JP2008056756A - Polyimide film for metal lamination, method for producing the same, and metal-laminated plate - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a polyimide film for metal lamination without giving an effect to an adhesive and obtaining excellent bonding property-improving effect stably and inexpensively, and a method for producing the same and a metal-laminated plate. <P>SOLUTION: This polyimide film for laminating the metal is obtained by laminating the adhesive on the scratch-treated surface of the polyimide film obtained by scratch-treating the surface to form strip-formed unevenness. Also, the method for producing the polyimide film for laminating the metal is provided by scratch-treating the surface of the polyimide film by using a grinding tape obtained by coating fine grinding material particles on its surface, and then laminating the adhesive on the scratch-treated surface of the polyimide. Further, the metal-laminated plate is obtained by laminating metal foil on the adhesive of the polyimide film for the metal lamination. <P>COPYRIGHT: (C)2008,JPO&INPIT

Description

  The present invention relates to a polyimide film for metal lamination with improved adhesion between a polyimide film and a metal foil, a production method and a metal laminate using the polyimide film, and more specifically, without affecting the adhesive and excellent The present invention relates to a metal-laminated polyimide film capable of stably and inexpensively improving the adhesiveness, a manufacturing method, and a metal laminate using the polyimide film.

  Polyimide films are known to have excellent insulation, heat resistance, electrical properties, and mechanical properties. Therefore, electrical insulation materials for wires, heat insulation materials, flexible circuit board (FPC) base films, It is widely used as a base film for carrier tape for tape automated bonding (TAB), a tape for fixing IC lead frames, and the like. Among these, in applications such as FPC, TAB carrier tape, lead frame fixing tape, etc., a polyimide film and a copper foil are usually bonded to each other through various adhesives.

  However, due to its chemical structure and high chemical resistance (solvent) stability, polyimide films often have insufficient adhesion to copper foil. It was necessary to apply.

  Specific examples of the surface treatment include, for example, sandblasting (see, for example, Patent Document 1), corona discharge treatment (for example, see Patent Document 2), plasma processing (for example, see Patent Document 3), and alkali treatment (for example, Patent Document 1). In addition, after performing these treatments, a copper foil was adhered to the treated surface of the polyimide film via an adhesive.

  However, for example, in alkali treatment, sandblast treatment, etc., after the polyimide film is formed, each treatment such as alkali treatment is performed, and further steps such as washing and drying are required. Therefore, productivity, stability, and cost are reduced. The problem included not only the aspect but also the environmental preservation aspect.

Recently, corona discharge treatment and plasma treatment have been proposed for the purpose of improving adhesiveness, and although the corresponding effect can be obtained, the long-term stability of the adhesive strength after the treatment is lacking. Use of high voltage energy and atmospheric gases such as tetrafluoromethane, oxygen, nitrogen, argon, carbon dioxide and mixed gas of these are used in plasma processing. There were problems in terms of increased costs, uneven processing, and environmental conservation.
JP-A-8-34866 JP 7-330930 A JP-A-2003-55487 Japanese Patent Laid-Open No. 8-12779

  The present invention has been achieved as a result of studying the solution of the problems in the prior art described above as an issue.

  Accordingly, an object of the present invention is to provide a polyimide film for metal lamination that can stably and inexpensively obtain an excellent adhesive improvement effect without affecting the adhesive, a manufacturing method, and a metal laminate using the polyimide film There is to do.

  As a result of intensive studies to solve the above-mentioned problems, the inventors have performed a specific rubbing treatment on the surface of the polyimide film, so that it is stable and practically sufficient at a low cost. It has been found that a polyimide film for metal lamination with improved adhesion can be obtained, and the present invention has been achieved.

  That is, in order to achieve the above object, according to the present invention, an adhesive is laminated on the rubbing surface of a polyimide film formed by rubbing the surface to form streaks. A featured polyimide film for metal lamination is provided.

