JP3351265B2 - Aromatic polyimide film and copper foil laminated film - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

TECHNICAL FIELD The present invention relates to a tape-shaped aromatic polyimide film comprising an aromatic polyimide containing a biphenyltetracarboxylic acid component and a paraphenylenediamine component as essential components as polymer constituent units, and an aromatic polyimide film comprising the same. It relates to the used copper foil laminated film. In particular, the present invention uses a solution of an aromatic polyimide precursor (for example, aromatic polyamic acid) containing biphenyltetracarboxylic dianhydride or a derivative thereof and paraphenylenediamine to form a film by a solution casting method. Aromatic polyimide film having excellent dimensional stability even under various environments obtained by, especially, a long aromatic polyimide film that facilitates high-density patterning and alignment during semiconductor mounting It is about.

[0002]

2. Description of the Related Art Aromatic polyimide films have high heat resistance,
Because of its excellent properties such as cold resistance, chemical resistance, electrical insulation, and mechanical strength, it is widely used in various fields. Above all, it is known that an aromatic polyimide film composed of a biphenyltetracarboxylic acid component and a paraphenylenediamine component has particularly high heat resistance and mechanical strength. Accordingly, when such an aromatic polyimide film is particularly focused on its excellent heat resistance and mechanical strength, a carrier for a flexible printed wiring copper-clad board (FPC) or a tape automated bonding (TAB) carrier is required. It can be said that it is suitable as a support used in the production of tapes and the like.

However, in the field where the polyimide film is used, the demand for high precision and high productivity has become more and more severe, and a laminate in which a metal foil (usually a copper foil) and a polyimide film are laminated with an adhesive is used. It has been pointed out that there is a problem of running stability, a problem of curling of the laminate, and a problem of alignment caused by distortion of leads. For example, in TAB applications, where demands for high precision are particularly severe, processing is performed in a tape shape with a sprocket hole of 35 mm width or 70 mm width. It has been pointed out that curling occurs in the laminated body, and the above-described alignment becomes difficult during high-density patterning and semiconductor mounting, resulting in a decrease in productivity.

For this reason, various improvements have been made focusing on the dimensional stability and expansion coefficient of the polyimide film. For example, JP-A-61-264027 and JP-A-61-264027
Japanese Patent No. 264028 describes a method for producing an aromatic polyimide film having high dimensional stability by reheating an aromatic polyimide film under low tension.

[0005] These known techniques have made it possible to obtain aromatic polyimide films with high dimensional accuracy. However, such aromatic polyimide films are cut into tapes and are cut in an automated machine. It is not always sufficient for a TAB tape that requires an operation of laminating an adhesive tape and then performing a necessary processing such as a perforation process, and then laminating a copper foil tape on it with high precision. It does not indicate reliability.

[0006]

SUMMARY OF THE INVENTION An object of the present invention is to provide a high-precision, especially when a metal foil such as a copper foil is laminated through an adhesive layer after being cut into a tape shape and run in an automatic device. An object of the present invention is to provide an aromatic polyimide film which can be laminated with a polyimide film. An object of the present invention is to provide an aromatic polyimide film which can be stably run even after a tape-shaped mechanical processing such as perforation is performed.

[0007]

The present invention SUMMARY OF] is an aromatic polyimide comprising biphenyl tetracarboxylic acid component and p-phenylenediamine component as a polymer constituting unit, length thickness in the range of 50~125μm
A continuous form of the film, the tensile strength of 30kg / mm ²
As described above, the tensile modulus is 500 kg / mm ² or more, and the coefficient of linear expansion measured at a temperature rise from 50 ° C. to 200 ° C. is 2.5.
× 10 ⁻⁵ cm / cm / ° C. or less, and a heat shrinkage rate of 0.05% or less when heated at 200 ° C. for 2 hours (especially 0.0
3% or less), and when arranged as a disc-shaped film having a diameter of 86 mm in a direction perpendicular to the horizontal plane,
The degree of curl represented by the horizontal distance from the center point of the disk to the edge of the disk is 3 mm or less (particularly 2 mm or less)
A is also in elongated aromatic polyimide film, wherein the maximum inclination in the width direction of the thickness of 10mm per 3μm or less (particularly 0.1 to 2.0 [mu] m). Book
Each physical property value of the aromatic polyimide film of the invention is described below.
Measured according to the measurement method and conditions described in the examples
It is a physical property value. The present invention also relates to the above-mentioned aromatic polyimide film, in a state where curl is not substantially measured,
On the surface of either side, and if curl is present, on the surface opposite to the curl side, the copper foil laminated film in which copper foil is laminated and joined via an adhesive is there.

The curl degree of the aromatic polyimide film of the present invention can be determined by using a measuring device as shown in FIG. That is, h of the measuring device of FIG.
The curl degree means the curl degree in mm units rounded to the decimal point. The maximum slope indicating the uniformity of the thickness of the aromatic polyimide film of the present invention is operated by a thickness measuring device along the width direction of the long polyimide film,
After obtaining the profile of the thickness as shown in FIG. 2, the maximum inclined portion is determined, and the difference (t) between the maximum value and the minimum value within 10 mm is shown in μm.

