JPH11277699A - Metal layer laminated film - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide the film wherein an aromatic polyimide film containing p-phenylenediamine as an essential component and good in dimensional stability and a metal layer are strongly bonded. SOLUTION: A laminated film is obtained by laminating a modified film, which is obtained by applying normal pressure plasma discharge treatment to at least the single surface of a film comprising an aromatic polyimide based on p-phenylenediamine, in which a fine particulate inorg. filler is dispersed, with a thickness of 5-150 μm and a volatile matter content of 1.0 wt.% or less and good in dimensional stability to a metal layer directly or through an adhesive.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a metal layer laminated film in which a metal layer is firmly laminated on an aromatic polyimide film directly or via a heat-resistant adhesive, and to an electronic component used therefor. A metal layer laminated film in which a metal layer is firmly laminated directly or through a heat-resistant adhesive on a modified surface of a polyimide film in which fine-particle inorganic fillers are dispersed in an aromatic polyimide, under normal pressure plasma discharge treatment, And an electronic component using the metal layer laminated film.

[0002]

2. Description of the Related Art Aromatic polyimide films are widely used for electronic devices such as cameras, personal computers, and liquid crystal displays. In order to use the aromatic polyimide film as a substrate material for flexible printed circuit (FPC), tape-automated bonding (TAB) and lead-on-chip (LOC), epoxy resin etc. A method of laminating a copper foil by using a heat-resistant adhesive is used.

[0003] Aromatic polyimide has heat resistance, mechanical strength,
Although the electrical properties are excellent, there is a problem that adhesion between the aromatic polyimide film and a metal foil (eg, copper foil) is not easy because the surface of a molded product such as a film is inactive. Conventionally, adhesives for enhancing the adhesion of the aromatic polyimide film to the metal have also been developed, but the adhesion between the adhesive and the surface of the aromatic polyimide film is also insufficient.

For this reason, a method of improving the adhesiveness of the surface of the aromatic polyimide film by subjecting the surface of the aromatic polyimide film to a discharge treatment such as a corona discharge treatment or a plasma discharge treatment has been studied and used.

For example, Japanese Patent Application Laid-Open No. 63-61030 discloses that the oxygen / carbon ratio on the film surface is increased by 0.01 to 0.1 by performing a corona discharge treatment, and the residual volatile amount is 0.45. It describes a polyimide film of not more than weight% and a metal foil laminated film in which a polyimide film and a metal foil (copper foil) are laminated with an adhesive.

JP-A-1-138242 discloses that an aromatic polyimide film is supported by a discharge electrode,
It describes a surface modification method of an aromatic polyimide film which is modified by performing a discharge treatment such as corona discharge, and a metal foil laminated film in which a polyimide film and a metal foil (copper foil) are laminated with an adhesive.

JP-A-3-56541 discloses a method for modifying an aromatic polyimide film in which an aromatic polyimide film is treated with an organic solvent in advance and then subjected to plasma treatment, and an aromatic polyimide film and a metal foil (copper foil). And a metal foil laminated film obtained by laminating the above with an adhesive.

Japanese Patent Application Laid-Open No. 5-1160 discloses an aromatic polyimide film in which a discharge treatment such as a plasma discharge is performed at normal pressure using an application electrode having a specific shape while supporting the aromatic polyimide film with a drum electrode. For modifying polyamide, and aromatic polyimide film and metal foil (copper foil)
And a metal foil laminated film obtained by laminating the above with an adhesive.

[0009]

SUMMARY OF THE INVENTION The method for modifying the surface of an aromatic polyimide film described in each of the above publications can be effectively applied to various heat-resistant resin films centering on an aromatic polyimide film. Have been. However,
The specific facts revealed in each description are that an aromatic compound produced by using pyromellitic dianhydride as a tetracarboxylic acid component and 4,4-diaminodiphenyl ether as a diamine component. Polyimide film, or manufactured using those materials, the product name is `` Kapton '' aromatic polyimide film, and a metal foil laminated film using it,
According to the examples described in the respective publications, it has been clarified that corona discharge treatment or plasma discharge treatment of this kind of aromatic polyimide film is effective in improving the adhesive strength.

However, according to a study on the improvement of the surface characteristics of the aromatic polyimide film by the present inventors, it has been found that aromatic polyimides whose surface characteristics cannot be sufficiently improved even by the above-mentioned known corona discharge treatment or plasma treatment. The film was found to be present.

