JP3178279B2 - Polyimide film with adhesive 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 improved method for producing a polyimide film with an adhesive. More specifically, it can be bonded to other conductors, has low warpage even after curing and etching of the adhesive, has high dimensional accuracy in various manufacturing processes, and has good adhesion when mounting other components. Method for producing a polyimide film with an agent,
Further, the present invention relates to a method for producing a laminate in which metal foils are laminated.

[0002]

2. Description of the Related Art Conventionally, an adhesive polyimide film in which an epoxy resin-based, polyamide-based, or acrylic resin-based adhesive is provided on one surface of an aromatic polyimide film comprising an aromatic tetracarboxylic acid component and an aromatic diamine component. Is
It has excellent electrical insulation, mechanical strength, heat resistance, dimensional stability, etc.
It is used for production of AB and the like.

However, the demand for high quality and high precision in the field of the electronics industry has been increasingly strong in recent years, and the dimensional accuracy in the manufacturing process and the positioning for mounting other parts have also been required for polyimide films with an adhesive. Improvement is needed. For this reason, a dimensionally stable polyimide film has been proposed as described in Japanese Patent Publication No. 4-6213.

However, after bonding the polyimide film with a metal foil using an adhesive-provided polyimide film provided with an adhesive, if the metal foil is removed by etching, warping may occur with the adhesive inside. Still, the above-mentioned problem in the polyimide film with the adhesive has not been completely solved.

[0005]

SUMMARY OF THE INVENTION It is an object of the present invention to provide high dimensional accuracy in a manufacturing process and small warpage even after curing of an adhesive, so that workability is good and positioning when mounting other parts is good. It is to provide a polyimide film with an adhesive and a laminate thereof.

That is, according to the present invention, the polymer comprises an aromatic tetracarboxylic acid component and an aromatic diamine component, has an elastic modulus of 400 kg / mm ² or more and a thickness of 5 to 12 mm.
For a polyimide film of 5 μm and an adhesive having a thickness of 4 to 60 μm provided on one side thereof, the thickness measured by the contact measurement method and each elastic modulus were related by the following formula, where X was 0.7 or more. The present invention relates to a method for producing a polyimide film with an adhesive, characterized by satisfying the following condition. ^{X = (T1 2 × E1)} / (T2 2 × E2 × 10 2) [ where, T1: thickness of the polyimide film (μm), E
1: Elastic modulus (kg / mm ² ) of polyimide film, T
2: thickness of cured adhesive (μm), E2: modulus of elasticity of cured adhesive (kg / mm ² )] In the above, the thickness of the polyimide film and the adhesive is a value measured by a contact measurement method. is there.

[0007] The present invention also relates to a method for producing a laminate, further comprising laminating a metal foil on the adhesive of the polyimide film with the adhesive according to the above-mentioned production method.

[0008] The modulus of elasticity (MD) of the polyimide film and the cured adhesive is ASTM-D-88.
The elastic modulus of the cured adhesive is different from that of the laminate, and the copper foil is etched on the both sides of the adhesive for measurement and removed after curing. Refers to the determined elastic modulus.

The polyimide film used in the present invention comprises an aromatic tetracarboxylic acid component and an aromatic diamine component and has an elastic modulus of 400 kg / mm ² or more, preferably 410 kg / mm ² or more, and particularly preferably 42 kg / mm ² or more.
It is 0 kg / mm ² or more, and preferably has excellent chemical resistance. If the elastic modulus is less than 400 kg / mm ² , it will be difficult to obtain a laminate exhibiting the effects of the present invention in which the dimensional change rate is small (therefore, the dimensional accuracy is high) and the warpage is small.

