JP3355986B2 - Aromatic polyimide film and laminate - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to an adhesive composition such as an adhesive, which exhibits excellent cutting and punching properties, easily adheres to the adhesive composition, and peels off from the adhesive composition layer. The present invention relates to an aromatic polyimide film exhibiting a high peel resistance value, and a laminate of the aromatic polyimide film and a conductive sheet.

[0002]

2. Description of the Related Art Conventionally, as an electronic component having high heat resistance, an aromatic polyimide film is generally provided with a conductor layer such as a copper foil on one or both sides thereof directly or via an adhesive. Aromatic polyimide is a polymer having excellent heat resistance and mechanical properties obtained by heating a polyamic acid produced from a tetracarboxylic acid component and an aromatic diamine component to a high temperature for dehydration cyclization. However,
In particular, polyimide films used for electronic components are required to have further various characteristics.

Japanese Patent Application Laid-Open No. 6-334110 discloses that as a resin material film suitable for manufacturing a lead frame, a polyimide film having an edge crack resistance of 50 to 70 kgf / 20 mm is excellent. Further, it is stated that the polyimide film must have some% of a hygroscopic solvent remaining.

In view of the high demands on various characteristics such as heat resistance, electrical insulation, and mechanical strength as an electronic component, aromatic polyimides containing a biphenyltetracarboxylic acid component as a tetracarboxylic acid component are used. It is also desirable to use an aromatic diamine component containing a phenylenediamine component. In addition, in order to use as a laminate laminated with a metal conductor sheet such as a copper foil using an adhesive layer, the aromatic polyimide film is made of a known polyimide-based adhesive or epoxy resin-based adhesive. It is necessary to show high adhesiveness to an adhesive such as an agent.

However, according to the study by the present inventors, the technique described in the above-mentioned Japanese Patent Application Laid-Open No. Hei 6-334110 utilizes a component containing a biphenyltetracarboxylic acid component as a tetracarboxylic acid component and uses an aromatic diamine component as an aromatic diamine component. It has been found that it is not possible to impart satisfactory properties to an aromatic polyimide film produced using a material containing a phenylenediamine component.

[0006]

SUMMARY OF THE INVENTION An object of the present invention is to provide a laminated substrate film, particularly for use in a lead frame.
An object of the present invention is to provide an aromatic polyimide film which has good punching properties required for semiconductor applications and maintains adhesiveness and dimensional stability.

[0007]

According to the present invention, a tetracarboxylic acid component containing at least 15 mol% of biphenyltetracarboxylic acid or a dianhydride or an ester thereof is combined with at least 5 mol% (preferably at least 15 mol%).
Consisting of a polyimide produced by reaction with an aromatic diamine component containing phenylenediamine having a thickness of 10
To 125 μm, wherein the aromatic polyimide film is 11 to 22 kg / 20 mm
An aromatic polyimide film having a specific edge resistance of / 10 μm and a volatile matter content of 0.4% by weight or less. The aromatic polyimide of the present invention
The above specific tear resistance of the film and as described herein
All other physical property values described in the following Examples
Value measured according to the described measurement method and measurement conditions
Means

[0008] The present invention also provides a process wherein the tetracarboxylic acid component containing at least 15 mol% of biphenyltetracarboxylic acid or dianhydride or ester thereof is reacted with an aromatic diamine component containing at least 5 mol% of phenylenediamine. Is an aromatic polyimide film having a thickness of 10 to 125 μm, comprising 11 to 22 kg /
A laminate formed by bonding an aromatic polyimide film having a specific crack resistance of 20 mm / 10 μm and a volatile matter content of 0.4% by weight or less to a conductive sheet via an adhesive layer is also used. is there.

[0009] In this specification, the end crack resistance (or specific end crack resistance) means the average value of the end tear resistance (or specific end crack resistance) of the sample (5 pieces) measured according to JIS C2318. Specifically, the center line of the V-shaped notch plate test bracket having the upper thickness of 1.00 ± 0.05 mm of the constant-speed tension-type tensile tester was made to coincide with the center line of the upper grip, and the top of the cut and the lower grip were Attach the handle so that the interval is about 30 mm. A test piece with a width of about 20 mm and a length of about 200 mm is passed through the hole of the bracket, folded into two parts, clamped at the lower part of the tester, pulled at a speed of about 200 mm per minute, and pulled apart. Is called end tear resistance.
Five test pieces were taken from the longitudinal direction and the lateral direction over the entire width, respectively, and the average value of the end crack resistance was determined and shown as the end crack resistance value. The specific edge tear resistance indicates an edge tear resistance per film thickness (10 μm conversion).

