nm Metal layer material: Copper film forming condition: Argon gas used, DC output 3kW Film thickness: 300nm

(Example 15) As an aramid film, Asahi Kasei Co., Ltd., trade name "Aramica" (thickness 12 μm)
And the same plasma etching treatment as in Example 1 was applied to this film substrate. R of the film substrate at this time
The a value was 3.39 nm. The surface-treated film was set in a sputtering apparatus, and an intermediate layer and a metal layer were formed on the plasma-etched surface under the following conditions to obtain a metallized aramid film. Intermediate layer material: Mo-Fe Film forming condition: Argon gas used, DC output 200W Film thickness: 2nm Metal layer material: Copper film forming condition: Argon gas used, DC output 3kW Film thickness: 300nm

(Example 16) As an aramid film base material, Toray Industries, Inc., trade name "Miktron" (thickness 12 μm)
And the same plasma etching treatment as in Example 1 was applied to this film substrate. R of the film substrate at this time
The a value was 2.75 nm. The surface-treated film was set in a sputtering apparatus, and an intermediate layer and a metal layer were formed on the plasma-etched surface under the following conditions to obtain a metallized aramid film. Intermediate layer material: Mo-Fe Film forming condition: Argon gas used, DC output 200W Film thickness: 2nm Metal layer material: Copper film forming condition: Argon gas used, DC output 3kW Film thickness: 300nm

(Comparative Example 1) As an aramid film, "Aramica" (trade name, Asahi Kasei Kogyo Co., Ltd.) (thickness 12 μm) was used as it was. Ra value of the film substrate is 1.56n
It was m. The film was set in a sputtering device, and a metal layer was formed on the plasma-etched surface under the following conditions to obtain a metallized aramid film. Metal layer material: Copper Film formation conditions: Argon gas used, DC output 3kW Film thickness: 300nm

(Comparative Example 2) As a aramid film substrate, Toray Industries, Inc., trade name "MICTRON" (thickness 12 μm) was used as it was. Ra value of the film substrate is 1.64n
It was m. The film was set in a sputtering device, and a metal layer was formed on the plasma-etched surface under the following conditions to obtain a metallized aramid film. Metal layer material: Copper Film formation conditions: Argon gas used, DC output 3kW Film thickness: 300nm

(Comparative Example 3) As an aramid film, "Aramika" (trade name, Asahi Kasei Kogyo Co., Ltd.) (thickness: 12 μm) was used as it was. Ra value of the film substrate is 1.56n
It was m. The film was set in a sputtering apparatus, and an intermediate layer and a metal layer were formed on the surface subjected to the plasma etching treatment under the following conditions to obtain a metallized aramid film. Intermediate layer material: Mo Film forming condition: Argon gas used, DC output 200W Film thickness: 2nm Metal layer material: Copper film forming condition: Argon gas used, DC output 3kW Film thickness: 300nm

(Comparative Example 4) As a aramid film substrate, Toray Industries, Inc., trade name "Miktron" (thickness 12 μm) was used as it was. Ra value of the film substrate is 1.64n
It was m. The film was set in a sputtering device, and a metal layer was formed on the plasma-etched surface under the following conditions to obtain a metallized aramid film. Intermediate layer material: Mo Film forming condition: Argon gas used, DC output 200W Film thickness: 2nm Metal layer material: Copper film forming condition: Argon gas used, DC output 3kW Film thickness: 300nm

(Comparative Experiment) After depositing a copper layer of 20 μm on the metallized aramid films of Examples 1 to 16 and Comparative Examples 1 to 4 by electrolytic copper plating, width 10 mm × length 1
A 50 mm strip test piece is cut out and IPC-TM-6
The bonding strength between the film base material and the metal thin film was measured by the method of 50 (American Printed Circuit Industry Association standard test method). In this test method, the aramid film side of the strip-shaped test piece was bonded and fixed to the outer circumference of a 6-inch diameter drum in the circumferential direction, and one end of the metal film was peeled from the aramid film with a jig at 50 mm / min. While pulling, the load required for it is measured. The results are shown in Table 1.

Further, the pressure cooker test (PCT) and the high temperature test were performed on each test piece, and the same bonding strength test as described above was performed on the metallized polyimide film after that to compare the bonding strength after the durability test. did. The results are shown in Table 1. The PCT condition is 121
C., humidity 100%, 2 atmospheres, 48 hours, high temperature test 150.degree. C., 24 hours.

[0059]

[Table 1]

[0060]

As described above, according to the present invention,
The surface of the aramid film is subjected to a surface roughening treatment to make the surface Ra value 2 to 10 nm, and molybdenum, silicon, silicon monoxide, Mo-Ta alloy, Mo-Si alloy, Mo-W.
Alloys, Mo-Al alloys and Mo-Fe alloys having an average thickness of 0.1 to 5 composed of one or more selected from
Since the intermediate layer having a thickness of nm is formed and the metal layer is formed, the bonding strength between the aramid film and the metal layer can be sufficiently increased.

[Brief description of drawings]

FIG. 1 is an enlarged cross-sectional view of an embodiment of a metallized aramid film according to the present invention.

[Explanation of symbols]

1 Aramid film 2 Middle class 4 metal layers

Front page continuation (51) Int.Cl. ⁷ identification code FI theme code (reference) C23C 28/02 C23C 28/02 5E343 C25D 5/56 C25D 5/56 AZ 7/00 7/00 J H05K 1/03 610 H05K 1/03 610H 3/38 3/38 AC F term (reference) 4F100 AA20B AB01B AB01C AB10B AB11B AB17 AB20B AB31B AK47A BA03 BA07 BA10A BA10C DD07A EH66 EJ15 EJ34A GB43 JL11 JM02 CA4K02 A12A32A02A4A04A12A12A32A4A02A4A04A12A4 AB17 BA12 BB09 BC02 DA06 GA01 4K029 AA11 BA35 BB02 CA05 FA05 4K044 AA16 AB02 BA02 BA06 BA10 BA19 BB03 BC05 CA07 CA13 CA14 CA15 CA18 5E343 AA16 BB22 BB23 BB24 DD25 DD36 DD22 BB25 DD36 DD23 BB22 DD33 DD24 BB49 DD57 BB49 BB52 BB53 BB52

Claims (2)

[Claims] 1. An aramid film whose surface has a Ra value of 2 to 10 nm after being subjected to a surface roughening treatment, and molybdenum on the surface of the aramid film,
Average thickness of one or more selected from silicon, silicon monoxide, Mo-Ta alloy, Mo-Si alloy, Mo-W alloy, Mo-Al alloy and Mo-Fe alloy. A metallized aramid film comprising an intermediate layer having a thickness of 0.1 to 5 nm and a metal layer formed on the intermediate layer and having an average thickness of 10 nm or more. 2. The Ra value of the surface of the aramid film is 2-1 by subjecting the surface of the aramid film to a plasma etching treatment.
On the surface of the aramid film that has been subjected to the plasma etching treatment and the step of 0 nm, molybdenum, silicon, silicon monoxide, Mo-Ta alloy, Mo-Si alloy, Mo-W alloy, Mo-Al alloy and Mo. A step of forming one or more selected from Fe alloys to form an intermediate layer having an average thickness of 0.1 to 5 nm, and a metal layer having an average thickness of 10 nm or more on the intermediate layer And a step of forming a metallized aramid film.