JP3482723B2 - Multi-layer aromatic polyimide film - Google Patents

Description

Description: BACKGROUND OF THE INVENTION 1. Field of the Invention
Aromatic polyimide film having an imide layer on the surface,
Extremely high heat resistance, dimensional stability and mechanical properties
And the thermoplastic aromatic polyimide layer and the aromatic
Multi-layer fragrance with strong adhesion between polyimide film
The present invention relates to a group III polyimide film. This multilayer
Aromatic polyimide film is coated with a thermosetting adhesive or the like.
A thin layer of thermoplastic aromatic polyimide and gold
It has high heat resistance because it can be joined with metal foil by thermocompression bonding
Thus, a laminated body can be obtained. Multilayer of the invention
Aromatic polyimide film for printed circuit boards and TAB
Useful for tapes, composite lead frames, etc. [0002] Conventionally, metal foils and heat-resistant films (for example,
For example, a composite material (eg, aromatic polyimide) support
For example, a copper-clad substrate) is composed of an aromatic polyimide film and gold.
Through a “thermosetting adhesive such as epoxy resin”
One thing that can be manufactured by lamination by heat bonding is
Was common. [0003] However, the heat-cured
The adhesive layer has a constant operating temperature at which appropriate adhesive strength can be maintained.
Since the temperature was at most 200 ° C or less,
Processing steps exposed to high temperatures or applications exposed to high temperatures
Can not be used with a metal foil etc.
A more heat-resistant composite material with a film
Was expected. As a countermeasure, a heat-resistant adhesive must be detected.
Various discussions have been conducted, but adhesives with high heat resistance
Requires a high temperature in the laminating process or a complicated laminating process.
Required, and the resulting laminate has sufficient adhesion
It is not practical because there are many problems such as not showing
Was. On the other hand, no thermosetting adhesive or the like is used.
Do not use a metal layer on the aromatic polyimide film support.
Those who manufacture the "adhesive-free composite material" that has been formed
Several laws are also being considered. [0006] For example, a method for producing an “adhesive-free composite material”
As the aromatic polyimide precursor (aromatic polyamid
Solution) is cast on a metal foil to form a composite material.
Manufacturing method or on aromatic polyimide film
Metal and / or vacuum deposited
Thus, a method for producing a composite material has been proposed. [0007] However, in the above-mentioned casting film forming method, a support layer is formed.
Very difficult or too thick
Is extremely long in the solvent evaporation / removal process in the film forming process.
There was a problem that time was low and productivity was low. Ma
In addition, the above-described metal plating method and / or metal evaporation method
It is difficult to make the metal layer thick enough.
In that respect, productivity was low. Furthermore, recently, a thermoplastic polyimide resin
To produce a laminate by laminating metal film and metal foil
Methods (JP-A-62-53827, JP-A-6-93)
238, JP-A-6-218880).
Have been. However, this method does not
The heat resistance, dimensional stability and mechanical properties of the
The characteristics of the metal foil laminate using this
Not. SUMMARY OF THE INVENTION The object of the present invention is to
Low heat-resistant aromatic polyimide film layer
At least one surface of a thermoplastic aromatic resin that can be laminated with another substrate
Multi-layer aromatic polyimide with a laminated polyimide layer
Film that adheres to other substrates, such as metal foil.
Multi-layer aromatic polyimide film with high heat resistance
It is to provide LUM. [0010] That is, the present invention provides:
A general formula is applied to both sides of the highly heat-resistant aromatic polyimide film.
I (However, X is O, CO or SO ₂ And n is 0 to 4
An aromatic diamine compound represented by the formula [1,
Except for 3-bis (3-aminophenoxy) benzene]
Aromatic tetracarboxylic dianhydride or its derivatives
Logarithmic viscosity obtained [natural logarithm (solution viscosity / solvent viscosity)
/ Concentration of solution, concentration of solution = polymer-0.5 g / 100
ml solvent, 30 ° C.] is 0.1 to 0.38.