[0010]

DESCRIPTION OF THE PREFERRED EMBODIMENTS Preferred embodiments of the present invention will be listed below. 1) Specific edge crack resistance is 11 to 15 kg / 20 mm / 10
The above aromatic polyimide film in the range of μm. 2) The above aromatic polyimide film having a volatile content of 0.05 to 0.3% by weight. 3) The above aromatic polyimide film having a volatile content of 0.05 to 0.2% by weight. 4) The above aromatic polyimide film further containing 0.1 to 3% by weight of an inorganic filler. 5) The above aromatic polyimide film produced by a solution casting method of polyamic acid. 6) The above aromatic polyimide film, the surface of which has been subjected to any one or more of surface treatment agent treatment, corona discharge treatment, flame treatment, ultraviolet irradiation treatment, glow discharge treatment, and plasma treatment. 7) The water absorption is 1.8% or less, and the tensile modulus is 450 kg /
mm ² or more and a coefficient of linear expansion (50 to 200 ° C.)
The above aromatic polyimide film having a ^{concentration of} 5 × 10 ⁻⁵ cm / cm / ° C. or less. 8) The above aromatic polyimide film having a dielectric breakdown voltage of 3 KV or more and a volume resistivity (25 ° C.) of 2 × 10 ¹⁶ Ω · cm or more. 9) The laminate described above, wherein the conductor sheet is a copper foil having a thickness of 8 to 50 μm. 10) The above laminate in which the adhesive layer is made of a thermoplastic adhesive or a thermosetting adhesive. 11) The above laminate in which the adhesive layer is made of a polyimide adhesive or an epoxy resin adhesive. 12) The above laminate for use in a lead frame of an electronic component.

In the present invention, the biphenyltetracarboxylic acid component includes 2,3,3 ′, 4′-biphenyltetracarboxylic acid, 3,3 ′, 4,4′-biphenyltetracarboxylic acid, and dianhydrides thereof. Or their esters can be used, and among them, 3,3 ', 4,4'-biphenyltetracarboxylic dianhydride is preferably used.

The aromatic tetracarboxylic acid component which can be used in combination with the biphenyltetracarboxylic acid component includes pyromellitic dianhydride, 3,3 ', 4,4'-benzophenonetetracarboxylic dianhydride, 2,2 ', 3,3'-benzophenonetetracarboxylic dianhydride, 2,2-bis (3,4-dicarboxyphenyl) propane dianhydride,
2,2-bis (2,3-dicarboxyphenyl) propane dianhydride, bis (3,4-dicarboxyphenyl) ether dianhydride, bis (2,3-dicarboxyphenyl) ether dianhydride Anhydride, 2,3,6,7-naphthalenetetracarboxylic dianhydride, 1,4,5,8-naphthalenetetracarboxylic dianhydride, 1,2,5,6-naphthalenetetracarboxylic dianhydride , 2,2-bis (3,4-
Dicarboxyphenyl) -1,1,1,3,3,3-hexafluoropropane dianhydride, 2,2-bis (2,3
-Dicarboxyphenyl) 1,1,1,3,3,3-hexafluoropropane dianhydride.

The phenylenediamine used in the present invention is:
Any of o-phenylenediamine, m-phenylenediamine, and p-phenylenediamine may be used.
Aromatic diamine components that can be used in combination with phenylenediamine include diaminodiphenyl ether, 4,4′-diaminodiphenylpropane, 4,4′-diaminodiphenylethane, 4,4′-diaminodiphenylmethane,
4'-diaminodiphenyl sulfide, bis [4- (4
-Aminophenoxy) phenyl] methane, 2,2-bis [4- (4-aminophenoxy) phenyl] propane,
2,2'-bis [4- (aminophenoxy) phenyl]
-1,1,1,3,3,3-hexafluoropropane,
Bis [4- (4-aminophenoxy) phenyl] ether and the like can be mentioned.

