JPH10226751A - Improved polyimide resin composition and heat-resistant resin film produced therefrom - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain a polyimide resin compsn. greatly improved in thermal or electrical conductivity without great detriment to the properties, such as mechanical properties and clarity, inherent in a polyimide resin and without changing the external appearance by dispersing a specified amt. of a solid additive selected from among a synthetic clay mineral, a synthetic mica, and glass beads in a polyimide resin. SOLUTION: This compsn. is prepd. by dispersing a solid additive selected from among a synthetic clay mineral, a synthetic mica, and glass beads, usually in an amt. of 5-50wt.%, in a polyimide resin. A film obtd. from the compsn. contg. the additive in a content of 5-25wt.% has such a high clarity that its relative total light transmission is 50% or higher, and a film obtd. from the compsn. contg. the additive in a content of 5-20wt.% has a thermal conductivity of 0.25W/mK or higher in addition to a relative total light transmission of 50% or higher.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

[0001] The present invention relates to an improved polyimide resin composition and a heat-resistant resin film comprising the same. Specifically, the polyimide resin, the inherent mechanical properties, or without significantly impairing excellent properties such as transparency, thermal conductivity, or a polyimide resin composition having improved conductivity and a heat-resistant resin film comprising the same .

[0002]

2. Description of the Related Art Heat-resistant resins, especially polyimide resins,
Utilizing its excellent properties such as heat resistance, chemical resistance, and electrical insulation, it is widely used in shapes such as films, tubes, and molded articles. For example, a flexible printed wiring board (hereinafter abbreviated as FPC) or a TA
It is used in various applications, such as base materials of B, insulating coatings such as electric wires, and not only films but also sheets and tubes in parts of OA equipment such as copying machines. In recent years, it has been used in various applications as an adhesive or the like by utilizing its characteristics even in the vicinity of a semiconductor.

However, around FPCs and semiconductors,
With the recent high-density packaging, the problem of heat radiation of the resin used as the base material and the insulating film and the problem of charging of the resin itself have become apparent. Specifically, heat storage occurs due to the use of a resin film that originally has poor heat dissipation, reducing the reliability of the electronic device itself. In a copying machine, etc., precise printing cannot be performed due to toner scattering due to electrification, etc. There was a problem. In addition, the use of a heat-resistant resin which does not originally have conductivity has a problem that the device itself is charged with static electricity or the like, thereby impairing the electrical reliability of the electronic device itself.

[0004] In order to solve these problems, measures have been taken such as forming a thin metal film such as aluminum having excellent thermal conductivity on a resin surface. This method has a problem that a large increase in manufacturing cost is caused. Although proposals have been made to mix fillers having excellent electrical conductivity and thermal conductivity such as carbon black, problems such as a significant change in the appearance (particularly color tone) of the film itself arise.

[0005] Further, in applications such as IC packages around semiconductors, it is necessary to solve the process problems such as the necessity of transparency as a product itself and the fact that defects cannot be found in the inspection process after using the film. Need transparency.

For example, in the case of TAB, a polyimide film is often used as a base material. The bonding between the TAB tape and the IC chip is performed by heating the adhesive via polyimide, which is the base material of the TAB, and pressing the adhesive on the IC chip.
While the thermal conductivity of the polyimide film itself is required, transparency is also required at the same time because it is necessary to finally perform positioning and the like from the polyimide film side. A film having both of these characteristics is strongly demanded by the industry.

For this reason, it has been proposed to mix a filler having excellent thermal conductivity such as carbon black. However, when carbon black is used, the transparency of the film itself is greatly impaired, and the film is substantially opaque. There is a problem that only a proper film can be obtained.

[0008]

In order to solve the above-mentioned conventional problems, the inventors of the present invention have made intensive studies on the addition of various fillers, and found that a specific filler is dispersed and contained in a polyimide resin. Thereby, various properties inherent to the polyimide resin, such as mechanical properties, without significantly impairing the transparency and the like, and without significantly changing the appearance,
The present inventors have found the surprising fact that thermal conductivity, or conductivity, is greatly improved, and arrived at the present invention.