Preferred embodiments of the aromatic polyimide film of the present invention are as follows. (1) The water absorption when left at 23 ° C. for 24 hours is 1.
The above aromatic polyimide film having a content of 8% or less (particularly 0.2 to 1.7%). (2) The L value indicating the color tone is 25 or more, the a value is 20 or less, and the b value is 18 or more (especially, the L value is 25 to 55, the a value is 5 to 20, and the b value is 18 to 35). The above aromatic polyimide film. (3) The above aromatic polyimide film having a residual volatile matter content of 0.1 to 0.6% by weight. (4) The above aromatic polyimide film having a tensile strength in the range of 30 to 50 kg / mm ² . (5) The above aromatic polyimide film having a tensile modulus in the range of 600 to 1200 kg / mm ² . (6) The coefficient of linear expansion is 0.4 × 10 ^{−5 to} 2.5 × 10 ⁻⁵ c
m / cm / ° C. (especially 1.0 × 10 ^{−5 to} 2.5 × 10 ⁻⁵ c
m / cm / ° C). (7) The aromatic polyimide film having a curl degree of 2 mm or less. (8) applying an aromatic polyamic acid solution on a flat substrate,
Obtain a self-supporting film by partially drying and solidifying, an aromatic polyimide film obtained by heating the self-supporting film, or curl is not measured,
Alternatively, a curl degree of 3
The above aromatic polyimide film measured in mm or less.

The biphenyltetracarboxylic acid component used to produce the aromatic polyimide of the present invention includes:
Derivatives of 3,3 ', 4,4'-biphenyltetracarboxylic acid, such as acid dianhydrides, esters, halides and halides thereof, may be used in combination with other aromatic tetracarboxylic acid components as required. Thus, 3,3 ′, 4,4′-biphenyltetracarboxylic dianhydride is particularly preferred. As the aromatic diamine, paraphenylenediamine is used alone or in combination with another aromatic diamine component.

In the present invention, if the biphenyltetracarboxylic acid component and the paraphenylenediamine component are contained in a total of 80 mol% or more (when the total amount of the tetracarboxylic acid component and the diamine component is 200 mol%), In addition to these, one or more other aromatic tetracarboxylic acid components and / or aromatic diamine components may be contained as long as the effects of the present invention are not impaired. Examples of the aromatic tetracarboxylic acid component that can be used in combination include pyromellitic dianhydride, various isomers of benzophenone tetracarboxylic dianhydride, and various isomers of naphthalenetetracarboxylic dianhydride. As the aromatic diamine component that can be used in combination, metaphenylenediamine, 4,
4'-diaminodiphenyl ether, 4,4'-diaminodiphenylpropane, 4,4'-diaminodiphenylethane, 4,4'-diaminodiphenylmethane, 4,
4'-diaminodiphenyl sulfide and the like.

In the aromatic polyimide film of the present invention, if the curl degree exceeds the above range, the running stability of the support substrate, particularly in the case of TAB, in the processing of a tape is deteriorated. And the alignment during high-density patterning and semiconductor mounting becomes difficult.

When the thickness unevenness is out of the above range, a wide (usually about 500 mm wide) aromatic polyimide film is slit into, for example, 35 mm width, and then a 35 mm width tape is wound. (Film) Tension is uneven for each 14 rolls, and the winding state of the 35 mm tape is likely to shift on both sides, causing troubles in the slitting process and reducing productivity. Note that the color tone is also important, and when the color tone is reduced, it is difficult to confirm the opposite surface during processing, and it becomes difficult to perform high-accuracy alignment during processing.

If the water absorption, the coefficient of linear expansion, and the heat shrinkage of the aromatic polyimide film are within the above ranges, the dimensional stability under various environments (high temperature, etching, etc.) becomes high, preferable. Further, when the tensile strength and the tensile elastic modulus are within the above ranges, handling tends to be easy, and thinning tends to be easy.

The aromatic polyimide film of the present invention can be preferably produced by the following production method. That is, first, biphenyltetracarboxylic acids and paraphenylenediamine are combined with N, N-dimethylacetamide or N-
In an organic polar solvent usually used for the production of polyimide such as methyl-2-pyrrolidone, preferably 10 to 80C
, And the polymer preferably has a logarithmic viscosity (measuring temperature: 30 ° C., concentration: 0.5 g / 100 ml solvent, solvent: N-methyl-2-pyrrolidone) of 500 to 4
500 poise polyamic acid (imidation ratio: 5%
Hereinafter) a solution is obtained.

Next, preferably, polyamic acid 100
0.01 to 1% by weight, based on parts by weight, of a phosphorus-containing compound such as (poly) phosphate and / or amine acid of phosphate, and 0.1 to 3 parts by weight based on 100 parts by weight of polyamic acid. An inorganic filler such as colloidal silica (preferably having an average particle size of 0.005 to 2 μm) is added to prepare a polyamic acid solution composition (dope solution).

