JP2000159887A - Polyimide film and its production - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide an excellent polyimide film having high modulus of elasticity, high storage elastic modulus, high extensibility, low coefficient of linear expansion comparable to that of a copper foil, and low coefficient of expansion on absorption of moisture. SOLUTION: The polyimide film is produced from a polyamic acid obtained by reacting p-phenylenebis(trimellitic acid monoester anhydride), oxydiphthalic acid dianhydride, p-phenylenediamine, 4,4'-diaminodiphenyl ether and at least one acid dianhydride selected from the group consisting of pyromellitic dianhydride, 3,3',4,4'-benzophenonetetracarboxylic dianhydride and 3,3',4,4'- biphenyltetracarboxylic dianhydride in an organic solvent.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a polyimide film having a good balance of physical properties and capable of providing low warpage and high dimensional stability in a product bonded to a metal, particularly copper.

[0002]

2. Description of the Related Art Polyimide films have heat resistance, insulation, solvent resistance, low-temperature resistance and the like, and are widely used as components for computers and IC-controlled electric and electronic devices.

In recent years, with the miniaturization and thinning of computers and electric / electronic devices controlled by ICs, wiring boards and ICs have been developed.
Packaging materials are also required to be smaller and thinner. For this reason, the wiring patterns to be applied thereto become finer, and it is necessary that polyimide films used for flexible wiring boards, TAB carrier tapes, and the like have small dimensional changes due to heating, pulling, and moisture absorption. Further, as the thickness of the material is reduced, it is necessary to maintain the “strain” of the entire laminate and to stabilize the processing steps.

In order to satisfy such a need, it is desired that the polyimide film has a small linear expansion coefficient, a high elastic modulus and a high storage elastic modulus, and a low moisture absorption expansion coefficient.

However, when a flexible wiring board or an IC package is manufactured, a polyimide film and a copper foil are laminated and processed.
It is not preferable that the coefficient of linear expansion differs greatly from the coefficient of linear expansion of copper. That is, if the linear expansion coefficient of the polyimide film is significantly different from that of the copper foil, the bonded product is warped, making it difficult to process, and as a result, the overall dimensional accuracy and yield are reduced. Therefore, those having a small difference in linear expansion coefficient from the copper foil are preferable.

Various attempts have been made to obtain a polyimide film having the above characteristics. First, it is widely known that a monomer having a rigid structure, that is, a monomer having high linearity may be used to increase the modulus of elasticity of a polyimide film. However, if a large amount of a monomer having high linearity is used, the coefficient of linear expansion of the film becomes too low, which makes the film unsuitable for use in laminating with a copper foil.

In order to realize a relatively high elastic modulus and not to lower the coefficient of linear expansion too much, a monomer having a relatively rigid structure is produced by a thermal curing method without using a chemical imidizing agent, There is an example in which a method of making the orientation in the plane direction sweet is adopted. However, the heat curing method has disadvantages in that the required heating time is longer than that of the chemical curing method and productivity is poor.

Further, when a rigid and highly linear monomer is used, the flexibility of the film is generally impaired, and there is a possibility that it is difficult to bend, which is one of the advantages of a flexible wiring board or the like. There is.

For applications such as semiconductor packages, it is required that the water absorption is as low as possible from the viewpoint of reliability of the semiconductor, and that the coefficient of hygroscopic expansion is also low from the viewpoint of dimensional stability.

In order to reduce the water absorption and the coefficient of expansion due to moisture absorption, it is effective to reduce the amount of imide groups in the molecular structure. For this reason, a long-chain monomer containing a plurality of bending groups in the main chain is often used. However, this results in a decrease in elastic modulus and an excessive increase in linear expansion coefficient, and sacrifices dimensional stability. In an extreme case, the polymer exhibits a thermoplastic property having a Tg at a low temperature of, for example, 200 ° C. or less, and is not suitable for use as a base film. In addition, when such a linear monomer having a long length is used, there is a problem that packing of a molecular chain becomes difficult, sufficient toughness cannot be exhibited, and in some cases, it becomes difficult to form a film itself. Was.