That is, as another kind of aromatic polyimide film, an aromatic tetracarboxylic acid component such as 3,3 ', 4,4'-biphenyltetracarboxylic dianhydride and p
-An aromatic polyimide film containing p-phenylenediamine as an essential component, such as a polyimide film obtained from phenylenediamine, is known. The aromatic polyimide film is composed of the above pyromellitic dianhydride and 4,4. -An aromatic polyimide film having better mechanical strength and dimensional stability than an aromatic polyimide film produced from diaminodiphenyl ether, and this kind of aromatic polyimide film has improved surface properties. It is known to be difficult. And p-
Even if an aromatic polyimide film containing phenylenediamine as an essential component is subjected to the above-described conventional discharge treatment, satisfactory surface modification (particularly, improved adhesion) cannot be realized. In addition, in the case of vacuum plasma discharge processing, there is a problem that high cost is required to make the vacuum.

Accordingly, an object of the present invention is to provide an aromatic polyimide film comprising an aromatic tetracarboxylic acid component and an aromatic diamine component having improved surface properties, especially adhesion, and comprising p-phenylenediamine as an essential component. A metal layer laminated film in which a metal layer is firmly laminated directly or via a heat-resistant adhesive on a modified surface of a polyimide film having at least one surface modified by an atmospheric pressure plasma treatment, and To provide electronic components that have been

[0013]

That is, the present invention relates to an aromatic polyimide comprising an aromatic tetracarboxylic acid component and an aromatic diamine component, wherein inorganic fine particles are contained in an aromatic polyimide containing p-phenylenediamine as an essential component. Distributed,
A metal layer having a thickness of 5 to 150 μm, good dimensional stability, a volatile content of 1.0% by weight or less, and a modified surface of a polyimide film having at least one surface modified by plasma treatment. And a metal layer laminated film that is firmly laminated directly or via a heat-resistant adhesive, and an electronic component as its application.

In the present invention, the surface-modified polyimide film comprises an aromatic tetracarboxylic acid component, preferably 3,3 ', 4,4'-biphenyltetracarboxylic acid 1
Species, or a combination of any two of 3,3 ', 4,4'-biphenyltetracarboxylic acid, pyromellitic acid, 3,3', 4,4'-benzophenonetetracarboxylic acid, or an anhydride or An aromatic tetracarboxylic acid component containing an ester and an aromatic diamine component containing p-phenylenediamine, preferably one kind of p-phenylenediamine or two kinds of p-phenylenediamine and 4,4-diaminodiphenyl ether P-
Polyimide film obtained from an aromatic diamine component containing phenylenediamine, under an atmosphere containing a rare gas,
Atmospheric-pressure plasma discharge treatment is performed by plasma discharge electrodes running on the surface of the plasma discharge electrodes covered with a dielectric such as an inorganic dielectric on a large number of surfaces arranged in two rows along the film running surface without contact. Depending on the method used, it can be easily obtained. The above-mentioned polyimide film includes a film slit in a tape shape.

In the aromatic polyimide film of the present invention, the amount of the inorganic filler element in the element composition on at least one side of the film is 0.03-1.5.
Atomic%, especially 0.05-1.0 atomic%, and the oxygen / carbon ratio at the surface is 0.01-0.2
Preferably, it is modified so as to increase 0, particularly 0.05-0.15.

[0016]

BEST MODE FOR CARRYING OUT THE INVENTION The metal layer laminated film of the present invention will be described in detail with reference to typical embodiments.
The aromatic polyimide film in the present invention is produced as follows, for example, as described in Japanese Patent Application No. 9-63751. First, 3,3 ', 4,4'-
Biphenyltetracarboxylic dianhydride, or 3,
Any one of 3 ′, 4,4′-biphenyltetracarboxylic dianhydride, pyromellitic dianhydride and 3,3 ′, 4,4′-benzophenonetetracarboxylic dianhydride
Species combinations [linear expansion coefficient (50-200 ° C.)
The composition may be appropriately determined so as to be 0 × 10 ⁻⁵ −2.5 × 10 ⁻⁵ cm / cm / ° C. An aromatic tetracarboxylic acid component and one kind of p-phenylenediamine, or p
An aromatic diamine (p-phenylenediamine is preferably 15 to 100 mol%) consisting of two combinations of phenylenediamine and 4,4-diaminodiphenyl ether with N, N-dimethylacetamide And N-methyl-2-pyrrolidone in organic polar solvents commonly used for the production of polyimides, preferably 10-
Polymerization is performed at 80 ° C. for 1-30 hours, and the logarithmic viscosity of the polymer (measuring temperature: 30 ° C., concentration: 0.5 g / 100 ml solvent, solvent: N-methyl-2-pyrrolidone) is 1-5, polymer concentration Is 10-25% by weight, and the rotational viscosity (30
(° C.) is 500-4500 poise to obtain a polyamic acid (imidization ratio: 5% or less) solution.