[0009]

SUMMARY OF THE INVENTION The gist of the improved polyimide resin composition according to the present invention for attaining this object is that a polyimide resin comprises a synthetic clay mineral, synthetic mica, and glass beads. At least one of solid additives selected from the group consisting of:

In addition, the thermal conductivity is at least 0.25 W / mK.

Further, the polyimide resin composition has a relative total light transmittance of 50% or more.

[0012] At least one of solid additives selected from the group consisting of synthetic clay minerals, synthetic mica, and glass beads.
The seed is contained in the polyimide resin composition in an amount of 5% by weight or more.

Further, the polyimide resin composition contains 5 to 50% by weight of a solid additive selected from the group consisting of synthetic clay minerals, synthetic mica, and glass beads.

Furthermore, the polyimide resin composition contains 5 to 20% by weight of a solid additive selected from the group consisting of synthetic clay minerals, synthetic mica, and glass beads.

The synthetic clay mineral has a particle size of 20 μm.
The following powders are to be hydrophilic or lipophilic synthetic clay minerals.

Further, the synthetic clay mineral is swellable in water or an organic solvent.

Further, the synthetic mica is a powder having a particle size of 20 μm or less, and is a hydrophilic or lipophilic synthetic mica.

Further, the synthetic mica is swellable in water or an organic solvent.

The glass beads have a particle diameter of 20 μm.
It is in the following powder.

The gist of the heat-resistant resin film according to the present invention resides in that the heat-resistant resin film comprises the improved polyimide resin composition.

[0021]

BEST MODE FOR CARRYING OUT THE INVENTION The improved polyimide resin and the heat-resistant resin film comprising the same according to the present invention can be used without significantly impairing various properties inherent to the polyimide resin, such as mechanical properties, transparency, etc. Has a feature that the thermal conductivity or the conductivity is greatly improved without largely changing. Specifically, the above-mentioned improved polyimide resin composition and a heat-resistant resin film comprising the same can be obtained by dispersing and containing a specific filler in the polyimide resin.

Hereinafter, a method for producing the improved polyimide resin composition according to the present invention will be described in detail. The improved polyimide resin composition according to the present invention is constituted by dispersing and containing at least one solid additive selected from the group consisting of a synthetic clay mineral, synthetic mica, and glass beads in a polyimide resin. However, the term "polyimide resin" as used herein refers to polyimide in a broad sense, and examples thereof include polyimide, polyamide imide, polyether imide, and polyester imide, and are not limited to non-thermoplastic, thermoplastic, and thermosetting properties. That is, the molecular structure of the polyimide does not matter.
As an example, preferably, the following general structural formula (1):

[0023]

Embedded image

The present invention is applied to a polyimide having a repeating unit of

In the formula, R ₁ is a tetravalent organic group, and specifically has at least one aromatic ring, and an aromatic ring is directly bonded to an adjacent carbonyl group to be bonded. It becomes. More specifically,

[0026]

Embedded image

(Wherein X is

[0028]

Embedded image

A divalent functional group selected from the group consisting of R ₄
Is CH ₃ —, Cl—, Br—, F—, CH ₃ O—, and when two or more are substituted, R ₄ may be the same or different. ) Is at least one selected from the group represented by

In the formula, R ₂ is a divalent organic group, specifically having at least one aromatic ring,
An aromatic ring is directly bonded to an adjacent nitrogen atom to be bonded. Further, specifically,

[0031]

Embedded image

(Wherein R ₄ is CH ₃ —, Cl—, Br
-, F-, CH ₃ is O-, if R ₄ is substituted 2 or more, may be identical, or may be different. )
At least one selected from the group represented by

Hereinafter, a method for producing a polyimide resin will be described. The polyimide resin represented by the general formula (1) can be obtained by dehydrating and ring-closing a polyamic acid polymer as a precursor thereof, and the polyamic acid solution is prepared by a conventionally known method using an acid dianhydride and a diamine. It is obtained by polymerizing in a polar organic solvent using substantially equimolar amounts of the components.