[0010] Such a polyimide film can be suitably produced, for example, by the following method.
That is, when producing a polyimide film having a thickness of 5 to 125 μm, a solution composition of an aromatic polyamic acid obtained from an aromatic tetracarboxylic acid and an aromatic diamine in an organic polar solvent is filtered and defoamed, It is cast to a uniform thickness on a substrate such as a metal drum or metal belt from a hopper or T-die, and is heated to 60 to 160 ° C by hot air or infrared rays.
And gradually remove the solvent and pre-dry until it becomes self-supporting, then peel off the self-supporting film from the metal drum or metal belt, then imidize and evaporate and remove volatile components such as solvent Thus, a polyimide film can be manufactured.

[0011] Aromatic tetracarboxylic acids above, preferably, 3,3 ^{', 4,4'} - biphenyltetracarboxylic acid or dianhydride, or the carbon number of the acid 1
Lower alcohol esterified product of 5, 2,3,3 ^' , 4 ^'
-Biphenyltetracarboxylic acid or its acid dianhydride,
Alternatively, an aromatic tetracarboxylic acid containing a biphenyltetracarboxylic acid such as a lower alcohol ester having 1 to 5 carbon atoms, preferably 50 mol% or more, particularly 60 mol% or more, based on all tetracarboxylic acid components. Acids are preferred. In particular, 3,3 ^' , 4,
When an aromatic tetracarboxylic acid containing 50 mol% or more, particularly preferably 60 mol% or more of ^4' -biphenyltetracarboxylic acid or its acid dianhydride is used, the modulus of elasticity and chemical resistance of the polyimide film finally obtained are used. It is preferable because it is excellent in such points.

As the aromatic tetracarboxylic acid component, in addition to biphenyltetracarboxylic acids, pyromellitic acid or its acid dianhydride, benzophenonetetracarboxylic acid or its acid dianhydride, bis (3,4-dicarboxylic acid) (Carboxyphenyl) methane or its acid dianhydride, 2,2
-Bis (3,4-dicarboxyphenyl) propane or an acid dianhydride thereof, bis (3,4-dicarboxyphenyl) sulfone or an acid dianhydride thereof, or a lower thereof having 1 to 5 carbon atoms Alcohol esters can be used.

The aromatic diamine component is, for example, p
-Or m-phenylenediamine, 3,5-diaminotoluene, phenylenediamines such as 2,5-diaminotoluene, preferably with respect to the wholly aromatic diamine component,
An aromatic diamine component containing at least 50 mol%, particularly at least 60 mol%, and more preferably at least 70 mol% can be suitably mentioned. In particular, an aromatic diamine component containing p-phenylenediamine at a content of 60 mol% or more, particularly 70 mol% or more, can be suitably mentioned. p
Use of an aromatic diamine containing phenylenediamine in an amount of 50 mol% or more is preferable because the polyimide film finally obtained is excellent in heat resistance, elastic modulus, and the like.

Further, as the aromatic diamine component, in addition to 4,4-phenylenediamines ^'- diamino diphenyl ether - ether, ^3,4' - diaminodiphenyl et - ether,
3,3 ^'- diaminodiphenyl et - diamino diphenyl ether, such as ether - ethers, ^4,4' - diaminodiphenylmethane, 4,4 ^'- diaminodiphenyl propane, 4,
4 ^'- diamino diphenyl sulfone, ^4,4' - can be used like diaminodiphenyl sulfide.

The above-mentioned aromatic polyamic acid is a polyimide precursor obtained by polymerizing an aromatic tetracarboxylic acid component and an aromatic diamine component at a low temperature of about 10 to 90 ° C. as described above. Logarithmic viscosity (measuring temperature: 30 ° C., concentration: 0.5 g / 100 ml)
Solution, solvent: N-methyl-2-pyrrolidone)
7, especially about 0.2 to 5 and about 2 to about 2 in the organic polar solvent.
It is preferred that the polymer is uniformly dissolved at a concentration of 50% by weight, especially 5 to 40% by weight. Logarithmic viscosity = natural logarithm (solution viscosity / solvent viscosity) / concentration of solution

The above-mentioned organic polar solvent may be any as long as it can uniformly dissolve the above-mentioned aromatic polyamic acid. For example, N, N-dimethylformamide, N, N
N, such as -diethylformamide, N, N-diethylacetamide, N, N-dimethylmethoxyacetamide
Examples thereof include N-di-lower alkylcarboxamides, N-methyl-2-pyrrolidone, dimethylsulfoxide, diethylsulfoxide, dimethylsulfone, diethylsulfone, and hexamethylsulfonamide.