Thermoplastics composed of thermoplastic aromatic polyimides
An imide layer is integrally laminated. (1) Coefficient of linear expansion (50 to 3)
00 ° C) is 1 × 10 ^-5 ~ 3 × 10 ^-5 cm / cm / ° C
(2) so that the copper foil and the thermoplastic polyimide layer adhere to each other.
The metal foil laminated film which is continuously pressed and laminated is 28
Swelling and peeling in solder heat resistance test at 8 ± 5 ° C for 10 seconds
Resistance to soldering and reproducibility in reliability tests
A multilayer aromatic polyimide film having good reliability and satisfying
It is. Hereinafter, the present invention will be described with reference to the drawings.
And will be described in detail. FIG. 1 and FIG.
It is sectional drawing which shows the example of a layer aromatic polyimide film.
The multilayer aromatic polyimide film of the present invention: 1
For example, as shown in FIG. 1 and FIG.
Thin film B: 3 (3 ') made of group polyimide has high heat resistance
At least in the base layer A: 2 comprising an aromatic polyimide of
Multi-layer polyimide film laminated on one side
It is. The above-mentioned multilayer aromatic polyimide film is
(Method a) Aromatic polyimide containing dehydrating agent and catalyst
An organic polar solvent solution of the precursor is cast and applied in a film form
After heating, the aromatic polyimide precursor is imidized to obtain
Self-supporting gel containing 20 to 90% by weight of volatile matter
Low logarithmic viscosity thermoplastic on at least one side of the plasticized film
A layer obtained by forming a layer of an aromatic polyimide solution
Is dried, preferably at a temperature of 50-200 ° C., and then
Heat treatment including a heat treatment step at a temperature of 00 ° C or higher
Low logarithm produced by completing solvent evaporation and imidation by
Viscous thermoplastic aromatic polyimide layer on at least one side
Having a multilayer aromatic polyimide film, or (method b)
High heat resistant aromatic polyimide precursor solution and low logarithmic viscosity
Extrusion Method of Polyamide with Thermoplastic Aromatic Polyimide Solution
After extrusion, the resulting laminate is preferably
Dry at a temperature of 0-200 ° C, then heat 300 ° C or more
Solvent by subjecting it to a heat treatment including a heat treatment step at a temperature.
Thermoplastic aromatic poly produced by complete evaporation and imidization
Multi-layer aromatic polyimide having imide layer on at least one side
Film or (c method) highly heat-resistant aromatic polyester
Laminated with thermoplastic aromatic polyimide
The surface to be treated is activated in advance for the purpose of imparting adhesiveness,
Low logarithmic viscosity thermoplastic laminated by coating method
Aromatic Polyimide with Functional Aromatic Polyimide Layer on Surface
Mido film or (d method) high heat-resistant aromatic poly
The imide film is preferably coated by a coating method.
Low logarithmic viscosity thermoplastics with added run coupling agent.
Low logarithmic viscosity thermoplastic fragrance laminated with aromatic polyimide
Multilayer polyimide film having aromatic polyimide layer on the surface
It is film. The above-mentioned aromatic polyimide film having high heat resistance
Is an aromatic tetracarboxylic dianhydride or a derivative thereof
And aromatic diamines in organic polar solvents known per se
By polymerization, casting, drying, imidization
You. In particular, high heat-resistant aromatic polyimide film
And at least 30 mol%, especially at least 50 mol% of biphenyl
Tetracarboxylic acid component (particularly 3, 3 ', 4, 4'-bifu
Phenyltetracarboxylic dianhydride) and at least 50 mol%
Phenylenediamine component (particularly p-phenylenediamine
A) obtained from polymerization and imidization from
Group III polyimide, heat resistance, mechanical strength, dimensions
It is preferable from the viewpoint of stability. The other remaining (if two types of
Uses tracarboxylic dianhydride and / or diamine
) As aromatic tetracarboxylic dianhydride
Lomellitic dianhydride and aromatic diamine
Diaminodiphenyl ether is preferred. As the above organic polar solvent, N, N-di-
Methylformamide, N, N-dimethylacetamide,
N-methyl-2-pyrrolidone, N-methylcaprolacter
Amide solvents such as dimethyl sulfoxide, hexame
Tylphosphoramide, dimethyl sulfone, tetramethyl
Rensulfone, dimethyltetramethylene sulfone, pyri
Gin, ethylene glycol and the like. In the present invention, the low logarithmic viscosity heat
It is necessary to use a plastic aromatic polyimide layer.