In the present invention, the aromatic polyimide film (or the surface-treated film) has a thickness of 1%.
It is preferably from 0 to 125 μm, particularly preferably from 25 to 75 μm, and particularly preferably from 45 to 55 μm. When the thickness of the aromatic polyimide film is less than the lower limit, self-supporting property is low, and when the thickness is more than the upper limit, a large cost is required for production. On the other hand, if the volatile matter content is more than 0.4% by weight, problems occur in the adhesiveness and dimensional stability. If the specific crack resistance of the aromatic polyimide film is outside the above range, the object of the present invention cannot be achieved.

When (1) the water absorption and (3) the coefficient of linear expansion (50 to 200 ° C.) are within the above ranges, the dimensional stability under various environments (high temperature, etching, etc.) is good. It is. Further, (2) when the tensile modulus is in the above range, the handling is good as a substrate film.

The aromatic polyimide film of the present invention comprises:
For example, it can be manufactured as follows. Preferably, first, a polyimide such as N, N-dimethylacetamide or N-methyl-2-pyrrolidone is prepared from the above tetracarboxylic dianhydride, preferably biphenyltetracarboxylic acid and phenylenediamine, preferably paraphenylenediamine. The polymer is polymerized in an organic polar solvent usually used at a temperature of preferably 10 to 80 ° C. for 1 to 30 hours, and the logarithmic viscosity of the polymer (measuring temperature: 30 ° C., concentration: 0.5 g / 100 mL)
Solvent, solvent: N-methyl-2-pyrrolidone)
5. A polyamic acid (imidation ratio: 5% or less) solution having a polymer concentration of 15 to 25% by weight and a rotational viscosity (30 ° C.) of 500 to 4500 poise is obtained.

Next, preferably, the polyamic acid 10
0.01 to 1% by weight, based on 0 part by weight, of an organic phosphorus-containing compound or an inorganic phosphorus compound such as an amine salt of (poly) phosphate and / or phosphate, and
0.1 to 3 parts by weight of colloidal silica, silicon nitride, talc, titanium oxide based on 100 parts by weight of polyamic acid,
An inorganic filler such as potassium phosphate (preferably having an average particle size of 0.005 to 5 μm, particularly 0.005 to 2 μm) is added to prepare a polyamic acid solution composition.

This polyamic acid solution composition is cast on a glass or metal support having a smooth surface to form a thin film of the solution, and when the thin film is dried,
Adjust the drying conditions (preferable temperature: 100 to 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% in the solidified film. A solidified film is formed, and the solidified film is peeled from the support surface.

Next, a surface treatment solution containing an aminosilane-based, epoxysilane-based or titanate-based surface treatment agent may be applied to one or both surfaces of the solidified film, and then further dried. As the surface treatment agent, γ-
Aminopropyl-triethoxysilane, N-β- (aminoethyl) -γ-aminopropyl-triethoxysilane, N- (aminocarbonyl) -γ-aminopropyl-
Triethoxysilane, N- [β- (phenylamino)-
Ethyl] -γ-aminopropyl-triethoxysilane,
Aminosilanes such as N-phenyl-γ-aminopropyl-triethoxysilane, γ-phenylaminopropyltrimethoxysilane, β- (3,4-epoxycyclohexyl) -ethyl-trimethoxysilane, γ-glycidyloxypropyl And heat-resistant surface treatment agents such as epoxysilanes such as trimethoxysilane and titanates such as isopropyl-tricumylphenyl-titanate and dicumylphenyl-oxyacetate-titanate. The surface treatment solution is prepared by adding the above surface treatment agent to 0.5 to 50.
It can be used as a solution of an organic polar solvent such as a lower alcohol or an amide-based solvent containing 1 wt%. The surface treatment liquid is preferably applied uniformly using a gravure coating method, a silk screen method, a dipping method or the like to form a thin layer.