First, a method for producing a polyamic acid will be described. First, in an atmosphere of an inert gas such as argon or nitrogen, the compound represented by the general formula (2)

[0035]

Embedded image

(In the formula, R ₁ represents a tetravalent organic group.) From the aromatic tetracarboxylic dianhydride represented by the formula, at least one or more acid dianhydrides are dissolved in an organic solvent. ,
Or, diffuse. Into this solution, at least one or more diamine components represented by the general formula (3) H ₂ N—R ₂ —NH ₂ (3) (wherein R ₂ represents a divalent organic group) are added to the organic solution. It is added in a state of being dissolved in a solvent, being dispersed in a slurry state, or in a solid state, to obtain a solution of a polyamic acid polymer.

At this time, the reaction temperature is from -10 ° C to 50 ° C.
Is preferred. The reaction time is about 30 minutes to 6 hours.

In this reaction, the diamine component may first be diffused or dissolved, and a solution or slurry of a solid or an organic solvent of an acid dianhydride may be added to the solution, contrary to the order of addition. .

In order to maintain the strength of the produced polyimide resin, the number average molecular weight is preferably 10,000 or more. It is often difficult to directly measure the molecular weight of a polyimide polymer. In such a case, inferential measurement is performed by an indirect method. For example, when the polyimide polymer is synthesized from polyamic acid, a value corresponding to the molecular weight of polyamic acid is defined as the molecular weight of polyimide.

The general formula (2)

[0041]

Embedded image

As the aromatic tetracarboxylic dianhydride represented by the general formula (1), essentially various tetracarboxylic dianhydrides can be used. More specifically, from the balance of various properties, the general formula R _{1 in} (2) is

[0043]

Embedded image

(Where X is

[0045]

Embedded image

Is a divalent functional group represented by Where R
₄ is CH ₃ —, Cl—, Br—, F—, CH ₃ O—, and when two or more are substituted, R ₄ may be the same or different. One or more aromatic tetracarboxylic dianhydrides exhibiting a tetravalent organic group represented by the formula (1) can be selected.

As the diamine compound represented by the general formula (3), essentially various diamines can be used. More specifically, from the balance of various properties, the diamine compound represented by the general formula (3) H _{2 N-R 2 -NH 2 (} 3) in R ₂ is of 9

[0048]

Embedded image

(Wherein R ₄ is CH ₃ —, Cl—, Br
—, F—, CH ₃ O—, and when two or more are substituted, R ₄ may be the same or different. One or more diamines which are divalent organic groups represented by the formula (1) can be selected.

The organic solvent used for the polyamic acid formation reaction includes, for example, dimethyl sulfoxide,
Examples include sulfoxide solvents such as diethylsulfoxide, formamide solvents such as N, N-dimethylformamide and N, N-diethylformamide, and acetamide solvents such as N, N-dimethylacetamide and N, N-diethylacetamide. it can. These can be used with only one kind of solvent or a mixed solvent of two or more kinds.
Also, a mixed solvent composed of these polar solvents and a non-solvent of polyamic acid can be used. Examples of non-solvents for polyamic acid include acetone, methanol, ethanol, isopropanol, benzene, methyl cellosolve, toluene, xylene, THF and the like.

Next, in the method for producing polyimide, a dehydrating agent typified by an acid anhydride such as acetic anhydride and a tertiary amine such as picoline, quinoline, isoquinoline and pyridine act on a polyamic acid as a precursor. In addition, it is preferable that the polyimide is converted into polyimide by a so-called chemical curing method using heat treatment in combination. Compared with the so-called thermal curing method in which the imidization reaction proceeds only by heating without the above-mentioned dehydrating agent or the like, the chemical curing method is used in the heat treatment process because the imidization reaction proceeds faster. Since it is completed in a short time, it is excellent in productivity and is an industrially advantageous method. Further, there is an advantage that the obtained polyimide has high mechanical strength and a low linear expansion coefficient.