This provides a highly reliable (reproducible) metal foil
A imide film is obtained. As the above-mentioned thermoplastic aromatic polyimide,
Is benzophenone as an aromatic tetracarboxylic acid component
Tetracarboxylic dianhydride, pyromellitic dianhydride,
3,3'4,4'-biphenyltetracarboxylic dianhydride
Substance, 2,3,3 ', 4'-biphenyltetracarboxylic acid
Preference is given to dianhydrides, of which 3,3'4
4'-biphenyltetracarboxylic dianhydride, 2,3
3 ', 4'-biphenyltetracarboxylic dianhydride is preferred.
More preferably, the aromatic diamine component is represented by the above general formula I.
Aromatic diamines such as diaminodiphenyl ether
Ters, di (aminophenoxy) benzenes, bis (A
(Minophenoxyphenyl) sulfones are preferred. Fluidity of the above thermoplastic aromatic polyimide
Aromatic dicarboxylic anhydride or aromatic
Amines at both ends of the amic acid
Or those with dicarboxyl groups blocked (sealed) are preferred
No. Aromatic dicarboxylic anhydride as a blocking agent
Terephthalic anhydride is particularly preferred as
Aniline is preferred as the amine. The above-described thermoplastic thermoplastic aromatic polymer having a low logarithmic viscosity
Use a thermoplastic polyimide solution to provide the
Preferably. The polyimide solution contains
A filler such as tan or silicon dioxide may be added. H
The addition of the filler may be at any stage. The above thermoplastic fragrance
The solution of the group III polyimide solution is obtained by polymerizing a polymer in an organic polar solvent.
A concentration of 5 to 50% by weight, in particular 7 to 45% by weight,
The rotational viscosity measured at 0 ° C. is 0.5 to 10,000 poise,
In particular, those having 0.7 to 5000 poise are preferably used.
It is. The above-mentioned thermoplastic aromatic polyimide layer is reduced in number.
At least the polyimide film provided on one side
6 to 250 μm, especially 8 to 200 μm, more preferred
It is about 10 to 150 μm. In addition, the thermoplastic
The aromatic polyimide layer is made of a high heat-resistant aromatic polyimide film.
2 to 100% by weight, based on the polymer weight,
It is preferably from 5 to 90% by weight. (A) Multi-layer aromatic polyimide film
Lum, for example, the patent application filed by the applicant
Manufactured by the method described in JP-A-63-42817.
Can be The high heat-resistant aromatic polyimide film
A method known per se for polyamic acid solutions of the composition
To contain a dehydrating agent and a catalyst.
And the polyamic acid is preferably heated to an imidization ratio of 2
0-80% partially imidized, volatile content 20-
90% by weight aromatic polyimide gelled film
Build. Acetic anhydride is used as the dehydrating agent, and
Soquinoline is preferred. Imidization of the gelled film
The rate is 1780cm by infrared spectroscopy ^-1 (Sucking from imide
) And 1510cm ^-1 (Absorption from benzene ring) or
I asked. The volatile content of the gelled film was measured.
The target film is dried at 420 ° C. for 20 minutes, and before drying.