One example of the method for producing the aromatic polyimide film of the present invention will be described below with reference to FIG. 1, which shows preferable heating conditions before curing in a curing furnace. That is,
The solidified film obtained as described above is further dried if necessary, and preferably the volatile content of the dried film is adjusted to be 10 to 45% by weight. Temperature (° C.) at the entrance of the curing furnace in the curing furnace shown in FIG. 1 with the edge held.
( 100-250 ° C) × After drying so that the residence time (minutes) is within the range of the oblique line, the maximum heating temperature: 400-500 ° C.
The dried film is heated and dried and imidized under the condition that the temperature is 0.5 to 30 minutes.
When the imidization is completed at a content of not more than weight%, an aromatic polyimide film can be suitably produced. Further, after the curing step, one or both sides of the aromatic polyimide film are alkali-treated (for example, after immersion in an aqueous alkali solution such as sodium hydroxide, and then washed and dried), and then the surface treatment liquid is applied and dried. , The film surface can be similarly surface-treated.

The aromatic polyimide film obtained as described above is preferably used under low tension or no tension.
Heat at a temperature of about 00 to 400 ° C. to perform stress relaxation treatment,
Take up.

In the above-mentioned aromatic polyimide film, the heating conditions before the curing in the curing furnace during the production described above are controlled within the range shown in FIG. 1 and the curing conditions are controlled within the above-mentioned temperature and time ranges. By doing so, the thickness is 10 to 125 μm, the volatile matter content is 0.4% by weight or less, and the specific crack resistance can be set to the value specified in the present invention. When the thickness of the aromatic polyimide film is larger than 125 μm, it is preferable to laminate a polyamic acid solution of two or more layers by a co-extrusion method, and then similarly dry and imidize to produce a thick polyimide film. Can be.

The aromatic polyimide film according to the present invention preferably has 3,3 as a tetracarboxylic dianhydride.
It can be easily obtained by a method of polymerizing 3 ′, 4,4′-biphenyltetracarboxylic dianhydride and paraphenylenediamine as an aromatic diamine, but as a polyamic acid, it satisfies the physical properties of the film. Within the range, other components may be polymerized together with 3,3 ′, 4,4′-biphenyltetracarboxylic dianhydride and paraphenylenediamine, and the type of bond may be random polymerization or block polymerization. Any of them may be used. Also,
If the total amount of each component in the finally obtained polyimide film is within the above range, a polyamic acid containing 3,3 ′, 4,4′-biphenyltetracarboxylic dianhydride and a polyamic acid containing paraphenylenediamine The acid may be used in combination with a polyamic acid component composed of other components. In any case, the target aromatic polyimide film can be obtained in the same manner as described above. Further, the aromatic polyimide film in the present invention is not limited to the above-mentioned thermal imidization, and can be similarly performed by chemical imidization as long as the conditions are within the above range.

The aromatic polyimide film according to the present invention is preferably subjected to a surface treatment by a corona discharge treatment, a plasma treatment, an ultraviolet irradiation, a flame treatment or the like when it is not treated with a surface treatment agent or when it is not treated with a surface treatment agent. An adhesive layer can be provided by applying an agent or laminating a film of these adhesives.

As a method for laminating a conductor layer on the surface of the aromatic polyimide film, preferably a film-treated surface, a conductor layer may be directly laminated by a vapor deposition method, a sputtering method, a plating method, or an adhesive layer. The conductor layer may be laminated via an agent. The adhesive for laminating the conductor layers via the adhesive may be a thermosetting type or a thermoplastic type. In particular, a polyimide adhesive, an epoxy resin adhesive, an acrylic resin adhesive, a polyamide resin adhesive, or the like is preferably used.

The conductor in the present invention includes metals such as aluminum, copper and copper alloys, and copper foil is generally used. The copper foil is an electrolytic copper foil or a rolled copper foil, and preferably has a tensile strength of 17 kg / mm ² or more. Further, the thickness is preferably 8 to 50 μm.

A circuit may be formed on the aromatic polyimide film of the present invention by laminating a conductor directly or, preferably, via an adhesive. When a circuit is formed on a conductor, a conductor is manufactured by laminating the conductor directly on an aromatic polyimide film or via an adhesive to produce a conductive substrate, and then, for example, an etching resist is formed on the surface of the conductor in a circuit pattern. After printing in a (wiring pattern shape) to form a wiring pattern of an etching resist for protecting the surface of the conductor at a portion where the wiring pattern is to be formed, an etching solution is used by a method known per se. In this case, the conductor can be removed by etching the portion where the wiring is not formed, and the etching resist is removed. A coat layer may be formed by directly coating the upper surface of the circuit pattern or after treating with a surface treatment agent such as a silane coupling agent, applying a coating material (liquid material), and drying by heating.