Next, preferably, the polyamic acid 10
0.01 to 3% by weight, based on 0 parts by weight, of a phosphorus compound, for example, an organic phosphorus-containing compound such as a (poly) phosphate ester and / or an amine circle of a phosphate ester or an inorganic phosphorus compound, and preferably a polyamic acid 0.1 to 3 parts by weight of an inorganic filler such as colloidal silica, silicon nitride, talc, titanium oxide, calcium hydrogen phosphate or the like (preferably having an average particle size of 0.005 to 5 μm,
In particular, 0.005-2 μm) is added to prepare a polyamic acid solution composition. These phosphorus compounds and inorganic fillers may be present uniformly in the entire film layer, or when forming a film having a two- or three-layer structure, the phosphorus compound and the inorganic filler should be contained in the above-mentioned ratio in at least one layer containing the surface. Is preferred.

This polyamic acid solution composition is cast on a glass or metal support having a smooth surface to form a thin film of the solution, and when the thin film is dried,
Adjust the drying conditions (preferable temperature: 100-16
0 ° C., time: 1 to 60 minutes) By drying, the solidified film has a volatile content of 30 to 50% by weight and an imidation rate of 10 to 60% by weight in the solidified film.
Is formed, and the solidified film is peeled from the surface of the support.

The solidified film obtained as described above is further dried, if necessary, preferably after adjusting the volatile content of the dried film to 10 to 45% by weight. While holding both edges in the width direction, after drying so that the temperature (° C.) × residence time (minute) at the entrance of the curing furnace in the curing furnace is within the range of the hatched line in FIG. Heating temperature: 400-
The dried film is heated and dried and imidized under the condition that the temperature at 500 ° C. is 0.5 to 30 minutes, and the imidization is performed at a residual volatile matter amount of 1.0% by weight or less, particularly 0.4% by weight or less. Upon completion, it can be suitably manufactured as an aromatic polyimide film.

The aromatic polyimide film obtained as described above is preferably used under low tension or no tension.
Heating at a temperature of about 00-400 ° C. to perform a stress relaxation treatment,
Take up. The heating conditions of the aromatic polyimide film before curing in the curing furnace during the above-mentioned production are controlled within the range of the hatched area in FIG. 1 of the above-mentioned application specification, and the curing conditions are adjusted to the above-mentioned temperature range. When the thickness is within the range, the thickness is 5 to 150 μm, the dimensional stability is good, the residual volatile matter amount is 1.0% by weight or less, particularly 0.4% by weight or less, and the specific crack resistance is large. be able to. If the residual volatile matter content in the film is more than 1.0% by weight, it is difficult to improve the adhesiveness. The polyimide film may polymerize each monomer component (random, block),
Alternatively, it can be similarly obtained by blending. Further, the aromatic polyimide film is not limited to the above-mentioned thermal imidization, and can be performed by either a catalyst or a chemical imidization as long as it is within the above-mentioned conditions.

The aromatic polyimide film in the present invention has a thickness in the range of 5-150 μm, preferably 2 to 150 μm.
A fine inorganic filler in the range of 5-125 μm;
Is included. The content of the inorganic filler in the aromatic polyimide film is preferably in the range of 0.02 to 5.0% by weight. In particular, the aromatic polyimide film according to the present invention preferably satisfies the following conditions from the viewpoint of high precision. (1) The tensile modulus is 500 kg / mm ² or more, and (2) the coefficient of linear expansion (5
0 to 200 ° C.) is 1.0 × 10 ⁻⁵ −2.5 × 10 ⁻⁵ cm
/ Cm / ° C. or less; (3) Heat shrinkage rate (250 ° C. ×
(2 hours) is 0.5% or less, and (4) the specific crack resistance is 11-25 kg / 20 mm / 10 μm.