The method of chemically dehydrating and ring-closing is carried out by adding a dehydrating agent having a stoichiometric amount or more and a catalytic amount of a tertiary amine to the above polyamic acid solution, supporting a support plate, an organic film such as PET, a drum or an endless belt, or the like. A film having a self-supporting property is obtained by casting or coating on a body to form a film, and evaporating the organic solvent.

It is well known that polyimide is equivalent to polyisoimide, but it is also possible to improve solvent solubility by selecting an isoimide structure.
In order to obtain a polyisoimide polymer, the above-mentioned chemical ring-closing agent may be replaced with a diimide such as dicyclohexylcarbodiimide (DCC) and / or a carboxylic acid such as trifluoroacetic acid, and then a reaction similar to the formation of the polyimide may be performed. .

Next, this is further heated and dried for imidization while drying to obtain a polyimide film comprising the polyimide polymer of the present invention. The heating temperature is from 150 ° C to 55 ° C.
Temperatures in the range of 0 ° C are preferred. There is no particular limitation on the rate of temperature rise during heating, but it is preferred that the temperature be heated gradually or continuously or intermittently so that the maximum temperature becomes the above-mentioned temperature. The heating time varies depending on the film thickness and the maximum temperature, but is generally preferably in a range from 10 seconds to 10 minutes after the maximum temperature is reached. When drying and imidizing a film having self-supporting properties by heating and drying, the film having self-supporting properties is peeled off from the support, and the end portions are fixed and heated in that state to provide excellent mechanical properties. A polymer is obtained. A stretching step may be included in the above-described polyimide production process.

Next, the solid additives dispersed and contained in the polyimide resin will be described. This solid additive is at least one selected from the group consisting of synthetic clay minerals, synthetic mica, and glass beads. These may be used alone or in combination of two or more. Hereinafter, description will be made sequentially.

One of the solid additives used in the present invention is a synthetic clay mineral. The synthetic viscosity mineral is preferably in a powder state for uniform dispersion, and preferably has a small particle diameter in order not to cause a large change in appearance. The average particle size is from 0.005 to 20 μm, preferably from 0.
The thickness is from 0.01 to 5 μm, particularly preferably from 0.01 to 1 μm. Among them, the above-mentioned swellable synthetic clay mineral is said to be finely dispersible on the order of nanometers and is preferably used.

The swellable synthetic clay minerals are roughly classified into a type that swells in water (referred to as hydrophilic) and a type that swells in organic solvents and the like (referred to as lipophilic). Good.

Among them, lipophilic synthetic clay minerals are preferred because an organic solvent is used in the process of producing a polyimide resin. As a specific example of this, for example, a trade name “synthetic smectite” manufactured by Corp Chemical Co., Ltd. can be given.

Next, the synthetic mica will be described. The synthetic mica has an average particle diameter of 0.005 to 20 μm, preferably 0.01 to 10 μm, and particularly preferably 0.01 to 5 μm.
m is used. In order not to cause a large change in appearance, a smaller particle size is preferable. Specific examples of such a product include, for example, trade names “Micro Mica” and “Somasif” manufactured by Corp Chemical Co., Ltd.

Although these synthetic mica can be classified into various types, there are hydrophilic and lipophilic ones as well as synthetic clay minerals. Both can be used, but for the same reasons as above,
Lipophilicity is preferred.

Next, the glass beads will be described. The particle size of the glass beads is 0.005 to 20 μm, preferably 0.01 to 10 μm. In order not to cause a large change in appearance, a smaller particle size is preferable. A specific example of such a product is “Toshiba Glass Beads” manufactured by Toshiba Barotini Co., Ltd.

The content of these solid additives with respect to the polyimide resin composition relates to an increase in the thermal conductivity of the polyimide resin composition and a maintenance of transparency.

