JP3395640B2 - Metal layer laminated film - Google Patents

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 an electronic component which is the use thereof. A metal layer laminated film in which a metal layer is firmly laminated directly or through a heat-resistant adhesive on a normal pressure plasma discharge treatment modified surface of a polyimide film in which a fine-particle inorganic filler is dispersed in an aromatic polyimide, And an electronic component using the metal layer laminated film.

[0002]

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

Aromatic polyimide has heat resistance, mechanical strength,
Although it has excellent electrical properties, there is a problem that the aromatic polyimide film and the metal foil (eg, copper foil) are not easily bonded to each other because the surface of the molded product such as the film is inactive. Further, conventionally, adhesives for improving the adhesiveness of the aromatic polyimide film with the metal have been developed, but the adhesiveness between these adhesives and the surface of the aromatic polyimide film is also insufficient.

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

For example, in JP-A-63-61030, the oxygen / carbon ratio on the film surface is increased by 0.01-0.1 by performing corona discharge treatment, and the residual volatile content is 0.45. A polyimide film containing less than or equal to wt% and a metal foil laminated film obtained by laminating a polyimide film and a metal foil (copper foil) with an adhesive are described.

Japanese Unexamined Patent Publication No. 1-138242 discloses that an aromatic polyimide film is supported by a discharge electrode,
A method for surface-modifying an aromatic polyimide film that 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 are described.

JP-A-3-56541 discloses a method for modifying an aromatic polyimide film in which an aromatic polyimide film is previously treated with an organic solvent and then plasma-treated, and the aromatic polyimide film and a metal foil (copper foil). A metal foil laminated film in which and are laminated with an adhesive is described.

Japanese Unexamined Patent Publication (Kokai) No. 5-1160 discloses an aromatic polyimide film in which an aromatic polyimide film is supported by a drum electrode and a discharge electrode such as plasma discharge is performed under normal pressure using an application electrode having a specific shape. Modification Method, Aromatic Polyimide Film and Metal Foil (Copper Foil)
A metal foil laminated film in which and are laminated with an adhesive is described.

[0009]

The method of 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 the aromatic polyimide film. Has been done. However,
What has been clarified as concrete facts in each description is 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 these materials, an aromatic polyimide film having a trade name "Kapton", and a metal foil laminated film using the same,
According to the examples described in the respective publications, it has been clarified that the corona discharge treatment and the plasma discharge treatment for the aromatic polyimide film of this kind are effective for improving the adhesive strength.

However, according to the research on the improvement of the surface characteristics of the aromatic polyimide film by the present inventor, the aromatic polyimide which cannot sufficiently improve the surface characteristics by the above-mentioned known corona discharge treatment or plasma treatment. A film was found to be present.

That is, as another type of aromatic polyimide film, an aromatic tetracarboxylic acid component such as 3,3 ', 4,4'-biphenyltetracarboxylic dianhydride and p are used.
-Aromatic polyimide films containing p-phenylenediamine as an essential component, such as polyimide films obtained from phenylenediamine, are known. -Diaminodiphenyl ether is an aromatic polyimide film having more excellent mechanical strength and dimensional stability than an aromatic polyimide film produced from the aromatic polyimide film. It is known to be difficult. And p- as described above
Even if the above-mentioned conventional discharge treatment is applied to an aromatic polyimide film containing phenylenediamine as an essential component, satisfactory surface modification (particularly improvement of adhesiveness) is not realized. Moreover, in the case of the vacuum plasma discharge treatment, there is a problem that it takes a high cost to make a vacuum.

Therefore, an object of the present invention is to provide an aromatic polyimide film comprising an aromatic tetracarboxylic acid component and an aromatic diamine component, which have improved surface characteristics, particularly adhesiveness, and which contains p-phenylenediamine as an essential component. A metal layer laminated film in which a metal layer is firmly laminated directly or through a heat-resistant adhesive on the modified surface of a polyimide film whose surface on at least one side has been modified by atmospheric pressure plasma treatment, and using it To provide the electronic components that were used.