[0028]

Embodiments of the present invention will be described below. In each of the following examples, the physical properties of the polyimide film were measured by the following methods. Water absorption: measured according to ASTM D570-63 (23
° C × 24 hours) Tensile modulus: Measured according to ASTM D882-64T (MD) Coefficient of linear expansion (50 to 200 ° C): A sample that has been heated at 300 ° C for 30 minutes and stress-relaxed is subjected to a TMA apparatus (tensile module).
(2g load, sample length 10mm, 20 ° C / min)

The imidization ratio: calculated from the ratio of absorbance at 1780 cm ^-1 and 1510 cm ^-1 by FI-IR (ATR method). The measurement was performed on the A side of the film. Volatile content (solidified film): 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 Volatile content (polyimide film): determined by the following formula. Volatile content = [(AB) / A] × 100 A: film weight after heating at 150 ° C. for 10 minutes B: film weight after heating at 450 ° C. for 20 minutes

Dielectric breakdown voltage: ASTM D149-64
(25 ° C.) Volume resistivity: measured according to ASTM D257-61 (25 ° C.) Dielectric constant: measured according to ASTM D150-64T (2
5 ℃, 1KHz)

Example 1 54.6 kg of N, N-dimethylacetamide was added to a polymerization tank having an inner volume of 100 liter, and then 3,3 ′, 4,4′-biphenyltetracarboxylic dianhydride was added. 826 kg and 3.243 kg of paraphenylenediamine were added and polymerized at 30 ° C. for 10 hours, and the logarithmic viscosity of the polymer (measuring temperature: 30 ° C., concentration: 0.5 g / 100 ml solvent, solvent: N, N
-Dimethylacetamide) was obtained at a concentration of 1.60 and a polymer concentration of 18% by weight. In this polyamic acid solution, monostearyl phosphate triethanolamine salt at a ratio of 0.1 part by weight to 100 parts by weight of the polyamic acid and an average particle diameter of 0.1 part by weight (based on solid content) of 0.5 part by weight. 0
8 μm of colloidal silica was added and uniformly mixed to obtain a polyamic acid solution composition. The rotational viscosity of this polyamic acid solution composition was 3000 poise. This polyamic acid solution composition is continuously extruded from a slit of a T-die mold onto a smooth support of a casting / drying furnace to form a thin film of the solution, and dried at an average temperature of 141 ° C. to obtain a long film. A solidified film was formed. By peeling from the surface of the support, a long solidified film was obtained. Then N,
An aminosilane surface treatment solution of N-dimethylacetamide was uniformly applied to both sides of the long solidified film, and then dried to obtain a surface-treated dried film. This dried film had a volatile content of 27% by weight consisting of a solvent and produced water. Then, while holding the surface-treated dry film in the width direction, it is cured in a curing furnace (temperature at the inlet × residence time = 240 ° C. × 2 minutes, maximum temperature × maximum temperature residence time = 480 ° C. × 1) Minutes), a long aromatic polyimide film having a thickness of 25 μm, both surfaces of which were treated with a surface treating agent, was continuously produced. Table 1 shows the results of measurement and evaluation of this aromatic polyimide film.

Example 2 An elongated solidified film was obtained in the same manner as in Example 1 except that the slit width of the T-die was changed. The dried film was obtained by heating and drying in the same manner as in Example 1 without applying the surface treatment liquid to both surfaces of the long solidified film. This film had a volatile content of 27% by weight. Then, while holding the dried film in the width direction, it is cured in a curing furnace (temperature at the inlet × residence time = 200 ° C. × 4 minutes, maximum temperature × maximum temperature residence time =
(480 ° C. × 3 minutes), and a long aromatic polyimide film having a thickness of 50 μm was continuously produced. Table 1 shows the results of measurement and evaluation of this aromatic polyimide film.