In the polyimide film for metal lamination of the present invention,
The film surface roughness Rz measured according to JIS B-0601 (2001) of the scratched surface is 0.7 to 10 μm,
The height difference of the stripe-like irregularities on the scratched surface is in the range of 0.05 to 10 μm,
The maximum height Ry of the height difference of the stripe-shaped unevenness on the scratched surface is in the range of 4 to 10 μm;
The maximum width of the stripe-like irregularities on the scratched surface is in the range of 0.1 to 20 μm, and the number of stripe-like irregularities on the scratched surface is in the range of 0.1 to 10,000 / mm, All are mentioned as preferable conditions.

Moreover, the manufacturing method of the polyimide film for metal lamination according to the present invention is as follows.
The surface of the polyimide film is rubbed with a polishing tape coated with fine abrasive particles on the surface, and a metal foil is laminated on the rubbed surface of the polyimide film via an adhesive.
The abrasive particles are any of silicon carbide, aluminum oxide, chromium oxide, cerium oxide, diamond particles;
The abrasive particles have a particle size of 0.1 to 100 μm,
In the first stage, the surface of the polyimide film is abraded with an abrasive tape in which abrasive particles having a particle size of 0.1 μm or more and less than 10 μm are disposed, and then in the second stage, polyimide is coated with an abrasive tape in which abrasive particles having a particle size of 10 μm or more and 100 μm or less are disposed. Abrading the surface of the film and polishing the surface of the polyimide film with an abrasive tape in which abrasive particles having a particle size of 10 μm or more and 100 μm or less are arranged in the first stage, and then polishing the particle size of 0.1 μm or more and less than 10 μm in the second stage It is a preferable condition that the surface of the polyimide film is rubbed with a polishing tape on which material particles are arranged.

  Moreover, as a metal laminated board, it is a metal laminated board which laminated | stacked metal foil on the adhesive bond layer of these polyimide films for metal lamination.

  ADVANTAGE OF THE INVENTION According to this invention, the polyimide film for metal lamination which can obtain the outstanding adhesive improvement effect stably and cheaply can be provided as demonstrated below.

  Hereinafter, the present invention will be described in detail.

  As an example of the polyimide film used in the present invention, a polyimide film produced from a polyamic acid obtained from pyromellitic dianhydride as an aromatic tetracarboxylic acid and 4,4′-diaminodiphenyl ether as an aromatic diamine, 3 , 3 ', 4,4'-biphenyltetracarboxylic dianhydride, pyromellitic dianhydride, p-phenylenediamine, polyimide film produced from polyamic acid obtained from 4,4'-diaminodiphenyl ether , Pyromellitic dianhydride, 4,4′-diaminodiphenyl ether, polyimide film prepared from polyamic acid obtained from three components of 3,4′-diaminodiphenyl ether, pyromellitic dianhydride, 4,4′- Diaminodiphenyl ether, p-phenylene A polyimide film produced from a polyamic acid obtained from three components of amine, a polyimide film produced from a polyamic acid obtained from 3,3 ′, 4,4′-biphenyltetracarboxylic dianhydride and p-phenylenediamine, Examples thereof include a polyimide film produced from a polyamic acid obtained from 3,3 ′, 4,4′-biphenyltetracarboxylic dianhydride and 4,4′-oxydianiline. The decyclization of polyamic acid to polyimide may be either a chemical ring closure method or a thermal ring closure method. Further, for the purpose of improving workability, it is possible to contain 10% by weight or less of an inorganic or organic additive.

  The thickness of the polyimide film is desirably 3 to 200 μm. If the thickness is less than 3 μm, it is difficult to maintain the shape, and if it exceeds 200 μm, the flexibility is insufficient, so that it is not suitable for flexible circuit board applications. In order to improve the dimensional stability of the polyimide film, a low thermal shrinkage treatment may be performed by an annealing treatment or the like.

  The polyimide film used in the present invention needs to form streak-like irregularities by rubbing the surface.