[0013]

That is, the present invention is
A fine inorganic filler is dispersed in an aromatic polyimide which is composed of an aromatic tetracarboxylic acid component and an aromatic diamine component and contains p-phenylenediamine as an essential component, and has a thickness of 5-150 μm and a heat shrinkage ratio. (250 ° C x
2 hours) is less than 0.3% and volatile content is 0.4% by weight
Plasma discharge in which both surfaces of a polyimide film having the following good dimensional stability are arranged in two rows along the running surface of the film in an atmosphere containing Ar, N ₂ and H ₂ and covered with an inorganic dielectric. While running in the contactless space of the electrode, the plasma discharge treatment is carried out by the plasma discharge of those electrodes. The polyimide film modified by the atmospheric pressure plasma treatment is bonded to the polyimide adhesive or polyimide siloxane adhesive. Agent, polyimide-epoxy resin adhesive or polyimide siloxane-epoxy resin adhesive, heat resistant adhesive, rolled copper foil or electrolytic copper foil with adhesive strength (T peeling) of 1.2 kg / cm or more. The present invention relates to a laminated metal layer film.

The surface-modified polyimide film of the present invention comprises an aromatic tetracarboxylic acid component, preferably 3,3 ', 4,4'-biphenyltetracarboxylic acid 1.
Or a combination of two kinds of 3,3 ′, 4,4′-biphenyltetracarboxylic acid, pyromellitic acid and 3,3 ′, 4,4′-benzophenonetetracarboxylic acid, or their anhydrides or Aromatic tetracarboxylic acid component containing ester and aromatic diamine component containing p-phenylenediamine, preferably one kind of p-phenylenediamine, or two kinds of p-phenylenediamine and 4,4-diaminodiphenyl ether. P- which is a combination of
A polyimide film obtained from an aromatic diamine component containing phenylenediamine, under an atmosphere containing a rare gas,
The plasma discharge electrode, which has a large number of surfaces arranged in two rows along the running surface of the film, is covered with a dielectric such as an inorganic dielectric while running in a non-contact manner, and the plasma discharge treatment is performed at atmospheric pressure by these plasma discharges. It can be easily obtained depending on the method used. The above-mentioned polyimide film also includes those slit into a tape shape.

In the aromatic polyimide film according to the present invention, the amount of the element of the inorganic filler in the elemental composition on at least one side of the film is 0.03-1.5.
Atomic%, especially 0.05-1.0 atomic%, and an oxygen / carbon ratio on the surface of 0.01-0.2.
It is preferably modified so as to increase 0, particularly 0.05 to 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 manufactured as follows, as described in, for example, Japanese Patent Application No. 9-63751. First 3,3 ', 4,4'-
Biphenyl tetracarboxylic dianhydride, or 3,
Any one of 3 ', 4,4'-biphenyltetracarboxylic dianhydride, pyromellitic dianhydride and 3,3', 4,4'-benzophenonetetracarboxylic dianhydride 2
Combination of seeds [coefficient of linear expansion (50 to 200 ° C) is 1.
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 consisting of and one kind of p-phenylenediamine, or p
-N, N-dimethylacetamide and an aromatic diamine (p-phenylenediamine is preferably 15-100 mol%) consisting of a combination of two kinds of phenylenediamine and 4,4-diaminodiphenylether. In an organic polar solvent usually used for the production of polyimides such as N-methyl-2-pyrrolidone and the like, preferably 10-
Polymerized at 80 ° C. for 1 to 30 hours, the logarithmic viscosity of the polymer (measurement 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
A solution of polyamic acid (imidization rate: 5% or less) having a temperature of 500-4500 poise is obtained.

Next, this polyamic acid 10 is preferably used.
0.01 to 3% by weight relative to 0 parts by weight of a phosphorus compound, for example, an organic phosphorus-containing compound such as a (poly) phosphate ester and / or amine circle of a phosphate ester or an inorganic phosphorus compound, and preferably a polyamic acid 0.1-3 parts by weight per 100 parts by weight of an inorganic filler such as colloidal silica, silicon nitride, talc, titanium oxide, calcium hydrogen phosphate (preferably an average particle size of 0.005-5 μm,
In particular, 0.005-2 μm) is added to prepare a polyamic acid solution composition. These phosphorus compound and inorganic filler may be uniformly present in the entire film layer, or in the case of forming a film having a 2-3 layer structure, the phosphorus compound and the inorganic filler should be contained in the layer containing at least one surface in the above proportions. Is preferred.