Specifically, as the content of the above-mentioned solid additive in the polyimide resin composition increases, the thermal conductivity improves. However, when the content is more than 50% by weight, mechanical properties and the like are greatly reduced, and it is difficult to form a film. On the other hand, if the addition amount is less than 5% by weight, the effect of improving conductivity and heat conductivity is lacking. Therefore, for example, if the film shape can be maintained by increasing the film thickness, bonding to an appropriate base film, or the like, the content is 50 if the mechanical strength of the film by the polyimide composition is not required in the molded product. % By weight or more. However, when mechanical strength is required, a polyimide resin composition having excellent thermal conductivity of 0.25 W / mK or more while maintaining mechanical properties is obtained by using the above-mentioned solid additive as a polyimide resin. 5 to 50% by weight, preferably 5% by weight in the composition
The content is preferably 40 to 40% by weight, and those containing 5 to 25% by weight are particularly preferably used. For example, it is suitably used for applications requiring electrical conductivity and thermal conductivity, such as a base substrate and an insulating film used in the vicinity of an FPC or a semiconductor.

In addition, basically, the smaller the content of the above-mentioned solid additive in the polyimide resin composition, the better the transparency of the film. However, when the addition amount is less than 5% by weight, transparency is excellent, but the effect of improving heat conductivity and conductivity is lacking, and problems occur due to charging and heat storage of the resin composition. Also, 3
If the content is more than 0% by weight, the transparency is greatly reduced, and
If the amount exceeds 50% by weight, the transparency is lost. If the amount exceeds 50% by weight, not only the transparency is lost but also the mechanical properties are significantly reduced. Therefore, a resin film obtained from a polyimide resin composition having a content of 5 to 30% by weight, preferably 5 to 25% by weight, has a relative total light transmittance of 50% or more and has good transparency, and is more preferably. The polyimide film of 5 to 20% by weight has a thermal conductivity of 0.25 W / m.
K or more, the heat conductivity can be improved, and an excellent film having a relative total light transmittance of 50% or more and maintaining transparency can be obtained. For example, it is suitably used for applications requiring electrical conductivity, thermal conductivity, and transparency, such as applications such as IC packages around semiconductors and applications for TAB tapes.

When the solid additive content of the polyimide resin composition is 20 to 50% by weight, transparency is not maintained, but conductivity and thermal conductivity are effectively improved.

Even when the solid additive is contained in the polyimide resin composition in an amount of 50% by weight or more,
Although the transparency and the mechanical properties are degraded, the conductivity and the thermal conductivity are improved, so that the present invention can be applied to a molded article using the properties.

The improved polyimide resin composition according to the present invention is characterized in that the solid additive is dispersed and contained in the polyimide resin in a specific range of content. It can be added at any step of the production process of the improved polyimide resin composition.

That is, before the polymerization step of the polyimide resin or its precursor, such as polyamic acid or polyamic acid ester, during the polymerization, or in any step up to molding into a film or a tube, the timing of adding the solid additive is determined. You can choose.

Here, when the solid additive is added, stabilization of the quality such as the mechanical properties of the polyimide resin composition to be produced, conductivity and thermal conductivity to be improved, and appearance failure are not caused. For this purpose, it is important that the additives are uniformly dispersed in the resin without agglomeration. Therefore, at the time of mixing with the resin, it is preferable that the additive is sufficiently dispersed in the medium in advance and then mixed, or that the additive is stirred and mixed in a device capable of obtaining a sufficient mixing effect.

Here, among the above-mentioned solid additives, the above-mentioned swellable synthetic clay mineral itself has a capability of swelling, that is, self-dispersing. Even if it is not used, it can be dispersed well by adding it to the medium with a relatively simple device. For this reason, a special treatment or precautions are required by using a general-purpose equipment in any step before the film forming, using a suspension previously dispersed in a medium and a solution or melt of polyimide or its precursor resin. And uniform dispersion mixing is possible. Of course, the synthetic clay mineral may be added directly without being dispersed in the medium in advance. In any case, not only is the dispersion and mixing method superior, but also the polyimide resin composition obtained tends to have good homogeneity, and furthermore, good quality stability and good appearance.