  A streak-like unevenness means that a concave portion and a convex portion are continuously present on the surface of the film. A cross-sectional view of a film having streak-like irregularities of a typical shape is shown in FIG. In the figure, 9 indicates the original surface position of the film, 8 is a concave portion, and 7 is a convex portion. The height difference 5 of the unevenness is a value obtained by measuring the length of the vertex of the convex portion 7 and the vertex of the concave portion 8. 5 is drawn with the concave portion long, but the concave / convex pattern is not limited to this, and the convex portion is extremely low and may not rise so much from the film surface position 9 in some cases. The film of the present invention has a large number of such streaks on the surface. There are a large number of stripe-shaped irregularities with large height differences (those with deep grooves) and small height differences (those with shallow grooves), but those height differences are in the range of 0.05 to 10 μm. It is necessary to be. The presence of a large number of stripes with a height difference of less than 0.05 μm deteriorates the adhesion between the film and the metal foil, and the presence of more than 10 μm causes an undesirable tendency to deteriorate the mechanical properties of the film. There are times.

  The polyimide film used in the present invention preferably has a film surface roughness Rz measured according to JIS B-0601 (2001) of 0.7 to 10 μm, more preferably 2 to 9 μm, and more preferably 3 to 8 μm. Further preferred. The film surface roughness Rz shown here is a value measured with a laser microscope based on JIS B-0601 (2001) “Surface roughness”, and actually a scanning laser microscope “1LM15W” manufactured by Lasertec Corporation. In Nikon 50x lens (CF Plan Apo 50 × / 0.95 ∞ / 0 EPI), the film surface was photographed in “SURFACE2” mode, and then roughed with Mitani Corporation SALT. This is a value obtained by reading the value of Rz (ten-point average roughness) by setting the cut-off value at the time of creating the height curve to 0.025 mm, analyzing the area having an extended surface roughness of 0.01 mm 2 or more. These characteristics can be obtained by providing specific streak-like irregularities on the film surface.

Moreover, it is preferable that the stripe-shaped unevenness | corrugation exists in the range whose maximum height Ry of the height difference is 4-10 micrometers. The maximum height Ry here is specifically determined by using a Nikon 50x lens (CF Plan Apo 50 × / 0.95∞ / 0 EPI) with a scanning laser microscope “1LM15W” manufactured by Lasertec Corporation. This is a value confirmed by the maximum height Ry by analysis in an area having an extended surface roughness of 0.01 mm ² or more in SALT after photographing in the “SURFACE 2” mode. The presence of streak-like irregularities having a maximum height of 4 to 10 μm is preferable because the adhesion between the film and the metal foil is further improved.

  Furthermore, the width of the stripe-shaped unevenness is preferably adjusted to a range of 0.1 to 20 μm, and more preferably adjusted to a range of 0.1 to 10 μm. The width of the stripe-shaped unevenness here is a value obtained by measuring 6 in FIG. If it is below this range, the adhesion between the film and the metal foil is deteriorated, and if it exceeds, the mechanical properties of the film are deteriorated, which is not preferable.

  In particular, the number of stripe-shaped irregularities is preferably adjusted to a range of 0.1 to 10000 / mm, more preferably 10 to 1000 / mm, and more preferably 100 to 500 / mm. It is even more preferable to adjust. If it is below this range, the adhesion between the film and the metal foil is deteriorated, which is not preferable, and if it exceeds this range, the mechanical properties of the film are deteriorated.

  When the above-mentioned stripe-like unevenness is imparted to the surface of the polyimide film, it is necessary to rub the surface of the polyimide film with an abrasive tape having fine abrasive particles coated on the surface.

  For example, as shown in FIG. 1 to FIG. 4, streak-like irregularities can be formed by running a polishing tape in contact with a polyimide film.

  In FIG. 1, the polyimide film is fed from an unwinding roll 1 and wound around the winding roll 2 while rubbing the surface of the polishing roll 3 rotating in the direction opposite to the traveling direction.