Example 3 A long solidified film was produced in the same manner as in Example 2. Next, a dried film surface-treated in the same manner as in Example 1 was obtained. This film had a volatile content of 28% by weight. Next, while holding the dried film in the width direction, it is cured in a curing furnace (temperature at the inlet × residence time = 200 ° C. × 2.5 minutes,
(Maximum temperature × maximum temperature residence time = 480 ° C. × 3 minutes), and a continuous aromatic polyimide film having a thickness of 50 μm and having both surfaces treated with a surface treating agent was continuously produced. Table 1 shows the results of measurement and evaluation of this aromatic polyimide film.

Example 4 An elongated solidified film was obtained in the same manner as in Example 2 except that the slit width of the T-die was changed. Next, a dried film without surface treatment was obtained in the same manner as in Example 2. This film had a volatile content of 30% by weight. Then, while holding the dried film in the width direction, the film is cured in a curing furnace (temperature at the inlet × residence time = 140 ° C. × 5 minutes, maximum temperature × maximum temperature residence time = 480 ° C. × 3 minutes), A long aromatic polyimide film having a thickness of 75 μm was continuously manufactured. Both surfaces of this aromatic polyimide film were alkali-treated (soaked in 30% aqueous solution of sodium hydroxide for 30 minutes, then washed and dried).
Thereafter, the surface was treated in the same manner as in Example 1 to continuously produce a long aromatic polyimide film having a thickness of 75 μm, both surfaces of which were treated with a surface treating agent. Table 1 shows the results of measurement and evaluation of this aromatic polyimide film.

Example 5 An elongated solidified film was obtained in the same manner as in Example 2, except that the slit width of the T-die was changed. A dried film was obtained by heating and drying in the same manner as in Example 2 without applying the surface treatment liquid to both surfaces of the long solidified film. This film had a volatile content of 30% by weight. Then, while holding the dried film in the width direction, it is cured in a curing furnace (temperature at the inlet × residence time = 105 ° C. × 9 minutes, maximum temperature × maximum temperature residence time =
(450 ° C. × 15 minutes), and a long aromatic polyimide film having a thickness of 75 μm was continuously produced. Table 1 shows the results of measurement and evaluation of this aromatic polyimide film.

[Evaluation Examples] When the cut surfaces of the aromatic polyimide films obtained in Examples 1 to 5 were observed with a mold, linearity was maintained. Further, Examples 1 to 5
The aromatic polyimide film obtained in (1) is subjected to plasma treatment or the like as it is (if no surface treatment is performed), and then thermally treated with an electrolytic copper foil (35 μm) using an epoxy resin adhesive or a thermoplastic polyimide adhesive. Crimping (1
70 ° C., 40 kg / cm ² , 5 minutes), high peel strength (peel strength: 2 kg / cm or more, 180 °)
A laminate was obtained. The heat shrinkage of the aromatic polyimide films obtained in Examples 1 to 5 (25 ° C., 2 hours,
JIS C2318) was 0.3% or less in all cases.

[0037]

Table 1 Table 1 Example 1 2 3 4 5厚 み Film thickness (μm) 25 50 50 75 75 Surface treatment ( Yes / No Yes Yes Yes No No Crack resistance (Kg / 20mm) 32 68 67 84 93 Specific crack resistance (Kg / 20mm / 10μm) 12.8 13.6 13.4 11.2 12.4 Volatile content (%) 0.11 0.14 0.17 0.30 0.34 Water absorption (%) 1.27 1.34 1.35 1.20 1.35 Tensile modulus (Kg / mm ² ) 847 857 850 690 710 Linear expansion coefficient (× 10 ^-5 / ° C) 1.20 1.14 1.23 2.10 1.95 Dielectric breakdown voltage (KV) 6.6 10.4 10.3 9.8 9.6 Volume resistivity (× 10 ¹⁶ Ω · cm) 3.8 4.7 3.6 2.4 4.5 Dielectric constant (1 kHz) 2.95 3.03 3.10 3.00 3.05 ─────────────────────── ─────────────

[0038]

Since the present invention is configured as described above, it has the following effects. The aromatic polyimide film of the present invention has good punching properties, and retains adhesiveness, and can be processed with high precision. In addition, the laminate of the present invention has good adhesiveness and high precision workability.