In the polyimide film used in the present invention, for example, approximately equimolar amounts of the above-mentioned aromatic tetracarboxylic acid component and aromatic diamine component are dissolved in an organic polar solvent in about 1 mol.
An aromatic polyamic acid solution in which a high molecular weight aromatic polyamic acid obtained by polymerization at a low temperature of 00 ° C. or less is uniformly dissolved in an organic polar solvent at a concentration of about 2 to 50% by weight is formed into a film. A liquid thin film is formed on a support at a casting temperature of about 160 ° C. or less, and the thin film is dried on a support at a drying temperature of about 150 ° C. for about 0.1 to 1 hour. A self-supporting solidified film having a thickness of preferably 9 to 200 μm, which is formed by a film forming method such as a solution casting method for drying, is obtained by heating to imidize and remove the solvent.

The polyimide film used in the present invention is prepared by adding substantially equimolar amounts of the above-mentioned aromatic tetracarboxylic acid component and aromatic diamine component to the above-mentioned solvent at about 100 ° C.
A tertiary amine compound such as pyridine or β-picoline or a chemical conversion agent such as acetic anhydride is added to a high molecular weight aromatic polyamic acid solution obtained by polymerization at a low temperature as described below, and mixed uniformly. The composition obtained as above is preferably used as a film-forming dope solution and cast at a casting temperature of about 150 ° C. or less on a support surface to form a liquid thin film, preferably a film-forming method. A self-supporting solidified film having a thickness of 9 to 200 μm is obtained by heat treatment. A polyimide film having a thickness of 10 to 125 μm is preferably used. The obtained polyimide film may be further processed by plasma treatment or corona treatment if necessary.

The above-mentioned dope solution for producing a polyimide film used in the present invention is preferably one containing a phosphorus-containing compound and a fine inorganic filler. Although there is no particular limitation on the phosphorus compound, for example, monostearyl phosphate, monocaproyl phosphate, monooctyl phosphate, monolauryl phosphate, monomyristyl phosphate,
Phosphate esters such as dioctyl phosphate and distearyl phosphate, and amine salts of these phosphates are preferable, and colloidal silica is preferable as the inorganic filler. The amount of these components is such that the phosphorus compound is 0.01 to 1 part by weight per 100 parts by weight of the aromatic polyamic acid polymer.
It is preferable that the amount by weight of the inorganic filler is 0.02 to 6 parts by weight.

The above-mentioned polyimide film used in the present invention is obtained by heat-treating a self-supporting solidified film preferably at a temperature of 100 to 400 ° C. for about 0.2 to 5 hours to form the film. Preferably, the polyamic acid is imidized so that substantially no amide-acid bond is present, and is produced by evaporating and removing volatile components such as the solvent from the film.

The above heat treatment is carried out by a first heat treatment at a relatively low temperature of about 100 to 170 ° C. for about 1 to 30 minutes, and then by a second heat treatment at a temperature of 170 to 220 ° C. for about 1 to 30 minutes. And about 1-30 at high temperature of 220-400 ° C
It is preferable to carry out stepwise so as to perform the third heat treatment for minutes. If necessary, a fourth high-temperature heat treatment may be performed at a high temperature of 400 to 600 ° C. Further, in the continuous heat treatment at 250 ° C. or more, it is preferable to perform the heat treatment using a pin tenter, a clip, a frame, or the like. By this high-temperature heat treatment, the content of the volatile component is reduced to 0.4% (% by weight) or less, particularly 0.3% or less when the film thickness is 100 μm or less.
Even when the thickness of the film is larger than 100 μm, 1.1
% Or less, particularly preferably 0.9% or less, so that there is no variation in the adhesive strength of the laminated body, and the dimensional accuracy and workability are improved.