  In FIG. 2, the polyimide film exiting the unwinding roll 1 is wound around the winding roll 2 while rubbing between the polishing roll 3 and the pressing roll 4 rotating in the opposite direction. The surface pressure at this time is preferably 1 to 10 kg / 500 mm.

  In FIG. 3, the polyimide film exiting the unwinding roll 1 is wound around the winding roll 2 while rubbing between two polishing rolls 3 and 3 ′ rotating in opposite directions. Here, if the surface pressure is increased, it becomes difficult to run the film. Therefore, the surface pressure is preferably set to 0.1 to 5 kg / 500 mm.

  Furthermore, when the polishing process is continuously performed twice or more, the processes can be performed side by side as shown in FIG.

  When processing only one side of the film, it can be processed by the method shown in FIG. 1, FIG. 2, or FIG. 4, but FIG. 2 or FIG. 4 can control the pressure when the polishing roll is brought into contact with the film. It is preferable because unevenness can be efficiently imparted. When processing both surfaces of a film, it can obtain by processing as shown in FIG. The tension applied to the film during these treatments is preferably adjusted in the range of 10 to 50 N / m, and the treatment speed is preferably adjusted in the range of 5 to 40 m / min.

  The polishing roll has only to have a hard surface and a rough state, but a polishing tape in which a polishing agent is coated on a tape may be attached to a normal roll. Examples of the abrasive tape include a type in which a PET film is used as a base and abrasive particles are coated thereon. The thickness of the PET film as the base is preferably in the range of 25 to 75 μm because it is easy to handle. Examples of the abrasive particles include silicon carbide, aluminum oxide, chromium oxide, cerium oxide, and diamond. The particle size of these abrasive particles may be in the range of 0.1 to 100 μm depending on the degree of roughening. Preferably, it is in the range of 1 to 50 μm, and more preferably in the range of 5 to 40 μm. If the particle size is larger than this range, the film may be excessively roughened and the mechanical properties such as strength may be impaired, or the film may be broken during processing, and if the particle size is smaller than this range, the film and the metal foil may be damaged. Since the effect which improves adhesiveness becomes low, it is not preferable. In addition, it is possible to process with multiple abrasives. First, use an abrasive with a particle size of less than 10 μm, then apply fine streaks on the entire surface, then use an abrasive with a particle size of 10 μm or more. In addition, there is a method of providing streak-like irregularities having a high height difference and a large width, and vice versa.

  The direction of the stripe-shaped unevenness is given along the direction parallel to the machine feed direction (MD) of the film, given along the direction parallel to the width direction (TD) of the film, and obliquely with respect to the machine feed direction. However, as shown in FIGS. 1 to 4, the method of applying along the machine feed direction (MD) of the film can be simplified most easily. Therefore, it is preferable.

  As for other polishing methods, a disc-shaped disk type may be used as the polishing tape, and this may be caused to contact the surface of the film while rotating, thereby causing streak-like irregularities to be generated in completely random directions. Note that plasma treatment may be further performed after the rubbing treatment.

  In order to produce the polyimide film for metal lamination of the present invention, an adhesive is then laminated on the scratched surface of the polyimide film. In the present invention, generally known thermoplastic polyimide adhesives, epoxy resin adhesives or acrylics are used. A system adhesive can be used. Examples of the method for laminating the adhesive include coating, spraying, and laminating.

  Furthermore, in order to manufacture a metal laminated board, a metal foil is laminated | stacked on the adhesive bond layer of the polyimide film for metal lamination obtained above. As a lamination method at this time, a known method such as pressure bonding or lamination can be used.

  In this way, by applying streak-like irregularities to the film surface by rubbing treatment, the adhesiveness when laminating the rubbing surface of this polyimide film and a metal foil represented by copper foil via an adhesive is improved. Significant improvement is possible.