When this polyamic acid solution composition is cast on the surface of a glass or metal support having a smooth surface to form a thin film of the solution, and the thin film is dried,
Adjust the drying conditions (preferable conditions are 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 imidization rate of 10 to 60% by weight.
Is formed, and the solidified film is peeled off from the surface of the support.

The solidified film obtained as described above is further dried, if necessary, and preferably adjusted so that the volatile content of the dried film is 10 to 45% by weight, and then the dried film is dried. With the both edges in the width direction being gripped, the maximum temperature after drying was set so that the temperature (° C) x residence time (minutes) at the cure furnace inlet in the cure furnace was within the shaded area in Fig. 1 of the application specification. Heating temperature: 400-
The dried film is heated and dried and imidized under the condition that the temperature of 500 ° C. is 0.5 to 30 minutes, and the imidization is performed at a residual volatile content of 1.0% by weight or less, particularly 0.4% by weight or less. When completed, it can be suitably manufactured as an aromatic polyimide film.

The aromatic polyimide film obtained as described above is preferably treated under low tension or no tension.
Stress relaxation treatment by heating at a temperature of about 00-400 ° C,
Roll up. The aromatic polyimide film is controlled such that the heating condition before curing in the curing furnace at the time of manufacturing is controlled within the shaded area in FIG. 1 of the above-mentioned application specification and the curing condition is controlled at the above temperature range. When the content is 5 to 150 μm, the dimensional stability is good and the residual volatile content is 1.0% by weight or less, especially 0.4% by weight or less, and the specific end tear resistance is large. be able to. If the amount of residual volatiles in the film is more than 1.0% by weight, it is difficult to improve the adhesiveness. The above-mentioned polyimide film may polymerize each monomer component (random, block),
Alternatively, the same can be obtained by blending. The aromatic polyimide film is not limited to the above-mentioned thermal imidization, and can be carried out by either catalyst or chemical imidization within the range of the above conditions.

The thickness of the aromatic polyimide film in the present invention is in the range of 5-150 μm, preferably 2
Inorganic filler in the form of fine particles in the range of 5-125 μm
Is included. The content of the inorganic filler in the aromatic polyimide film is preferably 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 accuracy. (1) The tensile elastic modulus is 500 Kg / mm ² or more, and (2) the linear expansion coefficient (5
0 to 200 ° C.) is 1.0 × 10 ⁻⁵ −2.5 × 10 ⁻⁵ cm
/ Cm / ° C or lower, and (3) heat shrinkage ratio (250 ° C x
(2 hours) is 0.5% or less, and (4) specific end tear resistance value is 11-25 kg / 20 mm / 10 μm.

The aromatic polyimide film which is the object of the plasma discharge device (normal pressure plasma treatment, that is, plasma discharge treatment at 0.8-1.2 atm) according to the present invention has an inorganic film on the surface thereof as described above. A method of forming a film surface by forming a large number of protrusions (covered with polyimide) formed by a filler is used. Incidentally, the usual aromatic polyimide film,
On the side where the dope solution containing the inorganic filler in a dispersed state was in contact with the support (generally referred to as the B side), the adhesiveness reached a practically sufficient level, but on the opposite side. The surface (generally referred to as side A) has poor adhesion.

In the plasma discharge treatment of the present invention, in particular, the A-side of an aromatic polyimide film containing an inorganic filler (which is also applied to an aromatic polymer film containing another inorganic filler) is subjected to a plasma discharge treatment. As a result, the aromatic polyimide layer coating 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) can be observed by ESCA analysis described later. It is thought that this is because the exposed surface is exposed and an effective increase in adhesive strength is realized.

Therefore, the plasma discharge treatment of the present invention is
The treatment is preferably performed on the A-side (non-support-side surface) of the aromatic polyimide film containing the inorganic filler, but it is preferable to perform the plasma discharge treatment on both sides of the aromatic polyimide film.