The content of the volatile component in the polyimide film is calculated by the following formula. Volatile component (% by weight) = [(W ₀ −W) / W ₀ ] × 10
0 W ₀ : weight after drying in air at 150 ° C. × 10 minutes (sample: 1
00 × 100 mm ² ) W: Weight after drying in air at 450 ° C. × 20 minutes (sample: 1)
00 × 100mm ² )

The polyimide film with an adhesive according to the present invention comprises a polyimide film having a thickness of 5 to 125 μm having an elastic modulus of 400 kg / mm ² or more and an adhesive having a thickness of 4 to 60 μm provided on one surface thereof. A polyimide film with an adhesive, wherein X defined by the following formula is 0.7 or more, preferably 0.7 or more and 4.1 or less. X = (T1 ² × E1) / (T2 ² × E2 or × 10 ² ) [However, T1: thickness (μm) of polyimide film, E
1: Elastic modulus (kg / mm ² ) of polyimide film, T
2: thickness of adhesive after curing (μm), E2: modulus of elasticity of adhesive after curing (kg / mm ² )] If X defined by the above formula is smaller than 0.7, polyimide with adhesive Undesirably, the warpage of the film increases.

The polyimide film with an adhesive of the present invention is obtained, for example, by applying a liquid adhesive to the polyimide film and then drying it, or by laminating an adhesive sheet on the polyimide film. In general, the polyimide film provided with the adhesive layer is bonded with a metal foil to the adhesive surface after application and drying of the adhesive or simultaneously with lamination of the polyimide film and the adhesive sheet, and the adhesive is cured. To form a laminate.

In the polyimide film with an adhesive of the present invention, by setting X defined by the above formula to 0.7 or more, the cured adhesive polyimide film, generally a metal foil, is removed by etching over the entire surface. The warpage evaluated by the local radius of the polyimide film and the film made of only the adhesive (cured) can be reduced. That is, the polyimide film with an adhesive of the present invention has a local radius indicating the flatness after curing of preferably 100 mm or more, particularly preferably 110 mm or more, and high flatness, that is, small warpage.

The above-mentioned radius of locality is a value calculated by the method shown in JIS standard C5012 by the following formula. Locality radius = L ² / 8h [L: length of sample (mm), h:
Warp height (mm)]

The adhesive used in the present invention includes epoxy resin, polyamide, acrylic resin, and the like.
A heat-resistant thermosetting adhesive such as a polyimide-based adhesive may be used. The adhesive may be of a solution type, or
Type. The adhesive has a thickness of 4-60μ after solidification
m is preferable.

The polyimide film with an adhesive of the present invention has an adhesive property while maintaining the original heat resistance and mechanical properties of the polyimide film, has less warpage after curing, and has a laminate with a metal foil (usually In the circuit, the warpage is greatly improved as compared with the conventional laminate.

The laminate of the present invention can be obtained by laminating a metal on the adhesive surface of a polyimide film with an adhesive. Examples of the metal foil include metal foils such as electrolytic copper foil, rolled copper foil, and 42 alloy.

The laminate of the present invention has a small warpage, high dimensional accuracy, and is suitably used for applications exposed to a high-temperature working environment. The laminate of the present invention is, for example, FPC, TA
B and the like can be suitably used.

[0031]

Embodiments of the present invention will be described below. In the following description, “parts” indicates “parts by weight”. In each of the following examples, the thickness of the cured adhesive, the thickness of the sample removed by etching the copper foil after curing by laminating copper foil on both sides of the adhesive separately, a thickness measuring instrument (manufactured by Ono Sokki Seisakusho Co., Ltd. And a digital dial gauge DG-751].