Weight W ₁ And weight W after drying _Two From the following equation
Was. Volatile content (% by weight) = [(W ₁ -W _Two ) / W ₁ ] ×
100 At least one surface of the gelled film is thermoplastic
The solution of the aromatic polyimide or its precursor is
Knowledge method (knife coater, comma coater, gravure
Coater, etc.) and preferably dried at 50-170 ° C
And heating including a step of heating to a temperature of 300 ° C. or more
By the treatment, a temperature of 200 to 350 ° C. or more is particularly preferable.
Degree of heating to promote imidization, multilayer aromatic polyimide
A film can be obtained. The multilayer aromatic polyimide film obtained by the method (b)
Lum preferably has the features already filed by the applicant.
Manufactured by the method described in JP-A-3-180343.
can do. In other words, aromatic polyester with high heat resistance
An aromatic polyamic acid (precursor) solution to give the amide;
Extruding two or more layers of thermoplastic aromatic polyimide solution
Using a molding die, a two-layer or more thin film
After casting on a support and drying, peeling off from the support
Remove the solvent by heating at a temperature of 300 ° C or more as in
To complete multi-layer aromatic polyimide film
Can be. The multilayer aromatic polyimide film obtained by the method (c)
Lum is preferably the high heat-resistant aromatic polyimide film.
Aminosilane treatment, plasma treatment,
Is activated by corona discharge, etc.
Aromatic polyimide solution is prepared by a method known per se, for example,
For example, blade coater, knife coater, impregnation coater,
Comma Coater, Reverse Roll Coater, Graviako
-Apply using a tar, etc., and after drying,
The solvent is removed by heating at a temperature of 00 ° C.
A polyimide film can be obtained. The multilayer aromatic polyimide film obtained by the method (d)
Lum is preferably the high heat-resistant aromatic polyimide film.
Adhesion to high heat-resistant aromatic polyimide film
Aminosilane, epoxy silane,
Added silane coupling agent such as mercaptosilane
Apply a thermoplastic aromatic polyimide solution, and after drying,
Remove the solvent by heating at a temperature of 300 ° C or more as described above.
Thus, a multilayer aromatic polyimide film can be obtained.
You. The amount of the silane coupling agent depends on the
Preferably 0.2 to 5% by weight based on the weight of the polyimide
No. The material obtained by any of the above methods
Using the multilayer aromatic polyimide film of the invention of
For example, Japanese Unexamined Patent Publication No.
No. 3,847, JP-A-4-33848.
By the method, a thermoplastic aromatic polyimide layer and metal foil
Can obtain a heat-pressed metal foil laminated polyimide film.
Can be. Embodiments of the present invention will be described below. The following examples
Indicates parts by weight, and the measurement in each example is as follows.
The test was performed according to the test method. Logarithmic viscosity Logarithmic viscosity = natural logarithm (solution viscosity / solvent viscosity) ÷ solution concentration
The solution concentration is 0.5 g of polymer dissolved in 100 ml of solvent.
Measured. Rotational viscosity Measured at 30 ℃ using Bismetron of Tokyo Keisoku Co., Ltd.
Specified. Glass transition temperature (Tg ) Determined by differential scanning calorimetry (DSC) or filled
The rubber sample was determined by thermomechanical analysis (TMA). Adhesive strength Metal foil laminated film (multi-layer aromatic polyimide film and
Metal foil: 35μm thick copper foil and thermoplastic polyimide
Layer and metal foil are laminated so that they adhere to each other)
The wearing strength was set to “9” of IPC-TM-650 (2.4.9.).
0 ° -peeling method ”. Solder resistance Measurement based on IPC-TM-650 (2.4.13)
In a solder bath maintained at a temperature of 288 ± 5 ° C.
The metal foil laminated film of the sample obtained in
Float for 10 seconds so that it comes in contact with the
The presence or absence of swelling, peeling, etc. of the layer film is visually judged (pass / fail).
Determined). Tensile test, linear expansion coefficient Tensile strength and elongation according to ASTM D-882
The modulus and modulus were measured. Linear expansion coefficient is sample film
Of the sample film after heat treatment at 400 ° C.