When the above-obtained polyimide resin and the improved polyimide resin composition containing the above-mentioned solid additives as constituents have thermoplastic properties, they are molded into a film, sheet, tube or the like. Used for various purposes.

When forming into a shape such as a thermoplastic film, a sheet, or a tube, the polyimide resin and the additive are supplied to the molding machine simultaneously or through separate supply ports during extrusion molding or injection molding. Alternatively, it is also possible to form a so-called master batch in which a polyimide resin and a high additive amount are kneaded first, and then supply the master batch product and the polyimide resin to a molding machine to perform molding. In this case, the method for preparing the master batch may use a molding machine such as an extruder, or may be used to uniformly mix the polyimide resin and the additive using a medium such as an organic solvent, and then supply the mixture to the molding machine. You may.

In the case of casting into a film, there are a melt extrusion method, a solution cast method, and a molding method such as extrusion molding and injection molding. In any case, in order to avoid aggregation of additives due to high viscosity. To
A kneading method using a high shear force by a known method is preferably used.

In order to avoid aggregation of the additives, various surface treatments may be performed. A known method such as a physical mechanical method for reducing the specific surface area or a chemical method such as a silane coupling agent treatment can be applied to such a surface treatment.

When the polyimide resin composition is formed into a film shape, it means a film shape in a broad sense, including a thin film having a thickness of several microns to a sheet having a thickness of several hundred μm. Within this thickness range, 10 μm to 150 μm
A film having a thickness of m is suitably used for the insulating layer and the like.

Also, in the case of a tube-like shape, one having a thickness in the range of 10 μm to 150 μm is preferably used.

The improved polyimide resin composition and the heat-resistant resin film comprising the same according to the present invention have a thermal conductivity of 0.25 W / mK or more and / or a relative total light transmittance of at least 0.25 W / mK. Because it is more than 50%
Significant improvements in thermal conductivity or conductivity can be achieved without significantly impairing various properties inherent to the polyimide resin, such as mechanical properties or transparency, and without significantly changing the appearance. Therefore, the present invention is also useful in applications requiring high thermal conductivity or conductivity, such as FPC and high-density mounting around semiconductors, and in fields requiring transparency such as IC packaging.

The embodiments have been described above in order to clarify the usefulness of the improved polyimide resin composition according to the present invention and the heat-resistant resin film comprising the same.
The present invention is not limited thereby, and the present invention is based on the knowledge of those skilled in the art without departing from the gist thereof,
The present invention can be implemented with various improvements, changes, and modifications.

[0079]

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

The thermal conductivity of the improved polyimide resin composition according to the present invention refers to a laser flash method (measuring device; TC-7000 manufactured by Vacuum Riko Co., Ltd., measuring temperature: 25 ° C., atmosphere: in vacuum ( About 1 × 10 ^-2 Tor
The evaluation was performed using the thermal conductivity in the film thickness direction measured by r)).

The conductivity of the present invention is determined by measuring the volume resistivity in the thickness direction of the film (measuring device: S
M-10, measurement conditions; temperature 20 ° C., humidity 60%).

Examples 1 to 21 are examples of the improved polyimide resin composition according to the present invention.

Examples 1 to 4 A DMF solution of a polyamic acid obtained by using 4,4-diaminodiphenyl ether as an aromatic diamine and pyromellitic dianhydride as an aromatic tetracarboxylic dianhydride (solid Minor concentration 1
A 5% solution viscosity of 3,000 poise) was prepared.

On the other hand, a liquid was prepared by dispersing a synthetic clay mineral, synthetic scumite “lipophilic scumite (STN)” (manufactured by Corp Chemical) in DMF (dispersion concentration: 15% by weight).