Reference Example 1 3,470 parts of N, N-dimethylacetamide
3 ^{', 4,4'} - biphenyl tetracarboxylic acid and anhydrides 294.33 parts p- phenylenediamine 108.14
The resulting mixture was reacted for about 10 hours to obtain a polyamic acid solution. The logarithmic viscosity of this polyamic acid is 2.66,
The viscosity of the solution at 30 ° C. was 3100 poise.

Reference Example 2 N-methyl-2-pyrrolidone contained 1980 parts of 3,3 ^' ,
4,4 ^'- biphenyltetracarboxylic acid dianhydride 14
7.2 parts, 100.1 parts of pyromellitic dianhydride, p- phenylenediamine 75.7 parts of 4,4 ^'- diaminodiphenyl et - polyamic acid solution by reacting approximately 6 hours was added 60.6 parts of ether a Obtained. The logarithmic viscosity of the polyamic acid was 2.51, and the viscosity of the solution at 30 ° C. was 2900 poise.

Reference Example 3 In 3037 parts of N, N-dimethylacetamide,
3 ^{', 4,4'} - biphenyltetracarboxylic acid dianhydride 294.22 parts of 4,4 ^'- diaminodiphenyl et - added 200.24 parts of ether is reacted at room temperature for about 10 hours to obtain a polyamic acid solution . The logarithmic viscosity of this polyamic acid is 2.71, and the viscosity at 30 ° C. of the solution is 2600.
Poise.

Reference Example 4 4,4 ^'in 2570 parts of N, N-dimethylacetamide
After adding 200.24 parts of -diaminodiphenyl ether, add 218.12 parts of pyromellitic dianhydride and add about 6
The reaction was carried out for an hour to obtain a polyamic acid solution. The logarithmic viscosity of this polyamic acid was 1.60, and the viscosity at 30 ° C. of the solution was 300 poise.

Example 1 To 100 parts of the polyamic acid polymer prepared in Reference Example 1, 0.1 part of monostearyl phosphate triethanolamine salt and 0.5 part of colloidal silica (silica having an average particle diameter of 75 nm) were used. Then, the mixture was stirred at room temperature (25 ° C.) for 6 hours to obtain a polyamic acid composition. The composition was cast and applied on a stainless steel belt.
After drying at 20 ° C. for 10 minutes, the film was peeled off from the stainless steel belt surface to obtain a self-supporting film. The resulting self-supporting film is gripped with a pin tenter and heated at 150 ° C. for 5 minutes, then heated to 200 ° C., heated at that temperature for 7 minutes, heat-treated at that temperature for 7 minutes, and further heated to 250 ° C. The temperature was raised for 9 minutes, and finally the temperature was raised to 450 ° C., followed by a heat treatment at that temperature for 7 minutes to imidize the polymer and dry the film to obtain a polyimide film having a thickness of 125 μm. Manufactured. The tensile modulus of this polyimide film was 780 kg / mm ² , and the content (% by weight) of volatile components was 0.7%.

Between the polyimide film (belt surface) and the electrolytic copper foil (35 μm), a sheet-like polyimide adhesive (thickness after curing is 20 μm, weight of polyimide siloxane, phenol novolak resin and epoxy resin) A composition having a ratio of 5: 2: 3 and a tensile modulus of the cured adhesive of 220 kg / mm ² ) were sandwiched between the laminates at 130 ° C.
(Using a roll) to form a three-layer body. This three-layer body is 10
The adhesive was cured by heating at 0 ° C. for 2 hours, 120 ° C. for 1 hour, and 180 ° C. for 6 hours to produce a laminate. The adhesive strength of this laminate (180 ° peel strength, ASTM-D-903
by. ) Are shown in Table 1. Further, the copper of the laminate was entirely etched with an aqueous ferric chloride solution (concentration: 30% by weight) to obtain a polyimide film having an adhesive bonded thereto. The radius of localization was measured.