The dope solution is cast on a surface of a support such as a metal drum or belt having a smooth surface to form a thin film of the dope solution. Next, when the thin film is dried, drying conditions are prepared (the inlet-outlet in the casting / drying furnace is divided into a plurality of zones, and preferable conditions are temperature: 100-160 ° C., time: 1). By drying, a long solidified film layer having a volatile content of 36 to 41% by weight and an imidization ratio of 10 to 60% in the solidified film is obtained. Can be Next, the long solidified film layer is peeled from the surface of the support to obtain a long solidified film.

Next, the both ends of the elongated solidified film in the width direction are preferably not held at 115 to 160 ° C.
After drying for 5 to 10 minutes, the volatile content of the dried film is 1
After being prepared so as to have a weight ratio of 3 to 35% by weight and an imidization ratio of 20 to 70% by weight, the dried film is held at about 100 ° C. or more in a curing furnace while holding both edges in the width direction of the dried film. The drying film is further dried and imidized at a maximum heating temperature of preferably 350 to 500 ° C. for 1 to 50 minutes, and preferably the residual volatile matter content is 1.0% by weight or less, particularly 0.1 to 0. At 6% by weight, a long aromatic polyimide film having an imidization ratio of 95% or more can be obtained. Then, the obtained long aromatic polyimide film,
Furthermore, preferably under low tension or no tension,
It is heated at a temperature of about 400 ° C., subjected to a stress relaxation treatment, and wound up. What cut | disconnected this elongate film into strip shape also has the characteristic of this invention, and it is within the scope of this invention as long as the effect of this invention is exhibited.

In the aromatic polyimide film of the present invention, preferably, the volatile content and the imidation ratio of the solidified film of the thin film (cast film) on the surface of the support at the time of production are controlled within the above ranges, The solidified film is dried without gripping both edges in the width direction to adjust the volatile content and the imidation ratio within the above-mentioned preferred range, and this time under high temperature while gripping both edges in the width direction. By performing imidization by heating and finally adjusting to optimal conditions such as performing stress relaxation treatment, a combination of multiple processes,
Even though the film is as thick as 50 to 125 μm (particularly 75 to 125 μm), a low curl degree can be achieved without impairing other physical properties.

That is, the present inventor casts a polyamic acid solution on a smooth support surface to form a thin film, selects conditions for drying the thin film, and further adds a stress relaxation step to obtain a final film. The inventors have found that it is possible to optimally curl a long and thick aromatic polyimide film that can be obtained in an optimal manner, and have completed the present invention. Optimum drying conditions differ depending on the film thickness, conditions such as the drying temperature, its temperature gradient, and drying time. Therefore, once a polyimide film is manufactured under a certain condition, the curl degree is first measured, and then, based on the curl surface (A, B) and the degree, the manufacturing conditions such as temperature are preferably changed. The optimum state can be found by changing the degree of curl.

In the aromatic polyimide film of the present invention, the viscosity of the polyamic acid solution at the time of production, the volatile content, and the heating and drying conditions are preferably within the above-mentioned preferred ranges. Adjustment of thickness unevenness and adjustment of color tone can be performed.

The polyimide film of the present invention can be easily obtained by a method of polymerizing biphenyltetracarboxylic dianhydride and paraphenylenediamine.
The polyamic acid contains biphenyltetracarboxylic acids and paraphenylenediamine as essential components in a polymer constitutional unit, and a total of 80 mol% or more (in 200 mol% in total), preferably 100 mol% or more (200 mol%
Medium) as long as it is contained, and other components may be polymerized together with biphenyltetracarboxylic acids and paraphenylenediamine as long as the above conditions are satisfied.
The type of connection may be any of random connection and block connection. Further, as long as the above conditions are satisfied, the main component is a polyamic acid composed of biphenyltetracarboxylic acids and paraphenylenediamine, and the other polyamic acid component is replaced with another aromatic diamine component, for example, pyromellitic dianhydride and diaminodiphenyl ether. May be used in combination. In any case, the target aromatic polyimide film can be obtained in the same manner as described above. However, from the viewpoint of the rigidity (elastic modulus) of the film, the ratio of the essential components is preferably 120 mol% or more in total. In addition, the aromatic polyimide film of the present invention is not limited to the above-mentioned thermal imidization, and can be similarly obtained by chemical imidization.

The aromatic polyimide film of the present invention, as it is, or when it is curled, is heat-treated to eliminate the curl, and is subjected to radiation treatment such as plasma treatment or corona discharge treatment, or Applying a film surface activation treatment known per se such as aminosilane treatment, and laminating with a metal foil such as a copper foil via a thermoplastic adhesive such as a thermosetting adhesive or a thermoplastic polyimide resin, for various uses. , Especially for TAB.

[0024]

EXAMPLES In the following Examples and Comparative Examples, the physical properties, imidation ratio, volatile content and residual volatile content of the polyimide film were measured by the following methods. Each measurement value is indicated by an average value of an arbitrary number (usually 5).