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

In FIG. 1, reference numeral 11 is a housing of the 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 covered with a dielectric such as an inorganic dielectric (preferably glass) are arranged in two rows along the film running surface in two rows. (The inside is cooled to about 10-50 ° C). Plasma discharge chamber 12
Is a gas supply source 1 for supplying a gas containing a rare gas such as argon forming a discharge atmosphere in the discharge chamber.
4 is provided with a gas introduction pipe 15 connected thereto, and an inlet 16 and an outlet 17 for the aromatic polyimide film to be plasma-treated are provided.

The gas atmosphere for carrying out the plasma discharge treatment in the present invention contains argon as a main component,
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 this gaseous atmosphere.

Outside and inside the plasma processing apparatus,
A large number of film transport rollers 18 are provided for assisting the non-contact running in the space of the plasma discharge electrode of the aromatic polyimide film.
Aromatic polyimide film 20 unrolled from reel 19
Of the aromatic polyimide film 20 that has been processed and finally delivered to the winding roll 21.

The outline of the plasma processing apparatus used for the plasma discharge processing of the present invention is as shown in FIG. 1. For example, the number of discharge chambers can be increased or decreased, the arrangement can be changed, the number of plasma discharge electrodes can be increased or decreased, and the arrangement can be changed. It goes without saying that changes and the like can be made. The plasma discharge treatment of the present invention uses, for example, the plasma treatment apparatus shown in FIG. 1 to bring an aromatic polyimide film containing an inorganic filler in a dispersed state into contact with a plasma discharge electrode during discharge in the direction of the arrow. It is preferable to use such a discharge treatment, because the discharge treatment on both sides of the film is realized by continuously running without the discharge.

In the modified polyimide film treated by plasma discharge as described above, the amount of the element of the inorganic filler in the elemental composition on at least one side of the film is 0.0.
Those exhibiting an increase of 3 to 1.5 atom% and an increase in the oxygen / carbon ratio of 0.01 to 0.20 on the surface thereof are preferable.

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

In the metal layer laminated film of the present invention, the metal layer is firmly laminated directly on the modified surface of the polyimide film modified as described above or directly via a heat resistant adhesive (the adhesive strength is usually 1 0.0 kg / cm or more). 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-phenolic resin, phenol. -Butyral resin, epoxy-NBR resin, epoxy-phenol resin, epoxy-nylon resin, epoxy-polyester resin, epoxy-
Acrylic resin, acrylic resin, polyamide-epoxy-phenol resin, polyimide resin, polyimide-epoxy resin, polyimide siloxane-epoxy resin or other thermosetting adhesive, or polyamide resin, polyester resin, Thermoplastic adhesives such as polyimide-based resins and polyimide-siloxane-based resins can be used. In particular, polyimide-based adhesives, polyimide-epoxy resin-based adhesives, polyimide siloxane-epoxy resin-based adhesives, and epoxy resin adhesives are preferably used.

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

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 bonded,
It can be preferably used for a computer or an FPC.

The electronic component of the present invention can be obtained, for example, by forming a circuit on the above metal layer laminated film, if necessary, after forming a metal layer laminated tape. The circuit is formed by printing, for example, an etching resist on the metal surface of the metal layer laminated film in a circuit pattern shape (wiring pattern shape) to protect the surface of the metal layer where the wiring pattern is formed. After forming the wiring pattern of the etching resist, the metal of 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 can be removed. If necessary, the upper surface of the circuit pattern may be treated directly or with a surface treatment agent such as a Syra coupling agent, and then a coating material (liquid material) may be applied and dried by heating to form a coating layer. 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 internal volume of 100 liters, and then 3,3 ′, 4.
4'-biphenyltetracarboxylic dianhydride 8.826
kg and para-phenylenediamine (3.243 kg) were added, and the polymerization reaction was carried out at 30 ° C. for 10 hours to obtain the logarithmic viscosity of the polymer (measurement temperature: 30 ° C., concentration: 0.5 g / 100 ml solvent, solvent: N, N-dimethylacetamide. ) Is 1.6
0, a polyamic acid (imidization ratio: 5% or less) solution having a polymer concentration of 18% by weight was obtained. This polyamic acid solution was added with 0.
1 part by weight of a triethanolamine amine salt of monostearyl phosphate and 0.5 part by weight (solid content basis) of colloidal silica having an average particle diameter of 0.08 μm 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 through 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 be solidified into a long shape. A film (volatile content 28% by weight) was obtained.