As described above, the aromatic polyimide film to be subjected to the plasma discharge apparatus (normal pressure plasma treatment, ie, plasma discharge treatment at 0.8 to 1.2 atm) in the present invention has an inorganic film on its surface. A method of forming a plurality of projections (covered with polyimide) formed by a filler to form a film surface is used. Incidentally, the usual aromatic polyimide film,
On the side (generally referred to as side B) on which the dope liquid containing the inorganic filler in a dispersed state was in contact with the support, the adhesion reached a level sufficient for practical use, but on the opposite side. The adhesion of the surface (generally referred to as side A) is poor.

In the plasma discharge treatment of the present invention, the surface A of an aromatic polyimide film containing an inorganic filler (also applied to an aromatic polymer film containing another inorganic filler) is subjected to the plasma discharge treatment. As a result, the aromatic polyimide layer covering the inorganic filler on the surface is oxidized, destroyed, removed, etc., so that the surface of the inorganic filler (or the vicinity of the surface) is observed to the extent observed by ESCA analysis described later. It is thought that this is due to the fact that an effective increase in the adhesive force is realized.

Therefore, the plasma discharge treatment of the present invention
It is preferably applied to the surface A (non-support side surface) of the aromatic polyimide film containing the inorganic filler, but it is preferable to apply the plasma discharge treatment to both surfaces of the aromatic polyimide film.

Next, the plasma discharge treatment of the aromatic polyimide film containing an inorganic filler of the present invention will be described. The plasma processing in the present invention is desirably performed using a plasma processing apparatus schematically shown in FIG. 1 of the accompanying drawings.

In FIG. 1, reference numeral 11 denotes a housing of a plasma processing apparatus, in which a plurality of plasma discharge chambers 12 are provided. Inside the plasma discharge chamber 12, a large number of plasma discharge electrodes 13 whose surfaces are coated with a dielectric such as an inorganic dielectric (preferably glass) are arranged in two rows in two rows along the film running surface. (The inside is cooled to about 10-50 ° C.) Plasma discharge chamber 12
A gas supply source 1 for supplying a gas containing a rare gas such as argon which forms a discharge atmosphere in the discharge chamber.
A gas introduction pipe 15 connected to the gas supply pipe 4 is provided, and an inlet 16 and an outlet 17 for an aromatic polyimide film to be plasma-treated are provided.

The gas atmosphere for carrying out the plasma discharge treatment in the present invention is mainly composed of argon,
A gas atmosphere in which 1 to 50 mol of nitrogen and 1 to 50 mol of hydrogen are added to 100 mol of argon is preferable. If desired, another inert gas such as helium (preferably 1-75 mol, especially 1-50 mol) may be added to the gaseous atmosphere.

Outside and inside the plasma processing apparatus,
A number of film transport rollers 18 are provided to assist the non-contact running of the aromatic polyimide film in the plasma discharge electrode space.
Aromatic polyimide film 20 unwound from shell 19
And works to finally deliver the treated aromatic polyimide film 20 to the take-up roll 21.

The outline of the plasma processing apparatus used in the plasma discharge processing of the present invention is as shown in FIG. 1. For example, the number of discharge chambers is increased / decreased, the arrangement is changed, the number of plasma discharge electrodes is increased / decreased, and the arrangement is changed. Of course, changes can be made. In the plasma discharge treatment of the present invention, for example, using the plasma treatment apparatus shown in FIG. 1, an aromatic polyimide film containing an inorganic filler in a dispersed state is brought into contact with a plasma discharge electrode during discharge in the direction of an arrow. Since the film is continuously run without causing a discharge treatment on both surfaces of the film, the discharge treatment is preferably performed using such a discharge treatment.

In the modified polyimide film subjected to the plasma discharge treatment as described above, the amount of the inorganic filler element in the element composition on at least one side of the film is 0.04%.
Those exhibiting an increase of 3-1.5 atomic% and having an oxygen / carbon ratio of 0.01 to 0.20 at the surface thereof are preferred.

When performing the plasma discharge treatment of the polyimide film, a pretreatment using an organic solvent can be performed as described in JP-A-3-56541.

The metal layer laminated film of the present invention has a metal layer firmly laminated on the modified surface of the polyimide film modified as described above directly or through a heat-resistant adhesive (usually having an adhesive strength of 1). 0.0 kg / cm or more). In the modified polyimide film subjected to the plasma discharge treatment, a vapor deposition method on the modified surface,
The metal layer may be directly laminated by a sputtering method, a plating method, or a combination thereof, or the metal layer may be laminated via a heat-resistant adhesive.