In general, the value of the storage modulus of a viscoelastic body (including a polyimide film) is lower than the value of the storage modulus at room temperature in the temperature range exceeding Tg (one digit, in some cases, in some cases). It is known that the storage elastic modulus at a temperature usually used for producing a film (for example, 300 ° C. or more and 400 ° C. or less) is extremely small. In some cases, it becomes difficult to produce a flat film without sag due to sagging or the like.

As described above, in order to realize all of the characteristics required of the polyimide film such as a high elastic modulus, a high storage elastic modulus, a low linear expansion coefficient, and a low water absorption, in addition to these characteristics, There are many points to be considered such as workability of the material, and if one of the properties is to be satisfied, there is a problem that other properties are sacrificed, and it is particularly difficult to obtain a polyimide film having all of a plurality of good properties. It was a situation.

[0013]

SUMMARY OF THE INVENTION The present inventors have solved the above problems and have developed a high elastic modulus, a high storage elastic modulus,
We are diligently examining the manufacture of polyimide films suitable for fine-printed flexible printed circuit boards and TAB films, which have all the characteristics of linear expansion coefficient close to copper, sufficient toughness, low water absorption coefficient and low moisture absorption expansion coefficient. As a result, the present invention has been achieved.

[0014]

DISCLOSURE OF THE INVENTION In view of the above-mentioned requirements, the present inventors have found a polyimide film having a specific composition and a method capable of specifically achieving and controlling a high balance of various properties, and a method for producing the same. Was.

The gist of the polyimide film of the present invention is p-phenylenebis (trimellitic acid monoester anhydride), oxydiphthalic dianhydride,
(Pyromellitic dianhydride, 3,3 ′, 4,4′-benzophenonetetracarboxylic dianhydride, 3,3 ′, 4
One selected from the group consisting of 4'-biphenyltetracarboxylic dianhydride), p-phenylenediamine, and 4,4'-diaminodiphenyl ether in an organic solvent. The contents shall be.

In the polyimide film, the above p
-Phenylene bis (trimellitic acid monoester anhydride) is 1 to 90 mol% based on the total acid dianhydride;
Oxydiphthalic dianhydride is 8 to the total acid dianhydride
Mol% to 85 mol% (pyromellitic dianhydride, 3,3 ′, 4,4′-benzophenonetetracarboxylic dianhydride, 3,3 ′, 4,4′-biphenyltetracarboxylic dianhydride). One selected from the group consisting of anhydrides)
Is 2 to 14 mol% based on the total acid dianhydride, and p-
Phenylenediamine is used in an amount of 25 to 90 based on the total diamine.
Mol%, and the content of 4,4′-diaminodiphenyl ether is 10 to 75 mol% based on the total diamine.

In such a polyimide film, 100
The average linear expansion coefficient between ℃ and 200 ℃ is 15-30pp
m, tensile elastic modulus is 4.5 to 8.5 GPa, elongation at break is 20% or more, coefficient of hygroscopic expansion is 10 ppm or less, Tg is 200 ° C or more, and storage elastic modulus at a temperature of 300 ° C or more and 400 ° C or less is 200 MPa. The content is as described above.

The gist of the method for producing a polyimide film of the present invention is to dissolve 4,4′-diaminodiphenyl ether in an organic solvent, and prepare a solution of (pyromellitic dianhydride, 3,3 ′, 4,4 ′). Benzophenone tetracarboxylic dianhydride, one selected from the group consisting of 3,3 ′, 4,4′-biphenyltetracarboxylic dianhydride)
, Followed by p-phenylenediamine, and p-phenylenebis (trimellitic acid monoester anhydride) to the organic solvent solution, followed by oxydiphthalic dianhydride to obtain a polyamic acid polymer. Is subjected to dehydration and ring closure to obtain a polyimide film.

Another aspect of the method for producing a polyimide film of the present invention is that p-phenylenediamine is dissolved in an organic solvent and (pyromellitic dianhydride, 3,
3 ′, 4,4′-benzophenonetetracarboxylic dianhydride, one selected from the group consisting of 3,3 ′, 4,4′-biphenyltetracarboxylic dianhydride), followed by p -Phenylenebis (trimellitic acid monoester anhydride) was added, 4,4'-diaminodiphenyl ether was added to the organic solvent solution, and then oxydiphthalic dianhydride was added to obtain a polyamic acid polymer. It is intended to obtain a polyimide film by dehydration and ring closure using an anhydride and a tertiary amine.