5 ° C / min in hand direction at 50 to 300 ° C
Was measured. Surface tension of film surface It was measured with a wetting index standard solution manufactured by Wako Pure Chemical Industries, Ltd. Reliability (reproducibility) Repeat the same operation 10 times and get the same result
Good results were obtained even once.
Was evaluated as defective. Reference Example 1 A nitrogen inlet tube, a thermometer, a reflux condenser, and a stirrer were provided.
N, N-dimethylacetoacetate as a solvent
3600 parts of amide (DMAc) and (a)
Tracarboxylic acid component; 3,3 ', 4,4'-biphenyl
Tetracarboxylic dianhydride (s-BPDA) 83.85
Part (285 mmol) and 2,3,3 ', 4'-biff
Phenyltetracarboxylic dianhydride (a-BPDA) 8
3.85 parts (285 mmol), (b) aromatic diamine
Component: bis [4- (4-aminophenoxy) phenyl]
259.5 parts of sulfone (4-BAPS) (600 mmol
C) an aromatic dicarboxylic acid component;
8.89 parts (60 mmol) of tallic acid (PA)
A DMAc solution of colloidal silica with a particle size of about 600
25 parts by weight so that the weight of the
Stir at 6 ° C for 6 hours to obtain a solution of polyamic acid (concentration: 10
% By weight, rotational viscosity: 30 poise). Reference Example 2 Azeotropic azeotrope was added to 500 parts of the polyamic acid solution prepared in Reference Example 1.
Add 50 parts of toluene for dehydration and do not blow nitrogen gas.
While stirring and distilling off the generated water,
The reaction is carried out at the reaction temperature for 4 hours to obtain a uniform thermoplastic aromatic polycarbonate.
DMAc solution of limide (10% by weight, rotational viscosity: 25
Poise) was manufactured. A portion of this polymer solution is
Into the polymer to precipitate a polymer containing silica,
The polyimide powder is recovered and the aromatic polyimide powder is recovered.
Is washed with hot methanol and dried to obtain a thermoplastic fragrance.
A group polyimide was obtained. Thermoplastic aromatic polyamide obtained
The Tg was 269 ° C. and the logarithmic viscosity was 0.38. Reference Example 3 1010 parts of DMAc was added to the reaction vessel used in Reference Example 1.
And (a) an aromatic tetracarboxylic acid component and
And 3,3 ', 4,4'-biphenyltetracarboxylic
113.0 parts of acid dianhydride (s-BPDA) (384 mm
Mol) and 2,3,3 ', 4'-biphenyltetraca
113.0 parts of rubonic dianhydride (a-BPDA) (38
4 mmol), and (b) 1 as an aromatic diamine component,
80.1 parts of 4-diaminophenyl ether (DADE)
(400 mmol) and 1,4-bis (4-aminophen)
Enoxy) benzene (APB) 116.9 parts (400
And (c) an aromatic dicarboxylic acid component
9.48 parts (64 mmol) of phthalic anhydride (PA)
Except that polyamic acid was added.
An acid solution was prepared. A solution of this polyamic acid (concentration:
30% by weight, rotational viscosity: 1,400 poise). this
Add azeotropic dehydration toluene 50 to 500 parts of polyamic acid solution
Part and add while stirring to generate nitrogen gas.
While distilling off water, react for 4 hours at a reaction temperature of about 165 ° C.
In response, a uniform thermoplastic aromatic polyimide DMAc
Production of solution (30% by weight, rotational viscosity: 1200 poise)
did. A part of this polymer solution is injected into methanol,
The polymer was precipitated, and the aromatic polyimide powder was recovered.
The aromatic polyimide powder with hot methanol?
And dried to obtain a thermoplastic aromatic polyimide powder. Profit
The logarithmic viscosity of the obtained polyimide powder was 0.38. Reference Example 4 A nitrogen inlet tube, a thermometer, a reflux condenser, and a stirrer were provided.