The polyimide film is slit into a tape having a width of 35 mm, and a 26 mm-width tape-shaped polyimide adhesive (thickness: 20 μm, polyimide siloxane, phenol novolak resin and epoxy resin) is formed thereon. Of a 5: 2: 3 weight ratio, and a cured adhesive having a tensile modulus of 220 kg / mm ² ) was laminated at 120 ° C. at the center of the polyimide tape (belt surface) to obtain a polyimide tape with an adhesive. -A sample was prepared. A sprocket hole and a device hole are punched on the polyimide tape with the adhesive, and a copper foil (35 μm) is bonded at 130 ° C., and the adhesive is applied at 100 ° C. for 2 hours and at 120 ° C. for 1 hour.
The adhesive was cured by heating at 180 ° C. for 6 hours. Subsequently, two points A and B were marked on the polyimide tape of the copper clad board, and the lengths of the intervals A and B were measured. further,
This copper-clad plate is patterned according to a conventional method, then subjected to etching, washing and drying steps, and then to IL (inner lead).
Circuit) and OL (over lead) etc.
A carrier tape was prepared (maximum operating temperature during the process: 90 ° C.). In this TAB carrier tape, the distance between A and B was measured.

The dimensional change rate was determined using the following equation. The smaller this value is, the smaller the change in dimension is and the better the dimensional accuracy is. Dimensional change rate = [(L ₀ −L) / L ₀ ] × 100 (%) L ₀ : length between A and B before etching L: length between A and B after etching 1 and Table 2.

Example 2 A sheet-like polyimide adhesive (thickness of 20 μm after curing, composition of polyimide siloxane, phenol-novolak resin and epoxy resin, and tensile modulus of elasticity of cured adhesive of 160 kg / mm as an adhesive) ^The procedure was performed in the same manner as in Example 1 except that ² ) was used. The results are summarized in Tables 1 and 2.

Example 3 As a polyimide film, an elastic modulus of 810 kg / mm ² and a volatile component content of 0.1 obtained by changing the thickness of a self-supporting solidified film by reducing the amount of the polyamic acid composition applied by casting. Example 2 was carried out in the same manner as in Example 1 except that a polyimide film having a thickness of 2% and a thickness of 75 μm was used, and an adhesive whose thickness was changed to 10 μm was used as the adhesive. Table 1 summarizes the results
And Table 2.

Example 4 A sheet-like polyimide-based adhesive (thickness of 20 μm after curing, composition of polyimide siloxane, phenol novolak resin and epoxy resin, and tensile modulus of elasticity of cured adhesive of 160 kg / mm as an adhesive) ^The procedure was performed in the same manner as in Example 3 except that ² ) was used. The results are summarized in Tables 1 and 2.

Example 5 An elastic modulus of 580 kg / mm ² and a volatile component content of 0 obtained in the same manner as in Example 1 except that the polyamic acid solution prepared in Reference Example 2 was used as the polyimide film. Example 9 was carried out in the same manner as in Example 1 except that a 1.9% polyimide film having a thickness of 125 μm was used, and an adhesive whose thickness was changed to 10 μm was used as the adhesive. Table 1 summarizes the results
And Table 2.

Example 6 A sheet-like polyimide adhesive (thickness of 20 μm after curing, composition of polyimide siloxane, phenol novolak resin and epoxy resin, and tensile modulus of elasticity of cured adhesive 160 kg / mm after curing) was used as the adhesive. ^Except using ² ), it carried out similarly to Example 5. The results are summarized in Tables 1 and 2.