[0020]

BEST MODE FOR CARRYING OUT THE INVENTION Hereinafter, a polyimide film according to the present invention will be described based on an example of an embodiment. In addition, the term "monomer" in the present invention refers to either a diamine or a tetracarboxylic dianhydride of a monomer.

The polyimide film according to the present invention can be produced from a polyamic acid prepared by a polyamic acid synthesis method known to those skilled in the art. Preferably, in the method for producing a polyimide film of the present invention, the dehydration ring closure may be performed in the presence of an imidating agent between an acid anhydride and a tertiary amine.

In the present invention, in order to synthesize a polyamic acid, in particular, p-phenylenebis (trimellitic acid monoester anhydride) having the following structural formula (hereinafter referred to as TMHQ) is used as an acid dianhydride.

[0023]

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And oxydiphthalic dianhydride having the following structural formula (hereinafter referred to as ODPA)

[0025]

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And pyromellitic dianhydride having the following structural formula (hereinafter referred to as PMDA)

[0027]

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And 3,3 ', 4 having the following structural formula:
4'-benzophenonetetracarboxylic dianhydride (hereinafter referred to as BTDA)

[0029]

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And 3,3 ′, 4 having the following structural formula:
4'-biphenyltetracarboxylic dianhydride (hereinafter referred to as B
PDA)

[0031]

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As a diamine, p- having the following structural formula
Phenylenediamine (hereinafter referred to as PDA)

[0033]

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And 4,4'-diaminodiphenyl ether having the following structural formula (hereinafter referred to as ODA)

[0035]

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Is used. The above monomers are dissolved in an organic solvent and polymerized to obtain a polyamic acid that can be used for producing the polyimide film according to the present invention.

In the following, TMHQ has a rod-like structure in combination with PDA, exhibits high elasticity of the film, and is somewhat thermally thermally flexible due to ester bond in the main chain structure. In this case, the coefficient of linear expansion does not significantly decrease as compared with the case where.
The ester bond also has the effect of relaxing the polarization of the imide ring, lowering the water absorption and lowering the water expansion.

However, TMHQ, when combined with PDA, is structurally too hard, still has a low coefficient of linear expansion, and has insufficient toughness. Even when the diaminodiphenyl ether is copolymerized, the linear expansion coefficient is too low and the toughness is insufficient when still trying to obtain a certain or more elastic modulus.

Using ODPA, PDA and diaminodiphenyl ether are polymerized, and a moderately high coefficient of linear expansion which is not inconvenient in combination with a moderately high elastic modulus and copper;
Also, sufficient toughness and the like can be realized. However, the structure of the present invention, in which TMHQ is further copolymerized to lower moisture absorption properties and maintain various properties favorably, is very effective because ODPA alone does not significantly reduce the water absorption rate itself.

Further, (PMDA, BTDA, BPDA
(1) selected from the group consisting of), while maintaining other favorable properties that can be realized by the combination of ODPA and TMHQ, and having a high storage of 200 MPa or more at a temperature of 300 to 400 ° C. The configuration of the present invention, which can newly provide an elastic modulus, is very effective.

As the organic solvent used in the polymerization step of the present invention, various solvents known to those skilled in the art can be used. For example, it is preferable to use a highly polar solvent having high solubility in polyamic acid, but it is also possible to add a poor solvent to these highly polar solvents. Examples of highly polar solvents include:
Amides such as N, N-dimethylformamide, N, N-dimethylacetamide, pyrrolidones such as N-methyl-2-pyrrolidone, phenol, p-chlorophenol,
Examples include phenols such as o-chlorophenol. Examples of poor solvents include toluene, tetrahydrofuran, acetone, methyl ethyl ketone, methanol, ethanol and the like. By mixing these solvents and adjusting the solubility parameter appropriately, the solubility can be enhanced.