2, 3, 3 ', 4'-
Biphenyltetracarboxylic dianhydride (a-BBPD
A) 26.48 parts (90 mmol), ω, ω '-(3-
Aminopropyl) polydimethylsiloxane (BAPS)
(Shin-Etsu Silicon Co., Ltd., X-22-161AS, l
= 8) 16.8 parts (20 mmol), and N-
Charge 300 parts of methyl-2-pyrrolidone (NMP),
After increasing the temperature to 50 ° C and dissolving in a nitrogen stream,
2,2-bis [4- (4-diaminophenoxy) phenyl
28] 74 parts of propane (BAPP) (70 mm
And stirred at this temperature for 1 hour.
50 parts of xylene was added to the solution and the temperature was raised to 200 ° C.
After stirring for 2 hours under reflux to remove water of reaction, polyimide
18% by weight of oxane dissolved polyimide solution
Obtained. Next, the polymer solution, which has been returned to room temperature, is filtered under pressure, and
Precipitate using on-exchange water, wash, and remove polyimide
Roxane (95% yield, imidization ratio: 100%, logarithmic viscosity
Degree: 0.52) was obtained. The Tg of this polyimide is 2
34 ° C. 100 parts of this polyimide and Polyimi
2% by weight of γ-glycidoxypropyl trim
Toxic silane (Shin-Etsu Silicon Co., Ltd.) and solvent
And 200 parts of tetrahydrofuran (THF) at 23 ° C.
And stirred for about 5 hours to obtain a homogeneous solution (concentration: 33% by weight, 3
(Viscosity at 0 ° C .: 45 poise). REFERENCE EXAMPLE 5 No aromatic dicarboxylic acid component was added,
Except that the concentration was 10% by weight.
A riamic acid solution was prepared. This aromatic polyamic
This thermoplastic aromatic resin was prepared from the acid solution in the same manner as in Reference Example 2.
DMAc solution of limide (10% by weight, rotational viscosity: 50
Poise) got. Further, in the same manner as in Reference Example 2,
Powder was obtained. The Tg of this polyimide (powder) is 269
C. and the logarithmic viscosity was 1.95. Example 1 (shown for reference) N, N-dimethyl
6200 parts of luacetamide (DMAc) and p-fe
270.35 parts of Nilendiamine (PPD) (2.5
And stirred at room temperature (about 30 ° C.) in nitrogen. this
Add 3,3 ', 4,4'-biphenyltetracarboxylic acid to the solution
735.55 parts of acid dianhydride (s-BPDA) (2.5
) And stirred for 6 hours to give a polymer concentration of 14% by weight.
To obtain a solution of an aromatic polyamic acid. Rotation of this solution
The viscosity was 1300 poise (30 ° C.). Isoquinoline 8 was added to this polyamic acid solution.
0.7 parts (0.63 mol), 510.5 parts of acetic anhydride
(5.0 mol), and 3050 parts of DMAc.
Endless metal rotating the obtained solution from T-die
After extruding on a belt to form a coating film, hot air at 65 ° C
Was applied to the surface and dried for 15 minutes and then formed
The gelled film was peeled from the metal belt. This fill
The heating loss of the rubber is 76% by weight, and the surface tension is 37 dy.
ne / cm. The polyimide solution prepared in Reference Example 2 was
As a gelling solution, use a comma coater to
Gelling at a speed of 2 m / min on a dry basis
Coating in an amount to give 20% by weight based on the film
Then, the obtained laminate was dried in a hot air oven at 80 ° C. this
Hold the laminated dry film with a pin tenter and
While moving continuously at a speed of 2 m / min, 200
3 minutes at 310 ° C., 3 minutes at 310 ° C., 3 minutes at 440 ° C.
Heat-treated at 350 ° C for 3 minutes to a thickness of 60 μm (thin layer
(Thickness: 10 μm, the same applies hereinafter) of two layers of aromatic polyimide
Film was obtained. This multilayer polyimide film and clean
Pressure of 50cm / min with the converted metal foil (electrolytic copper foil)
It was measured using a sample that was continuously crimped at
the same). Tables 1 and 2 show the measurement results. Example 2 The polyimide solution prepared in Reference Example 2 was used as a coating solution.