  Thus, it is possible to obtain a metal laminate in which the adhesion between the polyimide film and the metal foil is practically and sufficiently improved regardless of the type of the adhesive.

  Hereinafter, the present invention will be described more specifically with reference to examples. In addition, each characteristic in an Example is the value measured with the following method.

[Measurement of surface roughness Rz of film]
Based on JIS B-0601 (2001) "Surface roughness", it was measured with a laser microscope. That is, the surface of the film was photographed in the “SURFACE2” mode using a scanning laser microscope “1LM15W” manufactured by Lasertec Co., Ltd. and using a Nikon 50 × lens (CF Plan Apo 50 × / 0.95∞ / 0 EPI). Later, at SALT manufactured by Mitani Shoji Co., Ltd., the cut-off value when creating the roughness curve was set to 0.025 mm, and the area with an extended surface roughness of 0.01 mm 2 or more was analyzed. The average roughness value was read.

[Difference in the height of streaks]
Using the scanning laser microscope “1LM15W” manufactured by Lasertec Co., Ltd., using Nikon 50 × lens (CF Plan Apo 50 × / 0.95∞ / 0 EPI), the film surface was photographed in “SURFACE1” mode. The height difference (5 in FIG. 5) of each stripe-like unevenness was read from the chart obtained by analysis. The representative value is the average value of 5 points selected at random, and the maximum value is the maximum height Ry by analysis in the area of the extended surface roughness of 0.01 mm2 or more in SALT after photographing in the “SURFACE2” mode. Confirmed with.

[Striped uneven width]
Using the scanning laser microscope “1LM15W” manufactured by Lasertec Co., Ltd., using Nikon 50 × lens (CF Plan Apo 50 × / 0.95∞ / 0 EPI), the film surface was photographed in “SURFACE1” mode. Analysis was performed, and the L key (left) and R key (right) were determined for each streak, and the streak width (6 in FIG. 5) was read. The maximum width streak that can be seen in this field of view was used as a representative value.

[Number of stripe-shaped irregularities (density)]
The surface of the film was photographed in “SURFACE1” mode using a scanning laser microscope “1LM15W” manufactured by Lasertec Co., Ltd. and using a Nikon 50 × lens (CF Plan Apo 50 × / 0.95∞ / 0 EPI). The number of streaks that were observed was counted.

[Adhesive strength evaluation]
The rubbing process surface of a polyimide film and copper foil (Nikko Materials Co., Ltd. electrolytic copper foil BHY-13B-T 1oz) were bonded together on condition of the following through the following 3 types of adhesives.

  1) Thermoplastic polyimide adhesive (Kapton 100KJ, manufactured by DuPont Co., Ltd.) .. The surface of the polyimide film and the copper-treated surface are treated with a molding temperature of 330 ° C. and a molding time of 30 minutes and a molding pressure of 10.2 MPa (400 mm square plate). It was produced by sandwiching an adhesive with foil. The obtained laminate was cut to a width of 10 mm, and 90 ° peeling was measured at 100 mm / min.

  2) Acrylic adhesive (DuPont Co., Ltd. Pyrrax LF010). This adhesive was sandwiched in place of the thermoplastic polyimide (Kapton 100KJ), and pressed at 160 ° C. for 30 minutes. The obtained laminate was cut to 10 mm, and 90 ° peeling was measured at 100 mm / min.

3) Epoxy resin adhesive (Toa Gosei Co., Ltd .: Aronmighty BX-60) ··· Adhesive was applied to the rubbing surface of the polyimide film with a bar coater, and copper foil was further placed on the adhesive, and 100 ° C. After drying for 2 minutes and then curing with a hot press (150 ° C. × 50 kg / cm ² G × 30 minutes), the obtained laminate was cut into 10 mm, and 90 ° peeling was measured at 100 mm / min.