In a polyamic acid solution, 10.9 g, 21.9 g, 32.8 g, and 54.7 g of the dispersion of the above synthetic scumetite were added to 100 g of the polyamic acid solution.
Was added and kneaded with three rolls.
Before casting the obtained dope into a film, acetic anhydride / isoquinoline was added and mixed in an amount of 20 g / 2.5 g, and then cast on a film.
The film was heat-treated at 1 ° C. for 1 minute to obtain a film having a thickness of 75 μm. Table 1 shows the characteristic values of the obtained film.

[0086]

[Table 1]

(Examples 5 to 8) A liquid was prepared by dispersing and swelling “Somasif (ME-100)” (manufactured by Corp Chemical) in DMF (dispersion concentration: 15% by weight).

A polyamic acid solution prepared in the same manner as in Examples 1 to 4 (solid content: 15%, solution viscosity: 3,000 p
oise), 10.9 g, 21.9 g, and 30.9 g of the dispersion of the synthetic mica were added to 100 g of the polyamic acid solution.
2.8 g and 54.7 g were added, respectively, and 3
It was kneaded with this roll. Before casting the obtained dope into a film, acetic anhydride / isoquinoline was added in an amount of 20 g / 2.
Add 5 g and mix, then cast on film, 10
Heat treatment was performed at 0 ° C./6 minutes, 300 ° C./1 minute, and 450 ° C./2 minutes to obtain a 75 μm thick film. Table 1 shows the characteristic values of the obtained film.

(Examples 9 to 12) A solution was prepared by dispersing and swelling glass beads “Toshiba glass beads (MB-10)% (manufactured by Toshiba Barotini Co., Ltd.)” in DMF (dispersion concentration: 15% by weight).

A polyamic acid solution prepared in the same manner as in Examples 1 to 4 (solid content: 15%, solution viscosity: 3,000 p
oise), a dispersion of the above glass beads was mixed with 10.9 g of a dispersion and 21.9 g of 100 g of a polyamic acid solution.
g, 32.8 g, and 54.7 g were added, respectively, and kneaded with three rolls. Before casting the obtained dope into a film, 20 g of acetic anhydride / isoquinoline was used.
/2.5 g was added and mixed, then cast on a film and heat-treated at 100 ° C. for 6 minutes, 300 ° C. for 1 minute, and 450 ° C. for 2 minutes to obtain a film having a thickness of 75 μm. Table 1 shows the characteristic values of the obtained film.

(Examples 13 to 16) As aromatic diamines, 4,4-diaminodiphenyl ether and paraphenylenediamine were used in a molar ratio of 3: 7. As aromatic tetracarboxylic dianhydride, pyromellitic dianhydride was used. Polyamide acid DMF solution (solid content: 15%, solution viscosity: 3,000 poise) obtained by using 3,3 ', 4,4'-benzophenonetetracarboxylic dianhydride in a molar ratio of 5: 5. A film having a thickness of 75 μm was obtained in the same manner as in Examples 1 to 4, except that the film was not formed. Table 1 shows the characteristic values of the obtained film.

Examples 17 to 20 4.4-diaminodiphenyl ether and paraphenylenediamine were used as aromatic diamines in a molar ratio of 5: 5, and p-phenylenebis (trimellitic acid monoester) was used as aromatic tetracarboxylic dianhydride. NMP solution (solid content: 15%, solution viscosity: 3,000 p)
oise), except that a film having a thickness of 75 μm was obtained in the same manner as in Examples 1 to 4. Table 1 shows the characteristic values of the obtained film.