Next, the both edges of the dried film in the width direction were held and cured in a curing furnace (temperature at inlet × residence time = 200 ° C. × 2.5 minutes, maximum temperature ×
Maximum temperature retention time = 480 ° C. × 3 minutes), thickness 50 μm,
A long aromatic polyimide film having a residual volatile content of 0.18% by weight and an imidization ratio of 95% or more (0.2% by weight of Si
(Containing O ₂ ) was continuously obtained. The physical properties of this aromatic polyimide film were measured as follows. Tensile elastic modulus: ASTM D882-64T Linear expansion coefficient (50-200 ° C.): A sample which was heated at 300 ° C. for 30 minutes to relax the stress was used as a TMA device (tensile mode).
Heat shrinkage rate (250 ° C., 2 hours): JIS C2318 Edge tear resistance (or specific edge tear resistance): JIS C2318
It means the average value of edge crack resistance (or specific edge resistance) of the samples (5 pieces) measured according to Specifically, the center line of the V-shaped notch plate test fixture with an upper thickness of 1.00 ± 0.05 mm of the constant speed tension type tensile tester is made to coincide with the center line of the upper grip, and the notch apex and the lower grip are Interval about 30
Attach the handle so that it becomes mm. A test piece with 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 bottom of the tester, 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 each of the lengthwise direction and the widthwise direction over the entire width, and the average value of the end tear resistance was determined and shown as the end tear resistance value. The specific edge resistance is the edge resistance per film thickness (10 μm conversion).

The physical properties of this aromatic polyimide film are shown below. Tensile elastic 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 tear resistance: 66 kg / 20 mm Specific edge tear resistance: 13.2 kg / 20 mm / 10 μm

(2) Plasma discharge treatment Atmospheric pressure plasma treatment equipment having the same structure as the plasma treatment equipment shown in FIG. 1 (however, only one plasma discharge chamber is provided,
The plasma discharge treatment was carried out at 1 atm), and the plasma treatment was performed at the gas composition and film running speed in the plasma discharge treatment chamber shown in Table 1 below. Voltage is 200V /
One electrode. The inside of the electrode is water cooled (25 ° C).

[0041]

[Table 1]

(3) Surface composition analysis of plasma-discharge-treated film 1) Measurement of silicon (Si) atomic concentration (atomic%) The silicon concentration on the surface of an aromatic polyimide film subjected to plasma discharge treatment was measured by ESCA method. Measured. The results are shown in Table 2. 2) Aromatic polyimide film subjected to plasma discharge treatment for increasing oxygen / carbon ratio,
The oxygen / carbon ratio of each surface of the aromatic polyimide film not subjected to the plasma discharge treatment was measured using the ESCA method. The results are shown in Table 2 as the increment of oxygen / carbon ratio with respect to the aromatic polyimide film not subjected to the plasma discharge treatment.

(4) Metal layer laminated film (using adhesive)
Preparation of plasma discharge treated aromatic polyimide film or plasma discharge treated aromatic polyimide film and copper foil, the respective 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 was the surface, and the surface B, which was the surface that was in contact with the support surface during film production. A) Adhesive: heat-fusible polyimide resin (a-BPDA /
TPER Tg: 240 ° C.) b) Copper foil: electrolytic copper foil with a thickness of 30 μm c) Adhesion conditions: A thin adhesive (20 μ after drying) on the copper foil
m) After coating and drying at 130 ° C. for 15 minutes, plasma discharge treated polyimide films are overlaid, 300 ° C., 6.5 kg /
It was thermocompression-bonded at cm ² for 5 minutes and heat-treated at 180 ° C. for 1 hour. D) Adhesive 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 strengths of the A-side and B-side of the aromatic polyimide film not subjected to the plasma discharge treatment.