Measurement of curl degree: A disk-shaped sample having a diameter of 86 mm was sampled, each sample was neutralized, and then, using a device (curl measuring table) as shown in FIG. The plate is placed in a fixed state at the center of the plate, and the curl length (h, mm) is measured to obtain the maximum curl length. Numerical values are displayed as integers with one decimal place rounded off. Therefore, the smaller the numerical value, the less the curl. Further, the curl surface (concave surface side) is displayed on the A surface and the B surface, and is displayed together with the maximum curl length. The surface A means the surface on the side opposite to the surface of the support during casting, and the surface B means the surface on the side in contact with the surface of the support. As a polyimide film, generally, A-surface curl is more suitable in fields requiring higher precision than B-surface curl.

Measurement of thickness gradient: Using a film thickness continuous measuring instrument (an electronic micrometer manufactured by Anritsu Electric Co., Ltd.), a thickness profile in the width direction of the film (in this embodiment, a film having a width of 508 mm) (see FIG. 2). ) Is continuously measured to determine the portion of the maximum thickness gradient within the entire width, and is measured to indicate the maximum thickness gradient as the height value (t, μm) per 10 mm width of the film. .

Measurement of color tone: The color of L, a, and b is measured with a color solid using a colorimetric colorimeter according to the Hunter method manufactured by Nippon Denshoku Co., Ltd. L: Brightness increases as the size increases. a: The degree of red is shown on the (+) side, and the degree of green is shown on the (-) side. b: The degree of yellow is shown on the (−) side, and the degree of blue is shown on the (−) side.

Water absorption measurement: Measured according to ASTM D570-63 (23 ° C. × 24 hours) Tensile strength measurement: Measured according to ASTM D882-64T (MD: longitudinal direction) Tensile modulus measurement: Measured according to ASTM D882-64T (MD) Linear expansion coefficient (50-200 ° C) measurement: A sample that has been heated at 300 ° C for 30 minutes and stress-relaxed is measured with a TMA device (tensile mode, 2 g load, sample length 10 mm, 20 ° C / min).

Measurement of heat shrinkage (200 ° C. × 2 hours): 8
A test piece of 0 × 80 mm was prepared, and a standard condition (23 ± 2
℃), relative humidity 65 ± 5% for 24 hours, measured the length between the gauges, heated at 200 ℃ for 2 hours, then allowed to stand in a standard state for 24 hours, the length between the gauges Is measured and determined by the following equation. Heat shrinkage = [(L ₁ −L ₂ ) / L ₁ ] × 100 L ₁ : Length between gauges before heating (mm) L ₂ : Length between gauges after heating (mm) Imidation rate measurement : 17 by IR-IR (ATR method)
Determined from the ratio of the absorbance of 80 cm ^-1 and 1510 cm ^-1.
The measurement was performed on the A side of the film.

Measurement of volatile content: Determined by the following equation. Volatile content = [(AB) / A] × 100 A: Film weight before heating B: Film weight after heating at 420 ° C. for 20 minutes

Measurement of residual volatile matter content: Determined by the following equation. Residual volatile amount = [(CD) / C] × 100 C: weight after drying at 150 ° C. × 10 D: weight after heating at 450 ° C. × 20

Comparative Example 1 54.6 kg of N, N-dimethylacetamide was added to a polymerization tank having an internal volume of 100 liters, and then 8.826 kg of 3,3 ′, 4,4′-biphenyltetracarboxylic dianhydride And 3.243 kg of paraphenylenediamine, and the mixture was polymerized at 30 ° C. for 10 hours to obtain a logarithmic viscosity of the polymer (measuring temperature: 30 ° C., concentration:
A polyamic acid (imidization rate: 5% or less) solution having a solvent concentration of 0.50 g / 100 mL, a solvent of N, N-dimethylacetamide (1.60), and a polymer concentration of 18% by weight was obtained. In this polyamic acid solution, polyamic acid 100
0.1 parts by weight of triethanolamine salt of monostearyl phosphate and 0.5 parts by weight (based on solid content) of colloidal silica having an average particle diameter of 0.08 μm are uniformly added to parts by weight. To obtain a polyamic acid solution composition (dope solution).

The dope had a rotational viscosity of 3000 poise. This dope solution is continuously extruded from a slit of a T-die mold onto a smooth support of a casting / drying furnace (an inlet to an outlet is divided into a plurality of zones) to form a thin film of the dope solution, and the thin film is dried. The drying conditions were adjusted (average temperature of each zone: 142 ° C., temperature of the last zone: 145 ° C., residence time: 15 minutes) to obtain a long solidified film. This long solidified film has an average content of the volatile matter composed of the solvent and the generated water of 34.
% By weight, and the imidization ratio was 34%. The long solidified film was peeled off from the surface of the support, and heated and dried in a heating furnace (average temperature: 145 ° C.) for 2 minutes in a heating furnace without holding and fixing both edges in the width direction of the solidified film. . The volatile content of the dried film was 26% by weight, and the imidation ratio was 35%.