[Example 1]
A polyamic acid obtained from pyromellitic dianhydride and 4,4′-diaminodiphenyl ether is mixed with about 0.1% by weight of calcium hydrogen phosphate having an average particle size of 1 μm, and the resulting polyimide film having a thickness of 25 μm is mixed. Using a polishing tape using silicon carbide having a particle size of 20 μm as an abrasive, a rubbing treatment was performed at a running speed of 10 m / min in the manner shown in FIG.

  The resulting film had a static friction coefficient of 0.46, a surface roughness Rz of 1.14 μm, a height difference of streaks provided on the film surface of 0.54 μm, and a maximum height Ry of 1.27 μm. The maximum width of the stripe-shaped irregularities was 1.5 μm, and the number of the stripe-shaped irregularities was 219 / mm width.

  Table 1 shows the adhesive strength of the copper foil laminated with the scratch-treated surface of the polyimide film via an acrylic adhesive (Pyralax).

[Example 2]
Copper foil was laminated on the surface of the polyimide film obtained in Example 1 through a thermoplastic polyimide film Kapton 100KJ (manufactured by Dupont) under the conditions of 330 ° C. × 30 min × 10.2 MPa (400 cm ² ). The adhesive strength is shown in Table 1.

[Example 3]
A copper foil was laminated on the scratch-treated surface of the polyimide film obtained in Example 1 through an epoxy resin adhesive (manufactured by Toagosei Co., Ltd.) under hot pressing conditions of 150 ° C. × 50 kg / cm ² G × 30 minutes. The adhesive strength is shown in Table 1.

[Example 4]
A polyamic acid obtained from pyromellitic dianhydride and 4,4′-diaminodiphenyl ether is mixed with about 0.1% by weight of calcium hydrogen phosphate having an average particle size of 1 μm, and the resulting polyimide film having a thickness of 25 μm is mixed. Using a polishing tape using silicon carbide having a particle size of 9 μm as an abrasive, the same as in Example 1 was rubbed as shown in FIG.

  The resulting film had a static friction coefficient of 0.39, a surface roughness Rz of 1.39 μm, a height difference of streaks formed on the film surface of 0.44 μm, and a maximum height Ry of 1.12 μm. The maximum width of the stripe-shaped irregularities was 1.1 μm, and the number of the stripe-shaped irregularities was 350 / mm width.

  Table 1 shows the results of bonding the copper foil to the obtained scratch-treated film surface via an acrylic adhesive and measuring the adhesive strength.

[Example 5]
Polyimide film obtained from pyromellitic dianhydride and 4,4′-diaminodiphenyl ether is mixed with about 0.1% by weight of calcium hydrogen phosphate having an average particle diameter of 1 μm to produce a polyimide film having a thickness of 12.5 μm. In addition, a polishing tape using silicon carbide having a particle size of 9 μm as an abrasive was used to carry out a rubbing treatment in the same manner as in Example 1 as shown in FIG.

  The resulting film had a static friction coefficient of 0.52 and a surface roughness Rz of 1.18 μm. The height difference of streaks provided on the film surface was 0.64 μm and the maximum height Ry was 1.32 μm. The maximum width of the stripe-shaped irregularities was 1.7 μm, and the number of the stripe-shaped irregularities was 211 / mm width.

  Table 1 shows the results of laminating a copper foil on the obtained scratch-treated film surface via an acrylic adhesive and measuring the adhesive force.

[Example 6]
Polyimide film obtained from pyromellitic dianhydride and 4,4′-diaminodiphenyl ether is mixed with about 0.1% by weight of calcium hydrogen phosphate having an average particle diameter of 1 μm to produce a polyimide film having a thickness of 12.5 μm. In addition, a polishing tape using silicon carbide having a particle size of 40 μm as an abrasive was used for rubbing at a running speed of 10 m / min and a treatment surface pressure of 3 kg / 500 mm in the manner shown in FIG.