[0045]

[Table 2]

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

(5) Preparation of metal layer laminated film (vapor deposition-electrolytic plating) Each surface of the aromatic polyimide film subjected to the plasma discharge treatment (the surface which was not in contact with the surface of the support at the time of film production). (A-side, and B-side, which is the surface on the side that contacts the support surface during film production)
After cutting out to a holder size and installing it in the vapor deposition device,
A copper layer having a thickness of 0.2 μm was formed under the conditions of 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 vapor 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 this laminate was 1.5 kg / cm or more in all cases.

(5) Manufacture of electronic parts The copper clad plate which is the above laminated body is subjected to patterning according to a conventional method, and then subjected to etching, water washing and drying steps, and then a co-coating.
A flexible circuit board was manufactured by applying a coating material and drying it. During the manufacturing process, problems such as peeling and curling due to poor adhesion did not occur, and electronic parts could be manufactured with high accuracy.

[0049]

Since the present invention is configured as described above, it has the following effects.

In the metal layer laminated film of the present invention, the aromatic polyimide film and the metal layer are firmly adhered.
Further, the electronic component of the present invention is less likely to cause troubles such as peeling due to defective adhesion during the manufacturing process.

[Brief description of drawings]

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

[Explanation of symbols]

11 Plasma processing device housing 12 Plasma discharge chamber 13 Plasma discharge electrode whose surface is coated with an inorganic dielectric 14 Mixed gas supply source 15 Mixed gas introduction pipe 16 Aromatic polyimide film entrance 17 Aromatic polyimide film outlet 18 Film transport roller 19 Rolling film roll 20 Aromatic polyimide fill 21 Film winding roll

─────────────────────────────────────────────────── ─── Continuation of front page (51) Int.Cl. ⁷ Identification code FI H05K 3/38 H05K 3/38 A (58) Fields investigated (Int.Cl. ⁷ , DB name) B32B 1/00-35 / 00 C08J 7/00 H05K 1/03 H05K 3/38

Claims (4)

(57) [Claims] 1. A fine-particle inorganic filler in an aromatic polyimide which comprises an aromatic tetracarboxylic acid component and an aromatic diamine component and contains p-phenylenediamine as an essential component.
Having a thickness of 5-150 μm, a heat shrinkage ratio (250 ° C. × 2 hours) of 0.3% or less, a volatile content of 0.4% by weight or less, and good dimensional stability. While both surfaces of the film were run in an atmosphere containing Ar, N ₂ and H ₂ in a non-contact manner in a space of a plasma discharge electrode in which a large number of surfaces arranged in two rows along the running surface of the film were coated with an inorganic dielectric material. , A normal pressure plasma discharge treatment by those plasma discharges, a polyimide-based adhesive, a polyimide siloxane-based adhesive, a polyimide-epoxy resin-based adhesive or a polyimide on the modified surface of the polyimide film modified by the normal pressure plasma treatment. Through a heat resistant adhesive which is a siloxane-epoxy resin adhesive,
A metal layer laminated film obtained by laminating a rolled copper foil or an electrolytic copper foil with an adhesive strength (T peeling) of 1.2 kg / cm or more. 2. A modified polyimide film comprising an inorganic filler in an elemental composition on at least one side of the film.
The amount of the element of 0.03 to 1.5 atomic% increases, and the oxygen / carbon ratio on the surface is 0.01 to 0.20.
The metal layer-laminated film according to claim 1, which is modified so as to increase. 3. The polyimide film further has the following conditions (1) a tensile elastic modulus of 500 kg / mm 2 or more, and (2) a linear expansion coefficient (50 to 200 ° C.) of 1.0 × 10 -5.
−2.5 × 10 −5 cm / cm / ° C. or less, and (3) specific end tear resistance value is 11-25 kg / 20 mm / 10.
μm. The metal layer laminated film according to claim 1, which satisfies the above condition. 4. The atmospheric pressure plasma discharge treatment is 0.8-1.2.
The metal layer laminated film according to claim 1, which is performed in a gas atmosphere at atmospheric pressure.