The addition amount of the above acid dianhydride and diamine is as follows:
The above-mentioned p-phenylenebis (trimellitic acid monoester anhydride) is in the range of more than 0 to 90 mol%, preferably 1 to 90 mol%, based on the total acid dianhydride, and oxydiphthalic dianhydride is 9 to less than 85 mol%, preferably 8 to 85 mol%, based on the total acid dianhydride;
(Pyromellitic dianhydride, 3,3 ′, 4,4′-benzophenonetetracarboxylic dianhydride, 3,3 ′, 4
One selected from the group consisting of 4′-biphenyltetracarboxylic dianhydride) is in the range of more than 1 to 15 mol%, preferably 2 to 14 mol%, based on the total acid dianhydride
And p-phenylenediamine is 25 to 90 mol% based on the total diamine, and 4,4′-diaminodiphenyl ether is 10 to 75 mol% based on the total diamine.
It is.

The order of addition of each monomer for synthesizing polyamic acid is not particularly limited, and various methods are possible.
In a solvent, dissolve all the diamines, gradually add tetracarboxylic dianhydride to this to adjust the viscosity as an approximately equivalent, and further dissolve the remaining tetracarboxylic dianhydride as it is or in an appropriate solvent. In addition, it is common practice to make equivalence ratios equal, but not limited to this.

Depending on the order of addition, the properties of the film can be finely controlled.

Specifically, ODA and PDA are dissolved in a solvent, and (PMDA, BTDA, BPDA
One selected from the group consisting of
A method of adding HQ followed by ODPA;
Similarly, two kinds of diamines are dissolved in a solvent, and (one selected from the group consisting of PMDA, BTDA, and BPDA) is added thereto, followed by ODPA and T
A method of sequentially adding acid dihydrate in the order of MHQ; or a method of dissolving two diamines in the same manner and adding a mixture of three acid dianhydrides thereto; one of the two diamines Is dissolved in a solvent, and one kind selected from three kinds of acid dianhydrides is added thereto, then another kind of diamine is added, and then another two kinds of acid dianhydrides are added. , Etc. can be raised.

When one kind of diamine is added in a plurality of steps, the variations are further increased, and these allow finer adjustment of various properties.
Particularly, ODA is dissolved in an organic solvent, and (PMD
A selected from the group consisting of A, BTDA, and BPDA
), Followed by PDA, followed by TMHQ, followed by ODPA.
The polyimide film obtained has a higher Tg than the case where the order in which DA is exchanged is adopted, and is thus preferable.

In each case, the total molar amount of the diamine compound and the total molar amount of the acid dianhydride compound are used so as to be substantially the same.

The reason why the term "substantially the same" is used here is that if they are completely the same, the degree of polymerization is excessively increased, and as a result, the solution viscosity is excessively increased and the handling becomes difficult.
Specifically, the ratio of the total molar amount of the diamine compound to the total molar amount of the acid dianhydride compound is in the range of 0.95 to 1.05, preferably 0.98 to 1.02, and is not 1: 1. Is particularly preferred.

The addition ratio of each monomer is not particularly limited, but preferably, TMHQ
Is more than 0 mol% and 90 mol% or less, and ODPA
Is not less than 9 mol% and less than 85 mol%, (PMDA,
One selected from the group consisting of BTDA and BPDA)
Is not less than 1 mol% and less than 15 mol%, and PDA is not less than 25 mol% and not more than 90 mol% in all diamines;
ODA is 10 mol% or more and 75 mol% or less.

Particularly preferably, TMH in all acid dianhydrides is used.
Q is 1 mol% or more and 90 mol% or less, and ODPA
Is not less than 8 mol% and not more than 85 mol%, (PMDA,
One selected from the group consisting of BTDA and BPDA)
Is from 2 mol% to 14 mol%.

Most preferably, TMH in all acid dianhydrides
Q is 5 mol% or more and 50 mol% or less, and ODPA
Is not less than 47 mol% and not more than 81 mol%, and (PMD
A selected from the group consisting of A, BTDA, and BPDA
Is 3 mol% or more and 14 mol% or less, PDA is 50 mol% or more and 90 mol% or less, and ODA is 10 mol% or more and 50 mol% or less in all diamines.