Next, while holding both edges in the width direction of the dried film, the dried film is kept in a curing furnace (inlet temperature: 140 ° C., maximum temperature: 480 ° C., outlet temperature: 150 ° C.) for a residence time of 15 minutes. The dried film was dried and imidized to a width of 508 mm, a thickness of 75 μm, and a residual volatile matter content of 0.2.
A long aromatic polyimide film having a weight of 5% by weight and an imidation ratio of 95% or more was continuously produced. Next, the above aromatic polyimide film was coated with 80 g / m2 in the longitudinal direction of the film.
m ^{2 under} a tension applied to the high-temperature vertical heating furnace,
The film was heated at 325 ° C. for 3 minutes in the high-temperature vertical heating furnace, subjected to stress relaxation treatment, and wound up. Physical properties of the obtained aromatic polyimide film were measured.

Comparative Example 2 A dope solution produced in the same manner as in Comparative Example 1 was extruded onto a smooth support of a casting / drying furnace to form a thin film of the dope solution, and the conditions for drying the thin film were changed. The average temperature of each zone: 135 ° C., the temperature of the final zone: 140 ° C., the residence time: 15 minutes) By drying, the solidified film has a volatile content of 42% by weight as an average value of the solvent and the generated moisture. A long solidified film having an imidation ratio of 26% was formed. Next, the long solidified film was peeled off from the surface of the support, and heated and dried in a heating furnace (average temperature: 145 ° C.) for 2 minutes without gripping both widthwise edges of the solidified film. The dried film had a volatile content of 33% by weight and an imidization ratio of 30%.

Then, while holding both edges in the width direction of the dried film, the dried film is kept in a curing furnace (inlet temperature: 140 ° C., maximum temperature: 480 ° C., outlet temperature: 150 ° C.) for a residence time of 5 minutes. The dried film was dried and imidized to a width of 508 mm, a thickness of 75 μm, and a residual volatile matter content of 0.30.
A long aromatic polyimide film having a weight percentage of 95% or more and an imidation ratio of 95% or more was continuously produced. Finally, a stress relaxation treatment was performed under the conditions described in Comparative Example 1. Physical properties of the obtained aromatic polyimide film were measured.

Comparative Example 3 48.3 kg of N, N-dimethylacetamide was added to a polymerization tank having an internal volume of 100 liters, and then 8.826 kg of 3,3 ′, 4,4′-biphenyltetracarboxylic dianhydride And 3.243 kg of paraphenylenediamine, and the mixture was polymerized at 30 ° C. for 10 hours to obtain a logarithmic viscosity of the polymer (measuring temperature: 30 ° C., concentration:
A polyamic acid (imidization ratio: 5% or less) solution having a solvent concentration of 0.5 g / 100 ml, a solvent of N-methyl-2-pyrrolidone) of 1.50 and a polymer concentration of 20% by weight was obtained. In this polyamic acid solution, polyamic acid 100
0.1 parts by weight of triethanolamine salt of monostearyl phosphate and 0.5 parts by weight (based on solid content) of colloidal silica having an average particle diameter of 0.08 μm are uniformly added to parts by weight. To obtain a polyamic acid solution composition (dope solution).

The rotational viscosity of this dope was 5,000 poise. Drying was performed in the same manner as in Comparative Example 1 except that this dope solution was used, whereby the solidified film had a volatile content of 33% by weight composed of the solvent and generated water,
A long solidified film having an imidation ratio of 33% was formed. Next, the long solidified film was peeled off from the surface of the support, and the solidified film was heated in a heating furnace (average temperature: 145 ° C.) for 2 minutes without gripping both edges in the width direction of the solidified film. The dried film has a volatile content of 24% by weight,
The imidation ratio was 35%. Next, in a state where both edges in the width direction of the dried film were gripped, in the same manner as in Comparative Example 1, the width was 508 mm, the thickness was 75 μm, and the residual volatile matter amount was 0.29.
A long aromatic polyimide film having a weight percentage of 95% or more and an imidation ratio of 95% or more was continuously produced. Finally, a stress relaxation treatment was performed under the conditions described in Comparative Example 1. Physical properties of the obtained aromatic polyimide film were measured.

Comparative Example 4 As a diamine, 6.007 kg of 4,4′-diaminophenyl ether was used instead of 3.243 kg of paraphenylenediamine, and the amount of N, N-dimethylacetamide was increased from 54.6 kg to 67.6 kg. Except having changed, it implemented similarly to the comparative example 1.
A long aromatic polyimide film (so-called R type) having a thickness of 75 μm, a thickness of 75 μm, a residual volatile content of 0.61% by weight, and an imidization ratio of 95% or more was continuously produced. Finally, a stress relaxation treatment was performed under the conditions described in Comparative Example 1. Physical properties of the obtained aromatic polyimide film were measured.

Example 1 A dope solution produced in the same manner as in Comparative Example 1 was extruded onto a smooth support of a casting and drying furnace to form a thin film of the dope solution, and the conditions for drying the thin film were changed. By drying at an average temperature of each zone of 138 ° C., a temperature of the final zone of 142 ° C., and a residence time of 15 minutes), the content of the volatile matter composed of the solvent and the generated moisture is 39% by weight as an average value of the solidified film. And
A long solidified film having an imidation ratio of 29% was formed. Next, the long solidified film is peeled off from the surface of the support, and is heated in a heating furnace (average temperature: 145 ° C.) for 2 minutes without gripping the both edges in the width direction of the solidified film to volatilize. Content is 29% by weight, imidation ratio is 3
A dry film was formed that was 2%. Next, the drying film is dried for 15 minutes in a curing furnace (inlet temperature: 140 ° C., maximum temperature: 480 ° C., outlet temperature: 150 ° C.) while holding both edges in the width direction of the dried film. The film was dried and imidized to a width of 508 mm, a thickness of 75 μm, a residual volatile matter content of 0.26% by weight, and an imidization ratio of 95.
% Or more of a long aromatic polyimide film was continuously produced. Finally, a stress relaxation treatment was performed in the same manner as in Comparative Example 1 to obtain an aromatic polyimide film. Physical properties of the obtained aromatic polyimide film were measured.