When the metal layer is laminated via the above-mentioned adhesive, the adhesive may be thermosetting or thermoplastic as long as it has heat resistance. For example, epoxy resin, NBR-phenol resin, phenol -Butyral resin, epoxy-NBR resin, epoxy-phenol resin, epoxy-nylon resin, epoxy-polyester resin, epoxy-
Acrylic resin, acrylic resin, polyamide-epoxy-phenol-based resin, polyimide-based resin, polyimide-epoxy resin, polyimidesiloxane-epoxy-based resin or other thermosetting adhesive, or polyamide-based resin, polyester-based resin, Thermoplastic adhesives such as polyimide resin and polyimide siloxane resin are exemplified. In particular, a polyimide adhesive, a polyimide-epoxy resin adhesive, a polyimidesiloxane-epoxy resin adhesive, and an epoxy resin adhesive are preferably used.

The metal layer in the present invention includes metals such as aluminum, copper and copper alloys, and copper foil is generally used. Examples of the copper foil include an electrolytic copper foil and a rolled copper foil, and those having a tensile strength of 17 kg / mm ² or more are preferable. Further, its thickness is preferably 8-50 μm. Also, a polyimide adhesive, a polyimide-epoxy resin adhesive, a polyimidesiloxane resin or a polyimidesiloxane-epoxy resin adhesive having a thickness of 3 to 30 μm and a rolled or electrolytic copper foil having a thickness of 8 to 40 μm are used in combination. It is preferable that the surface roughness is low.

In the metal layer laminated film of the present invention, since the aromatic polyimide film has high heat resistance and dimensional stability and the metal layer and the film are firmly joined, TAB
Or FPC.

The electronic component of the present invention can be obtained, for example, by forming a metal layer laminated tape on the above-mentioned metal layer laminated film, if necessary, and then forming a circuit. The circuit is formed by, for example, printing an etching resist on the metal surface of the metal layer laminated film in the form of a circuit pattern (wiring pattern) to protect the surface of the metal layer where the wiring pattern is formed. After the wiring pattern of the etching resist to be formed is formed, the metal in the portion where the wiring is not formed is removed by etching using an etching solution by a method known per se, and the etching resist is removed. If necessary, the upper surface of the circuit pattern is treated directly or with a surface treating agent such as a sila coupling agent, and then a coating material (liquid material) is applied and then dried by heating. To form

[0037]

EXAMPLES (1) Production Example of Aromatic Polyimide Film (1) 54.6 kg of N, N-dimethylacetamide was added to a polymerization tank having an inner volume of 100 liters.
4'-biphenyltetracarboxylic dianhydride 8.826
kg and 3.243 kg of paraphenylenediamine, and polymerized at 30 ° C. for 10 hours to obtain a logarithmic viscosity of the polymer (measuring temperature: 30 ° C., concentration: 0.5 g / 100 ml solvent, solvent: N, N-dimethylacetamide) ) Is 1.6
A polyamic acid (imidation ratio: 5% or less) solution having a polymer concentration of 18% by weight was obtained. In this polyamic acid solution, 0.1 part by weight of polyamic acid was added.
Triethanolamine salt of monostearyl phosphate in an amount of 1 part by weight and colloidal silica having an average particle size of 0.08 μm in an amount of 0.5 part by weight (based on solid content) are added and uniformly mixed to obtain a polyamic acid. A solution composition was obtained. The rotational viscosity of this polyamic acid solution composition is 300
It was 0 poise. This polyamic acid composition is continuously extruded from a slit of a T-die mold onto a smooth support of a casting / drying furnace to form a thin film of the solution, and dried at an average temperature of 141 ° C. to form a long solid. A film (volatile content 28% by weight) was obtained.