By adding a small amount of a diamine monomer component (an amount of 10 mol% or less of the entire diamine) other than these five types of monomers, it is possible to finely adjust the characteristics of the obtained polyimide film. Although it depends on the monomer used, if the copolymerization is approximately equal to or less than this amount, the moisture absorption properties, thermal properties, and mechanical properties can be maintained at preferable levels.
Examples of the diamine monomer used in a small amount include dimethylbenzidine, 2,2′-bis (4-aminophenoxyphenyl) propane, 4,4′-bis (4-aminophenoxy) biphenyl, and halogen-substituted products such as fluorine. Examples can be given.

The polymerization reaction is not particularly limited as long as it is a temperature generally used for a polyamic acid polymerization reaction.
The temperature is preferably 60 ° C. or lower, more preferably 40 ° C. or lower. When the temperature is high, a ring opening reaction of the acid anhydride group is likely to occur, which may inhibit the polyamic acid generation reaction.

The polymerization reaction is preferably carried out in an inert gas such as nitrogen or argon, but may be carried out under other conditions.

The concentration of the polyamic acid in the solution is 5 to 30.
wt%, more preferably 10 to 25 wt%. If the concentration is lower than this, the solvent increases, and it takes time to dry the film after production. If the concentration is higher than this, the viscosity may increase and processing may be difficult.

The viscosity of the polyamic acid solution is not particularly limited as long as it can process a film.
About 00 to 10000 poise, preferably 500 to 6 poise
000 poise. If the viscosity is too low, the properties of the film are adversely affected, and it is also difficult to stabilize the thickness during processing. On the other hand, if the viscosity is too high, stirring of the solution becomes difficult, and a strong force is required when processing into a film,
It is inconvenient.

The resulting polyamic acid solution is formed into a film, and the polyamic acid is imidized to obtain a polyimide film. In general, the imidation includes a thermal method of dehydration by heating and a chemical method using a dehydrating agent or an imidization catalyst. Any of these methods may be used, and a chemical method and a thermal method may be used in combination. Add dehydrating agent and catalyst and heat,
The chemical method of drying is more efficient than the thermal method and can impart excellent properties to the film. Even when a dehydrating agent or an imidization catalyst is not used, if the five monomers of the present invention are used, it is possible to achieve the same characteristics by a method such as inserting a stretching step in the production process. In view of this, a chemical method is preferable.

The dehydrating agent used in the present invention is, for example, an aliphatic acid anhydride such as acetic anhydride, an aromatic acid anhydride and the like. The catalyst used for imidization is pyridine, α
And tertiary amines such as picoline, β-picoline, γ-picoline, trimethylamine, dimethylaniline, triethylamine and isoquinoline.

For example, examples of chemical methods for imidization are shown below, but the present invention is not limited to these. That is,
A solution obtained by adding a stoichiometric or more dehydrating agent and a catalytic amount of a tertiary amine to the obtained polyamic acid solution is applied to a support plate or PET.
Or a film made of an organic compound, such as a film, a drum, or an endless belt, which is cast or coated into a film.
It is dried at a temperature of 50 ° C. or less for about 5 to 90 minutes to obtain a self-supporting polyamic acid polymer coating film. Next, this is peeled off from the support to fix the end. Then 100 ° C
It is imidized by gradually heating it to about 500 ° C., and after cooling, it is removed from it to obtain a polyimide film.

Examples of the imidization by a thermal method include, but are not limited to, the same steps as in the chemical imidization method described above. That is, the polyamic acid solution is added to the support plate or P
The film may be cast or coated on a support such as a film, a drum or an endless belt made of an organic compound such as ET, and may be subjected to a heat treatment.

In the production of the film, a thermal deterioration inhibitor may be further added to prevent the film from deteriorating during firing. Other additives can be added to prevent the film from deteriorating during the production of the film. Examples of the thermal degradation inhibitor include phosphoric acid-based degradation inhibitors such as triphenyl phosphate, and benzophenones having or not having a substituent. Other additives include simple metals, organometallic compounds, and glass-based fillers.