  The resulting film had a coefficient of static friction of 0.44, a surface roughness Rz of 7.35 μm, a height difference of streaks provided on the film surface of 2.38 μm, a maximum height Ry of 8.38 μm, The maximum width of the stripe-shaped irregularities was 17.6 μm, and the number of stripe-shaped irregularities was 180 / mm width.

  Table 1 shows the results of laminating a copper foil on the obtained scratch-treated film surface via an acrylic adhesive and measuring the adhesive force.

[Example 7]
From 70 mol% of pyromellitic dianhydride, 30 mol% of 3,3 ′, 4,4′-biphenyltetracarboxylic dianhydride, 80 mol% of 4,4′-diaminodiphenyl ether, and 20 mol% of paraphenylenediamine. About 0.1 wt% of calcium hydrogen phosphate having an average particle diameter of 1 μm is mixed in the resulting polyamic acid, and a polishing tape using silicon carbide having a particle diameter of 20 μm as an abrasive material is manufactured on a polyimide film having a thickness of 25 μm. In the same manner as in Example 1, it was abraded in the manner shown in FIG.

  The resulting film had a coefficient of static friction of 0.33, a surface roughness Rz of 1.25 μm, a height difference of streaks formed on the film surface of 0.72 μm, and a maximum height Ry of 1.38 μm. The maximum width of the stripe-shaped irregularities was 1.7 μm, and the number of stripe-shaped irregularities was 225 / mm width.

  Table 1 shows the results of laminating a copper foil on the obtained scratch-treated film surface via an acrylic adhesive and measuring the adhesive force.

[Example 8]
A copper foil was laminated on the surface of the scratch-treated film of Example 7 via thermoplastic polyimide. The results are shown in Table 1.

[Example 9]
A copper foil was laminated on the surface of the scratch-treated film of Example 7 via an epoxy adhesive. The results are shown in Table 1.

[Example 10]
From 70 mol% of pyromellitic dianhydride, 30 mol% of 3,3 ′, 4,4′-biphenyltetracarboxylic dianhydride, 80 mol% of 4,4′-diaminodiphenyl ether, and 20 mol% of paraphenylenediamine. About 0.1% by weight of calcium hydrogen phosphate having an average particle diameter of 1 μm is mixed in the obtained polyamic acid, and the resulting polyimide film having a thickness of 12.5 μm has a running speed of 10 m / min, as shown in FIG. First, the surface pressure is 3 kg / 500 mm, and the surface is first abraded with an abrasive tape using silicon carbide with a particle size of 5 μm as an abrasive, and then the abrasive tape using silicon carbide with a particle size of 40 μm as an abrasive is used. Scraping was performed.

  The resulting film had a coefficient of static friction of 0.35, a surface roughness Rz of 5.34 μm, a height difference of streaks provided on the film surface of 2.23 μm, a maximum height Ry of 6.67 μm, The maximum width of the stripe-shaped unevenness was 9.5 μm, and the number of stripe-shaped unevenness was 268 / mm width.

  A copper foil was laminated on the obtained scratched film surface via an acrylic adhesive. The results are shown in Table 1.

[Comparative Example 1]
A polyamic acid obtained from pyromellitic dianhydride and 4,4′-diaminodiphenyl ether is mixed with about 0.1% by weight of calcium hydrogen phosphate having an average particle size of 1 μm, and the resulting polyimide film having a thickness of 25 μm is mixed. The copper foil was laminated through an acrylic adhesive without rubbing. The results are shown in Table 1.

[Comparative Example 2]
Instead of the acrylic adhesive of Comparative Example 1, a copper foil was laminated via a thermoplastic polyimide. The results are shown in Table 1.

[Comparative Example 3]
Instead of the acrylic adhesive of Comparative Example 1, a copper foil was laminated via an epoxy adhesive. The results are shown in Table 1.