Example 2 A dope solution produced in the same manner as in Comparative Example 1 was 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 dope solution. The thin film is dried (average temperature of each zone: 140 ° C., temperature of the final zone: 150 ° C., residence time: 10 minutes), and dried to obtain a volatile content of the solvent and generated water as an average value of the solidified film. A long solidified film having a content of 40% by weight and an imidization ratio of 24% was formed. Next, the long solidified film is peeled off from the surface of the support, and is heated in a heating furnace (average temperature: 140 ° C.) for 2 minutes without holding both edges in the width direction of the solidified film, and dried to form a dry film. The heating and heating were performed so that the volatile matter content of
Dried.

Then, while holding both edges in the width direction of the dried film, the inside of a curing furnace (inlet temperature: 110 ° C., maximum temperature: 480 ° C., outlet temperature: 150 ° C.) is retained for 10 minutes. The dried film was dried and imidized to a width of 508 mm, a thickness of 50 μm, and a residual volatile matter content of 0.1.
A long aromatic polyimide film having a weight of 7% by weight and an imidization ratio of 95% or more was continuously produced. Finally, Comparative Example 1
The stress relaxation treatment was performed under the conditions described in (1). Physical properties of the obtained aromatic polyimide film were measured.

Example 3 A dope solution produced in the same manner as in Comparative Example 1 was 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 dope solution. The thin film is dried (average temperature of each zone: 134 ° C., temperature of the final zone: 138 ° C., residence time: 30 minutes) and dried to obtain a volatile content of the solvent and the generated water as an average value of the solidified film. A long solidified film having a content of 37% by weight and an imidization ratio of 30% was formed.

Next, the long solidified film is peeled off from the surface of the support, and is heated in a heating furnace (average temperature: 120 ° C.) for 5 minutes without gripping both edges in the width direction of the solidified film. The dry film has a volatile content of 33
Heating and drying were carried out so that the imidation ratio was 32% by weight. Then, a curing furnace (inlet temperature: 140 ° C., maximum temperature:
(480 ° C, outlet temperature: 150 ° C), residence time: 30
In minutes, the dried film was dried and imidized to continuously produce a long aromatic polyimide film having a width of 508 mm, a thickness of 125 μm, a residual volatile content of 0.51% by weight, and an imidation ratio of 95% or more. Finally, a stress relaxation treatment was performed under the conditions described in Comparative Example 1. Physical properties of the obtained aromatic polyimide film were measured.

Example 4 A dope solution produced in the same manner as in Comparative Example 1 was extruded onto a smooth support of a casting / drying furnace to form a thin film of the dope solution, and the conditions for drying the thin film were changed. The average temperature of each zone is 138 ° C., the temperature of the final zone is 140 ° C., and the residence time is 15 minutes). A long solidified film having an imidation ratio of 27% was formed. Next, the long solidified film was peeled off from the surface of the support, and heated and dried in a heating furnace (average temperature: 145 ° C.) for 2 minutes without gripping both widthwise edges of the solidified film. The dried film has a volatile content of 31% by weight
And the imidation ratio was 32%.

Then, while holding both edges in the width direction of the dried film, the inside of a curing furnace (inlet temperature: 140 ° C., maximum temperature: 480 ° C., outlet temperature: 150 ° C.) was retained for 15 minutes. The dried film was dried and imidized to a width of 508 mm, a thickness of 75 μm, and a residual volatile matter content of 0.3.
A long aromatic polyimide film having a weight of 0% by weight and an imidization ratio of 95% or more was continuously produced. Finally, Comparative Example 1
The stress relaxation treatment was performed under the conditions described in (1). Physical properties of the obtained aromatic polyimide film were measured.

Example 5 53.6 kg of N, N-dimethylacetamide, 2.27 k of paraphenylenediamine
g, 4,4'-diaminodiphenyl ether 1.802
kg of 3,3 ′, 4,4′-biphenyltetracarboxylic dianhydride and 3.272 kg of pyromellitic dianhydride (3,3 ′, 4,4′-biphenyltetracarboxylic dianhydride). Polymerization was carried out in the same manner as in Comparative Example 1 except for the total mol% of the anhydride component and paraphenylenediamine: 120 mol%, and a polyamic acid solution (rotational viscosity: 14)
00 poise, 18% by weight). A dope solution prepared from the above polyamic acid solution in the same manner as in Comparative Example 1 was T
The casting is continuously cast from a slit of a die and extruded onto a smooth support of a drying oven to form a thin film of a dope solution (average temperature of each zone: 138 ° C., temperature of final zone:
140 ° C., residence time: 10 minutes)
The solidified film formed a long solidified film having a volatile content of 40% by weight composed of the solvent and produced water and an imidization ratio of 25%. Next, the long solidified film is peeled from the surface of the support, and is heated without heating both ends of the solidified film in the width direction (average temperature: 140 ° C.).
C.) for 2 minutes, and heated and dried so that the dried film had a volatile content of 31% by weight and an imidization ratio of 29%.