The polyimide film according to the present invention produced as described above has a high modulus of elasticity, a high modulus of storage, a high elongation at break, and a low linear expansion while having a certain heat resistance and adhesiveness. It is a well-balanced polyimide film having a coefficient, a low hygroscopic expansion coefficient, and each characteristic.

Specifically, the polyimide film according to the present invention has an average linear expansion coefficient of 100 to 200 ° C. of 15 to 30 ppm and a tensile modulus of 4.5 to 8.5 GP.
a, elongation at break is 20% or more, and coefficient of hygroscopic expansion is 10p
pm or less, Tg is 200 ° C or more, 300 ° C or more and 400 ° C
The characteristic that the storage elastic modulus at the following temperature is 200 MPa or more can be exhibited.

Here, the characteristics of the polyimide film according to the present invention are measured as follows. That is, the tensile modulus and the elongation at break are respectively AST
It refers to a measured value according to M-D882. The average linear expansion coefficient is obtained by measuring the value at a temperature of 100 ° C. to 200 ° C. using TMA120C manufactured by Seiko Denshi Kogyo Co., Ltd., at a rate of 10 ° C. per minute in the presence of nitrogen. . The coefficient of hygroscopic expansion is adjusted under the condition that a minimum load is applied so that the polyimide film does not sag (approximately 3 g for a sample of 5 mm × 20 mm). The dimensions are measured, then the humidity is adjusted to 90 RH%, and after the saturated moisture absorption, the dimensions are measured, and the dimensional change rate per 1% relative humidity difference is determined from both results. The glass transition temperature (Tg) was measured using a dynamic viscoelasticity measuring device (DMS20 manufactured by Seiko Instruments Inc.).
Measurement is carried out in the tensile mode using 0) while the temperature is raised at a rate of 3 ° C./min.

[0065]

EXAMPLES The present invention will be described in more detail with reference to the following examples, but the present invention is not limited to these examples.

Example 1 33.4 g (approximately 37.5 mol% of the total diamine) of ODA was dissolved in 780 g of dimethylacetamide in an ice bath in a nitrogen atmosphere.
3.9 g (about 4 mol% in total acid dianhydride) of PMDA
Was dissolved in 30.0 g (about 62.5 mol of the total diamine).
1%) of PDA was dissolved therein, and 63.1 g of TMHQ was added thereto.
(About 31 mol% in the total acid dianhydride) is gradually added, and the mixture is stirred and reacted well. Subsequently, 89.6 g of ODPA (about 65 mol% in the total acid dianhydride) is gradually added, and the measurement is performed at 23 ° C. This gave a polyamic acid solution of about 2500 poise.

100 g of this polyamic acid solution was cooled to about 0 ° C., and 13.5 g of acetic anhydride and 4.1 g of isoquinoline were added thereto, and the mixture was stirred uniformly and fired on a SUS plate to a thickness of 50 μm. It was cast to a predetermined thickness as described above and dried with hot air at 125 ° C. for 5 minutes. Thereafter, the film was peeled off from the SUS plate, and this was fixed in a state where four pieces were fixed.
1.5 minutes at 70 ° C, 1.5 minutes at 250 ° C, 3 at 350 ° C
For 3 minutes at 430 ° C. to obtain a polyimide film. Table 1 shows the results of measuring the tensile modulus, elongation at break, linear expansion coefficient, coefficient of hygroscopic expansion, Tg, and storage modulus at 350 ° C. of this film.

Example 2 33.6 g (approximately 37.5 mol% of the total diamine) of ODA was dissolved in 780 g of dimethylacetamide in an ice bath in a nitrogen atmosphere.
7.8 g (about 8 mol% in total acid dianhydride) of PMDA
Was dissolved in 30.3 g (about 62.5 mol of the total diamine).
1%) of PDA was dissolved therein, and 63.6 g of TMHQ was added thereto.
(About 31 mol% in the total acid dianhydride) was gradually added, and the mixture was stirred well and reacted. Subsequently, 84.7 g of ODPA (about 61 mol% in the total acid dianhydride) was gradually added, and the measurement was performed at 23 ° C. This gave a polyamic acid solution of about 2500 poise.

This polyamic acid solution was processed in the same manner as in Example 1 to obtain a polyimide film. A characteristic test was performed in the same manner as in Example 1. Table 1 shows the results.