And coated on both sides of gelled film
Otherwise, in the same manner as in Example 1, the thickness is 70 μm (thin
Layer thickness: 10 μm each)
Lum got it. The results are shown in Tables 1 and 2. Example 3 s-BPDA and PPD were polymerized in DMAc,
Aroma with lima concentration of 18% by weight and solution viscosity of 1600 poise
A group polyamic acid solution was obtained. The first aromatic polyamid
Using the citric acid solution and the aromatic polyimide solution of Reference Example 3
From a three-layer extrusion die onto a smooth metal support.
Extruded on a surface, cast and dried continuously with hot air at 140 ° C
And solidified film (self-supporting film, containing volatiles
Amount: 35% by weight), and the solidified film is used as a support.
After heating, gradually from 200 ° C to 450 ° C in a heating furnace
The temperature is raised to remove the solvent, and the polymer with high heat resistance
To obtain a three-layer aromatic polyimide film
Was. The results are shown in Tables 1 and 2. Example 4 s-BPDA and PPD were polymerized in DMAc to give a poly
Aroma having a mer concentration of 18% by weight and a solution viscosity of 1600 poise
A polyamic acid solution was prepared. This aromatic polyamid
Using a solution of citric acid, press on top of a smooth metal support
Cast out, dry continuously with hot air at 140 ° C, and solidify
To form a film (solvent content: 35% by weight)
200 ° C in a heating furnace
From 450 to 450 ° C to remove the solvent.
Aromatic polyimide film by imidizing polymer to
Got. The thickness of the polyimide film was 50 μm.
Was. The surface of this polyimide film is pressed in an oxygen atmosphere.
Razuma treated. Coating solution prepared in Reference Example 2
With a comma coater, plasma treated high heat resistant fragrance
At the speed of 2m / min
In an amount such that the total on both sides is 40% by weight on a dry matter basis,
-Drying the resulting laminate in a hot air oven at 80 ° C
did. Further, while continuously moving through the high-temperature furnace, 20
Heat treatment at 0 ° C for 3 minutes and 310 ° C for 3 minutes
A three-layer aromatic polyimide film having a thickness of μm was obtained. Table of results
1 and Table 2. Example 5 A solution obtained by diluting the solution prepared in Reference Example 3 with DMAc was prepared.
Weight% coating solution (rotational viscosity: 20 poise)
Except for using the same procedure as in Example 4, three layers of aromatic poly
An imide film was obtained. The results are shown in Tables 1 and 2. Embodiment 6 (Shown for reference) The coating solution prepared in Reference Example 4 was used as a comma coater.
Thus, the highly heat-resistant aromatic polyimide film prepared in Example 4
2m / min speed on both sides of film (plasma untreated)
Amount such that the total of both sides is 40% by weight on a dry matter basis
And the obtained laminate is heated in a hot air oven at 80 ° C.
Dried. While moving continuously in the high-temperature furnace,
Heat treated at 200 ° C for 3 minutes and 310 ° C for 3 minutes,
A 70 μm three-layer aromatic polyimide film was obtained. result
Are shown in Tables 1 and 2. Example 7 DMAc448 was placed in a cylindrical polymerization tank having an internal volume of 10 liters.
0 parts, 227.09 parts (2.1 mol) of PPD, 4,4 '
180.22 parts of diaminodiphenyl ether (0.9
Mol) and stirred at room temperature (about 30 ° C.) in nitrogen. This
S-BPDA 441.33 g (1.5 mol)
And pyromellitic dianhydride (PMDA) 327.18
(1.5 mol), and the mixture was stirred for 6 hours.