[Brief description of the drawings]

FIG. 1 shows a range of suitable heating conditions before curing in a curing furnace in an example of a method for producing an aromatic polyimide film of the present invention. Vertical axis Temperature at the entrance of cure furnace (° C) × Residence time (minutes) Horizontal axis Film thickness (μm) Oblique line Preferred range

──────────────────────────────────────────────────の Continued on the front page (51) Int.Cl. ⁷ Identification symbol FI C08G 73/10 C08G 73/10 C08J 7/00 301 C08J 7/00 301 303 303 304 304 304 306 306 CFG CFGZ C08K 3/00 C08K 3 / 00 C08L 79/08 C08L 79/08 H01L 23/50 H01L 23/50 Y // C08L 79:08 C08L 79:08 (72) Inventor Susumu Morishige 10 Ube Industries, 1978 Kogushi, Oji, Ube City, Yamaguchi Prefecture (56) References JP-A-61-264028 (JP, A) JP-A-56-118204 (JP, A) JP-A-6-334110 (JP, A) JP-A-2-131936 (JP) JP, A) JP-A-62-236827 (JP, A) JP-A-61-111359 (JP, A) (58) Fields investigated (Int. Cl. ⁷ , DB name) C08J 5/18

Claims (14)

(57) [Claims] 1. A polyimide prepared by reacting a tetracarboxylic acid component containing at least 15 mol% of biphenyltetracarboxylic acid or a dianhydride or ester thereof with an aromatic diamine component containing at least 5 mol% of phenylenediamine. Consisting of 10-12 thick
5 μm aromatic polyimide film, wherein the aromatic polyimide film is 11 to 22 kg / 20 mm / 10
μm specific crack resistance and a volatile matter content of 0.4
A weight percent or less of an aromatic polyimide film. 2. The specific crack resistance is 11 to 15 kg / 20 m.
The aromatic polyimide film according to claim 1, which is in a range of m / 10 µm. 3. The aromatic polyimide film according to claim 1, having a volatile content of 0.3% by weight or less. 4. The aromatic polyimide film according to claim 1, having a volatile matter content of 0.2% by weight or less. 5. The aromatic polyimide film according to claim 1, further comprising 0.1 to 3% by weight of an inorganic filler. 6. The aromatic polyimide film according to claim 1, which is produced by a solution casting method of polyamic acid. 7. The surface is subjected to any one or more of a surface treatment agent treatment, a corona discharge treatment, a flame treatment, an ultraviolet irradiation treatment, a glow discharge treatment, and a plasma treatment. Item 6. The aromatic polyimide film according to any one of Items 6. 8. A water absorption rate of 1.8% or less and a tensile modulus of 4
50 kg / mm ² or more and a coefficient of linear expansion (50 to 200
The aromatic polyimide film according to any one of claims 1 to 7, wherein (C) is 2.5 x 10 ^-5 cm / cm / C or less. 9. The aromatic material according to claim 1, wherein a dielectric breakdown voltage is 3 KV or more and a volume resistivity (25 ° C.) is 2 × 10 ¹⁶ Ω · cm or more. Polyimide film. 10. A polyimide prepared by reacting a tetracarboxylic acid component containing at least 15 mol% of biphenyltetracarboxylic acid or a dianhydride or ester thereof with an aromatic diamine component containing at least 5 mol% of phenylenediamine. Consisting of 10-1 thickness
25 μm aromatic polyimide film, wherein the aromatic polyimide film is 11 to 22 kg / 20 mm / 1
It has a specific crack resistance of 0 μm and a volatile matter content of 0.1 μm.
A laminate in which an aromatic polyimide film of not more than 4% by weight and a conductive sheet are bonded via an adhesive layer. 11. The laminate according to claim 10, wherein the conductor sheet is a copper foil having a thickness of 8 to 50 μm. 12. The laminate according to claim 10, wherein the adhesive layer is made of a thermoplastic adhesive or a thermosetting adhesive. 13. The laminate according to claim 10, wherein the adhesive layer is made of a polyimide adhesive or an epoxy resin adhesive. 14. The laminate according to claim 10, which is used for a lead frame of an electronic component.