Next, while holding both edges in the width direction of the dried film, the heating conditions in the curing furnace were changed (inlet temperature: 140 ° C., maximum temperature: 440 ° C., outlet temperature: 150 ° C., retention time). Time: 10 minutes), the dried film was dried and imidized, and was 508 mm wide and 50 μm thick.
m, the amount of residual volatile matter was 0.18% by weight, and a long aromatic polyimide film having an imidization ratio of 95% or more was continuously produced. Finally, a stress relaxation treatment was performed under the conditions described in Comparative Example 1. Physical properties of the obtained aromatic polyimide film were measured.

Example 6 The polyimide film obtained in Example 4 was subjected to a conventional method (conditions: plasma irradiation time: 1 hour, microwave oscillation output: 1 KW, plasma generation vacuum: 0.8 Torr, plasma processing gas: oxygen). A low-temperature plasma treatment was performed, and a sample was prepared using the above-mentioned adhesive as an adhesive, and evaluated. The results are summarized in Table 1.

[Evaluation of Aromatic Polyimide Film] (1) Evaluation of Running Stability in Tape Form The long aromatic polyimide films obtained in Comparative Examples 1 to 4 and Examples 1 to 5 were slit to have a width of 35 mm. A tape having a length of 50 m was prepared, and a thermosetting polyimide adhesive having a width of 26 mm [50 parts by weight of polyimide siloxane, 30 parts by weight of epoxy resin (trade name: Epicoat 807, manufactured by Yuka Shell Epoxy Co., Ltd.), phenol One side of a B-stage adhesive composed of 20 parts by weight of a novolak type curing agent (H-1 manufactured by Meiwa Kasei Co., Ltd.) and 0.01 part by weight of a curing catalyst (2-phenylimidazole) is cured with an adhesive tape covering polyethylene terephthalate on one side. Tg of product: 130
° C] was laminated so that the center line of the polyimide tape was overlapped with the side B of the polyimide tape to produce a polyimide tape with an adhesive. Sprocket holes and device holes are punched on the polyimide of this adhesive-attached polyimide tape (composed of polyethylene terephthalate / adhesive / aromatic polyimide tape), and a copper foil (35 μm) is placed at 130 ° C.
Under a condition of ² kg / cm ² and about 1 second, heat and pressure were applied between the rolls. Circuits such as inner leads and outer leads were formed on the copper foil by patterning and etching to produce a tape. This tape was evaluated as follows. In addition, Example 1-5 and Comparative Examples 1, 2, and 4
The film of Comparative Example 3 had no problem in the slitting process.
When the slit tape was wound with the film of No. 1, trouble occurred.

(2) Evaluation of running stability If the tape is curled, there arises a problem that the tape comes off the sprocket hole during the running of the tape, or conversely, the gear does not come off the sprocket hole when changing the running direction of the tape. CC indicates that there is a state in which the sprocket hole comes off or does not come off during running, BB indicates that such a state exists slightly, and AA indicates that there is no such problem.

(3) Measurement of curl of laminated copper foil laminate The TAB carrier tape was cut at a length of 70 mm, placed on a horizontal surface with the concave surface facing down, and the maximum curl length (mm)
Is measured. If the length is 2.0 mm or less, AA,
BB was 2.0 to 2.5, and CC was 2.5 mm or more.

(4) Alignment If the tape has a curl, it is pressed by a pressure so as to be flat at the time of alignment during processing, and after processing, the tape curls again when the pressure is removed. If such an operation is performed, distortion of the lead occurs, and accurate positioning cannot be performed. In addition, if there is a problem in the color tone, the alignment becomes difficult. If lead distortion occurs or alignment is not accurate, C
C, BB when the lead distortion was slightly generated or the alignment was slightly inaccurate, and AA when the lead distortion was not generated and the alignment was accurate. (5) Comprehensive Evaluation The overall evaluation as a TAB polyimide tape was judged as AA when it was excellent and as CC when there was an inconvenience.