Example 3 33.9 g (approximately 37.5 mol% of the total diamine) of ODA was dissolved in 780 g of dimethylacetamide in an ice bath in a nitrogen-substituted atmosphere.
1.8 g of PMD (about 12 mol% in total acid dianhydride)
A in 30.5 g (about 62.5 m in total diamine)
ol%) of PDA, and 64.1 g of TMHQ was added thereto.
(Approximately 31 mol% in the total acid dianhydride) was gradually added, and the mixture was stirred and reacted well. Subsequently, 79.8 g of ODPA (approximately 57 mol% in the total acid dianhydride) was gradually added, and the measurement was performed at 23 ° C. This gave a polyamic acid solution of about 2500 poise.

This polyamic acid solution was processed in the same manner as in Example 1 to obtain a polyimide film. A characteristic test was performed in the same manner as in Example 1. Table 1 shows the results.

Example 4 33.1 g (approximately 37.5 mol% of the total diamine) of ODA was dissolved in 780 g of dimethylacetamide in an ice bath in a nitrogen-substituted atmosphere.
7.1 g (about 5 mol% in total acid dianhydride) of BTDA
Was dissolved and 29.8 g (about 62.5 mo in total diamine) was dissolved.
1%) of PDA, and 62.6 g of TMHQ was added thereto.
(Approximately 31 mol% in total acid dianhydride) is added slowly, and the mixture is stirred well to cause a reaction. Subsequently, 87.5 g of ODPA (approximately 64 mol% in total acid dianhydride) is gradually added, and measurement is performed at 23 ° C. This gave a polyamic acid solution of about 2500 poise.

This polyamic acid solution was processed in the same manner as in Example 1 to obtain a polyimide film. A characteristic test was performed in the same manner as in Example 1. Table 1 shows the results.

Example 5 33.0 g (approximately 37.5 mol% of the total diamine) of ODA was dissolved in 780 g of dimethylacetamide in an ice bath in a nitrogen-substituted atmosphere.
7.7 g (about 12.5 mol% in total dianhydride) of B
The TDA was dissolved and 29.7 g (approximately 62.
5 mol%) of PDA was dissolved therein, and TMHQ62.
5 g (approximately 31 mol% in the total acid dianhydride) is gradually added, and the mixture is stirred well and reacted. Then, 77.1 g of ODPA (approximately 56.5 mol% in the total acid dianhydride) is gradually added, and
As a result of measurement at 3 ° C., a polyamic acid solution of about 2500 poise was obtained.

This polyamic acid solution was processed in the same manner as in Example 1 to obtain a polyimide film. A characteristic test was performed in the same manner as in Example 1. Table 1 shows the results.

(Example 6) Polymerization was carried out in the same manner as in Example 5 except that the order of addition of ODA and PDA was reversed, and a polyimide film was produced in the same manner and subjected to a property test. Table 1 shows the results.

[0077]

[Table 1]

Example 7 29.7 g (approximately 62.5 mol% of the total diamine) of PDA was dissolved in 780 g of dimethylacetamide in an ice bath in a nitrogen atmosphere.
7.7 g (about 12.5 mol% in total dianhydride) of B
TDA was dissolved, 62.5 g of TMHQ (about 31 mol% in the total acid dianhydride) was gradually added thereto, and the mixture was thoroughly stirred and reacted, and 33.0 g (about 37.5 mol in the total diamine).
%) Of ODA, followed by slow addition of 77.1 g of ODPA (about 56.5 mol% in total acid dianhydride).
As a result of measurement at 3 ° C., a polyamic acid solution of about 2500 poise was obtained. This polyamic acid solution was processed in the same manner as in Example 1 to obtain a polyimide film. A characteristic test was performed in the same manner as in Example 1. Table 1 shows the results.

(Comparative Examples 1 to 4) In the same manner as in Examples,
A method in which all diamine components are dissolved in dimethylacetamide, and then an acid dianhydride is added.
The polymerization reaction was carried out so as to obtain 0% and a viscosity of 2500 poise. Table 2 shows the components and their mol%. A polyimide film was obtained using these polyamic acid solutions in the same manner as in the examples, and the properties were measured. Table 2 shows the results.