Polyamide for High Heat Resistant Polyimide of 20% by Weight
A solution of carboxylic acid was obtained. The rotational viscosity of this solution is 1700 po
(30 ° C.). The resulting aromatic polyester with high heat resistance
Example except for using copolymerized polyamic acid for polyimide
In the same manner as in 3, a three-layer aromatic polyimide film was obtained.
Was. The results are shown in Tables 1 and 2. Embodiment 8 (Shown for reference) Copolymer for highly heat-resistant aromatic polyimide obtained in Example 7
Same as Example 4 except that a polyamic acid solution was used.
Heat-resistant polyimide film (plasma untreated)
Was. Reference Example 4 on both sides of this high heat resistant polyimide film
As in Example 6, using the coating solution prepared in
Thus, a three-layer aromatic polyimide film was obtained. The result
The results are shown in Tables 1 and 2. Comparative Example 1 The polyamic acid solution of Reference Example 5 was used as a coating solution.
A three-layer aromatic resin was used in the same manner as in Example 6 except that
A polyimide film was obtained. The results are shown in Tables 1 and 2. [Table 1] [Table 2] The present invention is configured as described above.
Has the effect described below.
You. A heat-resistant material having a low logarithmic viscosity with another base material, especially a metal foil
High adhesion strength to plastic aromatic polyimide film layer
No. In addition, with metal foil using a laminated polyimide film
The solder resistance of the laminated film is good. Further, a thermoplastic aromatic polyolefin having a low logarithmic viscosity is used.
Since an imide film is used, heat compression bonding with metal foil is
Since it can be performed under gentle conditions, reliable results can be obtained.
This enables continuous industrial production. Also, a highly heat-resistant aromatic polyimide film
The biphenyltetracarboxylic acid component is at least 30 mol%
And a polyphenylene diamine component comprising 50 mol%
Multilayer aromatic polyimide film obtained using imide
Has a linear expansion coefficient of 1 × 10 ^-Five ~ 3 × 10 ^-Five cm / cm /
° C, and can be used for high precision applications.

BRIEF DESCRIPTION OF THE DRAWINGS FIG. 1 is a sectional view showing an example of a two-layer aromatic polyimide film of the present invention. FIG. 2 is a sectional view showing an example of a three-layer aromatic polyimide film of the present invention. [Description of Signs] 1 Multilayer aromatic polyimide film 2 Base layer A made of aromatic polyimide having high heat resistance 3 Thin layer B made of thermoplastic aromatic polyimide 3 'Thin layer B made of thermoplastic aromatic polyimide

Continuation of the front page (56) References JP-A-6-218880 (JP, A) JP-A-62-248782 (JP, A) JP-A-6-2866053 (JP, A) JP-A-7-193349 (JP, A) , A) WO 94/021744 (WO, A1) (58) Fields investigated (Int. Cl. ⁷ , DB name) B32B 1/00-35/00

Claims (1)

(57) [Claims 1] A high heat-resistant aromatic polyimide film having a general formula I on both surfaces. (Where X is O, CO or SO ₂ , and n is 0 to 4)
An aromatic diamine compound represented by the formula [1,
Excluding 3-bis (3-aminophenoxy) benzene] and an aromatic tetracarboxylic dianhydride or a derivative thereof, a logarithmic viscosity [natural logarithm (solution viscosity / solvent viscosity)]
/ Concentration of solution, concentration of solution = polymer-0.5 g / 100
ml solvent, 30 ° C.] is a thermoplastic polyimide layer made of thermoplastic aromatic polyimide having a low logarithmic viscosity of 0.1 to 0.38, and (1) the coefficient of linear expansion of the laminated polyimide film (50-3
00 ° C) is 1 × 10 ^{−5 to} 3 × 10 ⁻⁵ cm / cm / ° C.
(2) a metal foil laminated film continuously pressed and laminated so that the copper foil and the thermoplastic polyimide layer adhere to each other,
A multilayer aromatic polyimide film that swells in a solder heat resistance test at 8 ± 5 ° C for 10 seconds and does not peel off, and has good reliability in reproducibility in a reliability test.