Next, while holding both edges in the width direction of the dried film, the dried film is cured in a curing furnace (temperature at the entrance × residence time = 200 ° C. × 2.5 minutes, maximum temperature ×
Maximum temperature residence time = 480 ° C. × 3 minutes), thickness 50 μm,
A long aromatic polyimide film (0.2% by weight of Si) having a residual volatile matter amount of 0.18% by weight and an imidization ratio of 95% or more.
The O ₂ content) was continuously obtained. Physical properties of the aromatic polyimide film were measured as follows. Tensile modulus: ASTM D882-64T Coefficient of linear expansion (50-200 ° C): A sample that was heated at 300 ° C for 30 minutes to relax the stress was applied to a TMA device (tensile module).
Heat shrinkage (250 ° C., 2 hours): JIS C2318 Edge crack resistance (or specific edge crack resistance): JIS C2318
Means the average value of the tear resistance (or the specific tear resistance) of the samples (5 pieces) measured according to the above. Specifically, the center line of the V-shaped notch plate test bracket having the upper thickness of 1.00 ± 0.05 mm of the constant-speed tension-type tensile tester was made to coincide with the center line of the upper grip, and the top of the cut and the lower grip were About 30 intervals
Attach the handle so that it becomes mm. A test piece having a width of about 20 mm and a length of about 200 mm is folded into two through the hole of the metal fitting, and is sandwiched between the grips at the lower part of the tester, and is about 2 minutes per minute.
The force at the time of pulling and tearing at a speed of 00 mm is called end tear resistance. Five test pieces were taken from the longitudinal direction and the lateral direction over the entire width, respectively, and the average value of the end crack resistance was determined and shown as the end crack resistance value. The specific edge tear resistance indicates an edge tear resistance per film thickness (10 μm conversion).

The physical properties of this aromatic polyimide film are shown below. Tensile modulus: 850 kg / mm ² Linear expansion coefficient (50-200 ° C.): 1.2 × 10 ⁻⁵ cm /
cm / ° C. Heat shrinkage (250 ° C., 2 hours): 0.3% or less Edge crack resistance: 66 kg / 20 mm Specific edge crack resistance: 13.2 kg / 20 mm / 10 μm

(2) Plasma discharge treatment An atmospheric pressure plasma treatment device having the same configuration as the plasma treatment device shown in FIG. 1 (however, only one plasma discharge chamber is provided.
Further, the plasma discharge treatment was carried out at 1 atm), and the plasma treatment was performed at the gas composition and the film traveling speed in the plasma discharge treatment chamber shown in Table 1 below. The voltage is 200V /
One electrode. The inside of the electrode is water-cooled (25 ° C).

[0041]

[Table 1]

(3) Analysis of Surface Composition of Film after Plasma Discharge Treatment 1) Measurement of Silicon (Si) Atomic Concentration (Atom%) The silicon concentration on the surface of the aromatic polyimide film subjected to the plasma discharge treatment was measured by the ESCA method. Measured. Table 2 shows the results. 2) Increase in oxygen / carbon ratio Aromatic polyimide film subjected to plasma discharge treatment,
The oxygen / carbon ratio of each surface of the aromatic polyimide film not subjected to the plasma discharge treatment was measured by using the ESCA method. The results are shown in Table 2 as an increase in the oxygen / carbon ratio with respect to the aromatic polyimide film not subjected to the plasma discharge treatment.

(4) Metal layer laminated film (using an adhesive)
Production of an aromatic polyimide film that has been subjected to plasma discharge treatment or an aromatic polyimide film that has not been subjected to plasma discharge treatment and a copper foil, on each surface of the film (on the side that was not in contact with the support surface during film production) A metal layer laminated film was prepared under the following conditions so that the adhesive was in contact with both the surface A, which is the surface, and the surface B, which was the surface in contact with the support surface during film production. B) Adhesive: heat-fusible polyimide resin (a-BPDA /
(TPER Tg: 240 ° C.) b) Copper foil: 30 μm-thick electrolytic copper foil c) Bonding condition: Thin adhesive on copper foil (20 μm after drying)
m) After coating and drying at 130 ° C. for 15 minutes, a plasma-discharge treated polyimide film is overlaid, and 300 ° C., 6.5 kg /
Crimp in cm ² 5 minutes heat was 1 hour heat treatment at 180 ° C.. D) Adhesion strength measurement: T peeling, peeling speed 50 mm / min

Table 2 shows the adhesive strengths of the surfaces A and B of the metal layer laminated film produced under the above conditions.
Table 2 also shows the adhesive strength of the aromatic polyimide film not subjected to the plasma discharge treatment on the A side and the B side.

[0045]

[Table 2]

As is clear from the results shown in Table 2,
By performing the atmospheric pressure plasma discharge treatment of the present invention,
The aromatic polyimide film containing p-phenylenediamine has a surface activated and exhibits high adhesiveness.