[0080]

[Table 2]

[0081]

As described above, the polyimide film of the present invention has excellent moisture absorbing properties which are not found in the conventional base polyimide film,
In particular, it has low hygroscopic expansion, high elasticity and high storage elasticity, but does not fall below the coefficient of linear expansion of copper. Therefore, when used as a copper-clad substrate or TAB tape, it exhibits extremely excellent warpage characteristics. it can. The polyimide film of the present invention is excellent in flexibility and heat resistance and does not impair the characteristics required as a base polyimide film, so that it can be used for electronic devices that are increasingly miniaturized.

 ──────────────────────────────────────────────────続 き Continued on the front page F term (reference) 4F071 AA60 AF15Y AF20Y AF21Y AF62Y AH12 AH13 BA01 BB02 BB07 BC01 BC10 4J043 PA06 QB26 QB31 RA34 RA36 SA06 SB03 TA14 TA22 TB04 UA122 UA131 UA132 UA142 UB121 ZA32 XA32 XB XA XB XA XA ZB11

Claims (5)

[Claims] 1. p-phenylenebis (trimellitic acid monoester anhydride) and oxydiphthalic dianhydride;
p-phenylenediamine, 4,4′-diaminodiphenyl ether, and (pyromellitic dianhydride,
3,3 ', 4,4'-benzophenonetetracarboxylic dianhydride and one selected from the group consisting of 3,3', 4,4'-biphenyltetracarboxylic dianhydride) A polyimide film produced from a polyamic acid obtained by reacting various kinds of monomers in an organic solvent. 2. In a polyimide film produced from the polyamic acid, the amount of the monomer added is p-
Phenylene bis (trimellitic acid monoester anhydride)
Is 1 to 90 mol% based on the total acid dianhydride, and oxydiphthalic dianhydride is 8 to 8 mol% based on the total acid dianhydride.
5 mol%, (pyromellitic dianhydride, 3,
3 ′, 4,4′-benzophenonetetracarboxylic dianhydride and one selected from the group consisting of 3,3 ′, 4,4′-biphenyltetracarboxylic dianhydride) are all acid dianhydrides 2 to 14 mol%, based on the total diamine, 25 to 90 mol% of p-phenylenediamine, and 10 to 75 mol% of 4,4′-diaminodiphenylether relative to the total diamine. The polyimide film according to claim 1, wherein: 3. The polyimide film according to claim 1, which has an average linear expansion coefficient of 100 to 200 ° C. of 15 to 30 ppm, a tensile modulus of 4.5 to 8.5 GPa, Elongation at break of 20% or more, coefficient of hygroscopic expansion of 10 ppm or less, Tg of 200 ° C. or more, 3
The storage elastic modulus at a temperature between 00 ° C and 400 ° C is 2
A polyimide film having a pressure of at least 00 MPa. 4. A method of dissolving 4,4′-diaminodiphenyl ether in an organic solvent, wherein (pyromellitic dianhydride,
3,3 ', 4,4'-benzophenonetetracarboxylic dianhydride, one selected from the group consisting of 3,3', 4,4'-biphenyltetracarboxylic dianhydride), followed by p-Phenylenediamine was added, p-phenylenebis (trimellitic acid monoester anhydride) was added to the organic solvent solution, and then oxydiphthalic dianhydride was added to obtain a polyamic acid polymer. And a tertiary amine to obtain a polyimide film by dehydration and ring closure. 5. A method of dissolving p-phenylenediamine in an organic solvent, wherein (pyromellitic dianhydride, 3,3 ′, 4,
4'-benzophenonetetracarboxylic dianhydride, 3,
One selected from the group consisting of 3 ′, 4,4′-biphenyltetracarboxylic dianhydride), followed by p-
Phenylene bis (trimellitic acid monoester anhydride)
, And 4,4′-diaminodiphenyl ether are added to the organic solvent solution, and then oxydiphthalic dianhydride is added. The resulting polyamic acid polymer is dehydrated using an acid anhydride and a tertiary amine. A method for producing a polyimide film, comprising closing a ring to obtain a polyimide film.