[0054]

Table 1 Table 1 Comparative Example Example 1 2 3 4 1 2 3 4 5 6 ──────────────────────────────────── Film thickness 75 75 75 75 75 50 125 75 50 75 Curl degree B4 A6 B5 B2 A0 A2 A1 A2 A2 A2 Thickness gradient 1.8 1.8 3.1 1.7 1.7 1.5 1.9 1.6 1.5 1.6 Color tone L value 35.1 27.0 35.0 70.2 34.8 49.3 30.0 34.3 49.7 34.0 a value 16.6 21.1 16.7 -3.9 16.8 9.6 19.8 17.1 11.4 16.9 b value 23.5 18.0 23.6 37.3 23.4 30.5 20.5 22.9 33.2 22.7 Water absorption 1.5 1.5 1.5 1.8 1.5 1.5 1.4 1.5 1.5 1.5 Tensile strength 32.9 34.8 33.5 37.2 35.2 43.3 31.4 35.5 37.1 35.1 Tensile modulus 650 680 660 360 680 860 660 690 505 688 Coefficient of linear expansion 2.2 2.1 2.1 4.3 2.1 1.6 2.1 2.1 2.2 2.0 Heat shrinkage 0.02 0.02 0.02 0.15 0.02 0.01 0.01 0.02 0.03 0.02 Peel strength 1.4 1.3 1.3 1.2 1.4 1.3 1.3 1.4 1.2 1. 6 走 行 Running stability CC BB CC CC AA AA AA AA AA AA Laminate curl CC CC CC CC CC AA AA AA AA AA AA Alignment BB CC BB CC AA AA AA AA AA AA総 合 Overall evaluation CC CC C CCC AA AA AA AA AA AA ─────────────────────────── ─────────

The units of each item in Table 1 are as follows.
Film thickness (μm), degree of curl (mm specified in the product), thickness gradient (μm / 10 mm specified earlier), water absorption (%),
Tensile strength (kg / mm ² ), tensile modulus (kg / mm ² )
² ), linear expansion coefficient (× 10 ⁻⁵ cm / cm / ° C.), heat shrinkage (%), peel strength (peel strength of laminate, 90 ° peel, kg / cm)

[0056]

As described above, the aromatic polyimide film of the present invention comprises:
When used as a substrate film for forming electronic circuits,
It is hard to come off from the sprocket hole, has good running stability during processing, enables high-density patterning, and facilitates positioning during processing. It also has high self-supporting properties (high density,
(High elasticity) Thinning is possible (cost reduction is possible).

The aromatic polyimide film of the present invention can be industrially obtained in large quantities with stable and constant quality as a raw material.

[Brief description of the drawings]

FIG. 1 shows a curl degree (h) of an aromatic polyimide film defined in the present invention and a measuring device thereof.

FIG. 2 shows an example of a profile used for determining a maximum thickness gradient (tμm / 10 mm) as an index of thickness unevenness defined in the present invention.

──────────────────────────────────────────────────続 き Continuation of the front page (72) Inventor Hiroshi Inoue 1-12-32 Nishihonmachi, Ube City, Yamaguchi Prefecture Ube Industries, Ltd. Polymer Research Laboratory (Ube) Inside (56) References JP-A-5-271438 (JP, A) JP-A-61-111359 (JP, A) JP-A-62-215631 (JP, A) JP-A-63-61029 (JP, A) JP-A-6-207014 (JP, A) ( 58) Field surveyed (Int.Cl. ⁷ , DB name) C08J 5/18 CFG

Claims (8)

(57) [Claims] 1. An aromatic polyimide containing a biphenyltetracarboxylic acid component and a paraphenylenediamine component as essential components as polymer constituent units, and having a thickness of 50.
A long film in the range of ~ 125 µm,
Tensile strength is 30 kg / mm ² or more, tensile modulus is 500
kg / mm ² or more, the heat shrinkage rate when the linear expansion coefficient measured at Atsushi Nobori is ^{2.5 × 10 -5 cm / cm /} ℃ or less and heated for 2 hours at 200 ° C. to 200 ° C. from 50 ° C. Is 0.05% or less, and the horizontal direction between the center point of the disc and the edge of the disc when the disc-shaped film having a diameter of 86 mm is arranged in a direction perpendicular to the horizontal plane. elongated aromatic polyimide film curl degree represented by the distance of a less than 3mm, also characterized in that the maximum inclination in the width direction of the thickness is 10mm per 3μm or less. 2. The aromatic polyimide film according to claim 1, which has a water absorption of 1.8% or less when left at 23 ° C. for 24 hours. 3. An L value indicating a color tone is 25 or more and an a value is 20.
The aromatic polyimide film according to claim 1, wherein the value of b is 18 or less. 4. The residual volatile matter content is 0.1 to 0.6% by weight.
The aromatic polyimide film according to claim 1, wherein 5. A linear expansion coefficient of 0.4 × 10 ^{−5 to} 2.5 ×
The aromatic polyimide film according to claim 1, which is in a range of 10 ^-5 cm / cm / ° C. 6. The aromatic polyimide film according to claim 1, wherein the curl degree is 2 mm or less. 7. A method of applying an aromatic polyamic acid solution on a flat substrate, partially drying and solidifying to obtain a self-supporting film, and heating the self-supporting film to obtain an aromatic polyimide film. 2. The aromatic polyimide film according to claim 1, wherein curl is not measured, or curl is measured at a curl degree of 3 mm or less on the side in contact with the flat substrate. 8. The aromatic polyimide film according to claim 1, wherein the curl is substantially not measured, and the curl side is formed on the surface on either side of the curl. Is a copper foil laminated film in which copper foil is laminated and bonded to the opposite surface via an adhesive.