[Comparative Example 4]
From 70 mol% of pyromellitic dianhydride, 30 mol% of 3,3 ′, 4,4′-biphenyltetracarboxylic dianhydride, 80 mol% of 4,4′-diaminodiphenyl ether, and 20 mol% of paraphenylenediamine. The resulting polyamic acid is mixed with about 0.1% by weight of calcium hydrogen phosphate having an average particle diameter of 1 μm, and the produced thickness of 12.5 μm is applied to the polyimide film via an acrylic adhesive without rubbing. A copper foil was laminated. The results are shown in Table 1.

  Since the polyimide film for metal lamination of the present invention has an excellent adhesive improvement effect, it can be suitably used for applications such as FPC, TAB carrier tape, lead frame fixing tape and the like.

It is explanatory drawing which shows the method of forming a stripe-shaped unevenness | corrugation on the film surface. It is explanatory drawing which shows the other method of forming a stripe-shaped unevenness | corrugation on the film surface. It is explanatory drawing which shows the further another method of forming a stripe-shaped unevenness | corrugation on the film surface. It is explanatory drawing which shows another method of forming a stripe-shaped unevenness | corrugation on the film surface. It is a schematic diagram which shows the stripe-shaped unevenness | corrugation on the film surface.

Explanation of symbols

1: Unwinding roll 2: Winding roll 3, 3 ′: Polishing roll 4: Pressing roll 5: Height difference of stripe-like unevenness 6: Width of stripe-like unevenness 7: Convex part 8: Concave part 9: Film surface position

Claims (12)

A metal-laminating polyimide film, wherein an adhesive is laminated on the rubbing-treated surface of a polyimide film in which streaks are formed by rubbing the surface. 2. The polyimide film for metal lamination according to claim 1, wherein a film surface roughness Rz measured according to JIS B-0601 (2001) of the scratched surface is 0.7 to 10 μm. 3. The polyimide film for metal lamination according to claim 1, wherein the difference in level of the stripe-shaped unevenness on the scratched surface is in the range of 0.05 to 10 μm. 4. The metal-laminated polyimide film according to claim 1, wherein the maximum height Ry of the height difference of the stripe-shaped unevenness on the scratched surface is in the range of 4 to 10 μm. 5. The metal-laminated polyimide film according to claim 1, wherein the maximum width of the stripe-shaped unevenness on the scratched surface is in the range of 0.1 to 20 μm. The number of stripe-shaped unevenness | corrugations in the said rubbing process surface exists in the range of 0.1-10000 piece / mm, The polyimide film for metal lamination | stacking of any one of Claims 1-5 characterized by the above-mentioned. The surface of the polyimide film is rubbed with a polishing tape having fine abrasive particles coated on the surface, and an adhesive is laminated on the rubbed surface of the polyimide film. The manufacturing method of the polyimide film for metal lamination | stacking of clause. The method for producing a metal-laminated polyimide film according to claim 7, wherein the abrasive particles are any of silicon carbide, aluminum oxide, chromium oxide, cerium oxide, and diamond. The method for producing a polyimide film for metal lamination according to claim 7 or 8, wherein the abrasive particles have a particle size of 0.1 to 100 µm. In the first stage, the surface of the polyimide film is abraded with an abrasive tape in which abrasive particles having a particle size of 0.1 μm or more and less than 10 μm are disposed, and then in the second stage, polyimide is coated with an abrasive tape in which abrasive particles having a particle size of 10 μm or more and 100 μm or less are disposed. The method for producing a polyimide film for metal lamination according to any one of claims 7 to 9, wherein the film surface is abraded. In the first stage, the surface of the polyimide film is abraded with an abrasive tape in which abrasive particles having a particle size of 10 μm or more and 100 μm or less are arranged, and then in the second stage, the polyimide is coated with an abrasive tape in which abrasive particles having a particle size of 0.1 μm or more and less than 10 μm are arranged. The method for producing a polyimide film for metal lamination according to any one of claims 7 to 9, wherein the film surface is abraded. A metal laminate, wherein a metal foil is laminated on the adhesive layer of the polyimide film for metal lamination according to any one of claims 1 to 6.

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