Example 7 As a polyimide film, an elastic modulus of 580 kg / mm ² and a volatile component content of 0.1 obtained by changing the thickness of a self-supporting solidified film by reducing the amount of the polyamic acid composition applied by casting. Example 6 was carried out in the same manner as in Example 6, except that a polyimide film having a thickness of 3% and a thickness of 75 µm was used, and an adhesive whose thickness was changed to 10 µm was used as the adhesive. Table 1 summarizes the results
And Table 2.

Comparative Example 1 A polyimide film having an elastic modulus of 810 kg / mm ² ,
The operation was performed in the same manner as in Example 1 except that a polyimide film having a volatile component content of 0.2% and a thickness of 75 μm was used. The results are summarized in Tables 1 and 2.

Comparative Example 2 Using the polyamic acid solution prepared in Reference Example 3 as a polyimide film, the modulus of elasticity obtained by changing the thickness of the self-supporting solidified film by reducing the amount of the polyamic acid composition applied by casting. Using a polyimide film of 380 kg / mm ² , a volatile component content of 0.5%, and a thickness of 75 μm,
A sheet-like polyimide-based adhesive (thickness of 10 μm after solidification, composition of polyimide siloxane, phenol-novolak resin and epoxy resin, tensile modulus of elasticity of cured adhesive of 160 kg / mm ² ) was used as the adhesive. Was carried out in the same manner as in Example 1. The results are summarized in Tables 1 and 2.

Comparative Example 3 An elastic modulus obtained by using the polyamic acid solution prepared in Reference Example 4 as a polyimide film and changing the thickness of the self-supporting solidified film by reducing the amount of the polyamic acid composition applied by casting. Using a polyimide film of 310 kg / mm ² , a volatile component content of 1.2%, and a thickness of 75 μm,
Other than using a sheet-like polyimide adhesive (thickness 20 μm after curing, composition of polyimide siloxane, phenol novolak resin and epoxy resin, tensile modulus of elasticity of the cured adhesive 80 kg / mm ² ) as the adhesive Is Example 1
Was performed in the same manner as described above. The results are summarized in Tables 1 and 2.

[0049]

[Table 1]

[0050]

[Table 2]

[0051]

Since the present invention is configured as described above, the following effects can be obtained.

The polyimide film with an adhesive of the present invention has high dimensional accuracy in the manufacturing process and small warpage after curing of the adhesive. Therefore, the workability is good, and the positioning when mounting other components is good.

The laminate with the metal foil using the polyimide film with the adhesive has a large adhesive strength within a practical range, and has good alignment when mounting other parts through various manufacturing processes.

Claims (5)

(57) [Claims] 1. A polymer comprising an aromatic tetracarboxylic acid component and an aromatic diamine component and having an elastic modulus of 400 kg /
mm ² or more at a and a polyimide film having a thickness of 5~125μm by, for adhesive thickness 4~60μm provided on one surface thereof, the relationship between each elastic modulus of each and the thickness measured by a contact type measuring method by the following formula A method for producing a polyimide film with an adhesive, characterized by satisfying the condition that X is 0.7 or more. ^{X = (T1 2 × E1)} / (T2 2 × E2 × 10 2) [ where, T1: thickness of the polyimide film (μm), E
1: Elastic modulus (kg / mm ² ) of polyimide film, T
2: thickness of adhesive after curing (μm), E2: elastic modulus of adhesive after curing (kg / mm ² )] 2. The method for producing a polyimide film with an adhesive according to claim 1, wherein the thickness of the adhesive is 4 to 20 μm. 3. The polymer according to claim 1, wherein the aromatic diamine component is p.
2. The method for producing a polyimide film with an adhesive according to claim 1, comprising 50% by mole or more of phenylenediamine and 50% by mole or less of 4,4-diaminodiphenyl ether. 4. The method for producing a polyimide film with an adhesive according to claim 1, wherein X is 0.7 or more and 4.1 or less. 5. A method for producing a laminate, further comprising laminating a metal foil on the adhesive of the polyimide film with the adhesive according to the production method according to claim 1.