(5) Preparation of Metal Layer Laminated Film (Evaporation-Electroplating) Each surface of the aromatic polyimide film subjected to the plasma discharge treatment (the surface that was not in contact with the support surface during film production). Both the A side and the B side which is the surface in contact with the support surface during film production)
Is cut out to a holder size and installed in a vapor deposition apparatus.
A 0.2 μm thick copper layer was formed at a substrate temperature of 150 ° C., a degree of vacuum of 2 × 10 ⁻⁴ Pa or less, a raw material copper purity of ⁴ N, and a deposition rate of 10-25 Å / sec. Further, a 10 μm copper layer was formed thereon by electrolytic plating. The adhesive strength (25 ° C.) measured for each of the laminates was 1.5 kg / cm or more.

(5) Production of electronic parts The above-mentioned copper clad laminate, which is a laminate, is subjected to patterning according to a conventional method, and is then subjected to etching, washing and drying steps.
A flexible circuit board was manufactured by coating and drying the material. During the manufacturing process, there was no trouble such as peeling or curling due to poor bonding, and the electronic component could be manufactured with high accuracy.

[0049]

Since the present invention is configured as described above, the following effects can be obtained.

In the metal layer laminated film of the present invention, the aromatic polyimide film and the metal layer are firmly adhered.
Further, in the electronic component of the present invention, troubles such as peeling due to poor bonding are less likely to occur during the manufacturing process.

[Brief description of the drawings]

FIG. 1 shows an example of a plasma processing apparatus used for performing plasma discharge processing on an aromatic polyimide film in the present invention.

[Explanation of symbols]

 DESCRIPTION OF SYMBOLS 11 Housing of plasma processing apparatus 12 Plasma discharge chamber 13 Plasma discharge electrode whose surface was covered with inorganic dielectric 14 Mixed gas supply source 15 Mixed gas introduction pipe 16 Aromatic polyimide film inlet 17 Aromatic polyimide film outlet 18 Film transport roller 19 Film unwinding roller 20 Aromatic polyimide fill 21 Film winding roll

──────────────────────────────────────────────────の Continued on the front page (51) Int.Cl. ⁶ Identification code FI H01B 3/30 H01B 3/30 H05K 1/03 610 H05K 1/03 610N 3/38 3/38 A

Claims (7)

[Claims] 1. An inorganic polyimide comprising an aromatic tetracarboxylic acid component and an aromatic diamine component, wherein p-phenylenediamine is an essential component in an aromatic polyimide.
Of a polyimide film having a thickness of 5 to 150 μm, good dimensional stability, a volatile matter content of 1.0% by weight or less, and at least one surface modified by a plasma treatment. A metal layer laminated film in which a metal layer is firmly laminated directly or through a heat-resistant adhesive on a textured surface. 2. The method according to claim 1, wherein the modified polyimide film has an inorganic filler in an elemental composition on at least one side of the film.
Shows an increase of 0.03-1.5 atomic%, and the oxygen / carbon ratio on the surface is 0.01-0.20.
The metal layer laminated film according to claim 1, which is modified so as to increase. 3. A plasma in which a modified polyimide film is coated with a dielectric such as an inorganic dielectric on a surface where a large number of polyimide films are arranged in two rows along a film running surface in an atmosphere containing a rare gas. The metal layer laminated film according to claim 1, wherein the metal layer laminated film is obtained by performing a normal-pressure plasma discharge treatment by plasma discharge thereof while running in a space of the discharge electrode without contact. 4. The heat-resistant adhesive is a thermoplastic or thermosetting polyimide adhesive, polyimidesiloxane adhesive, polyimide-epoxy resin adhesive or polyimidesiloxane-epoxy resin adhesive.
3. The metal layer laminated film according to item 1. 5. The polyimide film further has the following conditions: (1) a tensile modulus is 500 kg / mm ² or more; and (2) a linear expansion coefficient (50 to 200 ° C.) is 1.0 × 10 ^−5.
-2.5 × 10 ⁻⁵ cm / cm / ° C. or less, (3) Heat shrinkage (250 ° C. × 2 hours) is 0.5% or less, (4) Specific end crack resistance is 11− 25kg / 20mm / 10
μm. The metal layer laminated film according to claim 1, which satisfies the following. 6. The plasma discharge treatment under normal pressure is 0.8-1.2.
The metal layer laminated film according to claim 1, wherein the film is performed in a gas atmosphere of a pressure. 7. The method according to claim 1, wherein at least one of mechanical, physical and chemical treatments is applied to one of the polyimide layer and the metal layer of the laminated film. Become an electronic component.