Example 21 As an aromatic diamine, 2,2
2-bis [4- (4-aminophenoxy) phenyl] propane is converted to 2,2-bis (4-hydroxyphenyl) propanedibenzoate-3, as an aromatic tetracarboxylic dianhydride.
3 ', 4,4'-tetracarboxylic dianhydride (ESDA) and 3,
3 ', 4,4'-Benzophenonetetracarboxylic dianhydride (BTDA) was added at a weight molar ratio of ESDA: BTDA = 5: 5.
A DMF solution of polyamic acid (solid content: 15%, solution viscosity: 3,000 poise) was prepared. To 100 g of this polyamic acid solution, 150 g of DMF,
2.5 g of isoquinoline and 20 g of acetic anhydride were added, and the mixture was stirred for 2 hours under ice cooling. Thereafter, this solution was dripped little by little into methanol stirred at high speed. The filamentous polyimide precipitated in methanol was dried at 150 ° C. for 30 minutes, pulverized by a mixer, and heated at 250 ° C. for 2 minutes to completely perform imidization to obtain a polyimide powder. A filler-mixed resin powder obtained by mixing the ester imide and the glass beads with the proportion of the ester imide being 90% was extruded at 340 ° C. in a cylinder to obtain a tube having a diameter of 20 nm and a film thickness of 75 μm. Table 1 shows the characteristic values of the obtained tubes.

Comparative Example 1 As an aromatic diamine, 4,4-
Synthetic smectite was prepared by using a polyamino acid DMF solution (solid content 15%, solution viscosity 3,000 poise) obtained by using diaminodiphenyl ether as pyromellitic dianhydride as aromatic tetracarboxylic dianhydride. 75 μm in the same manner as in Example 1 except that no
A thick film was obtained. Table 1 shows the characteristic values of the obtained film.
Shown in

Comparative Example 2 As an aromatic diamine, 4,4-
The molar ratio of diaminodiphenyl ether and paraphenylenediamine is 3: 7, and pyromellitic dianhydride and 3,3 ', 4,4'-benzophenyltetracarboxylic dianhydride are used as aromatic tetracarboxylic dianhydrides. Using a polyamic acid DMF solution (solid content 15%, solution viscosity 3,000 poise) obtained at a ratio of 5: 5, a 75 μm thick film was obtained in the same manner as in Example 13 except that synthetic smectite was not added. Was obtained. Table 1 shows the characteristic values of the obtained film.

Examples 22 to 36 are examples of the improved heat-resistant resin film according to the present invention. In addition,
The relative total light transmittance is expressed by the following equation.

[0097]

(Equation 1)

Is represented by

(Examples 22 to 25) A DMF solution of a polyamic acid obtained by using 4,4-diaminodiphenyl ether as an aromatic diamine and pyromellitic dianhydride as an aromatic tetracarboxylic dianhydride (solid Minute concentration 15
% And a solution viscosity of 3,000 poise). Meanwhile D
Synthetic smectite "lipophilic smectite (ST
N) "(manufactured by Coop Chemical Co., Ltd.) was prepared by dispersing and swelling the dispersion (dispersion concentration: 15 wt%).

The above synthetic scumite dispersion was added to a polyamic acid solution, and 5.5 g, 10.9 g and 21.9 g of the dispersion were added to 100 g of the polyamic acid solution, and the mixture was kneaded with three rolls. did. Before casting the obtained dope on a film, 20 g / 2.5 g of acetic anhydride / isoquinoline was added and mixed, then cast on a film, and heat-treated at 100 ° C./10 minutes and 300 ° C./1 minute to 75 μm A thick film was obtained. Table 2 shows the characteristic values of the obtained film.

[0101]

[Table 2]

(Examples 26 to 28) A liquid was prepared by dispersing and swelling synthetic mica somasif (ME-100) (manufactured by Corp Chemical Co., Ltd.) in DMF (dispersion concentration: 15% by weight).

A polyamic acid solution prepared in the same manner as in Examples 22 to 25 (solid content: 15%, solution viscosity: 3,000
0 poise), 5.5 g of a dispersion liquid, 10.9 g of a dispersion liquid of 100 g of a polyamic acid solution,
Each to which 21.9 g was added was adjusted, and kneaded with three rolls. Before casting the resulting dope into a film, 20 g / 2.5 g of acetic anhydride / isoquinoline was added and mixed, and then cast on a film at 100 ° C./6
Heat treatment at 300 ° C for 1 minute, 450 ° C for 2 minutes and 75μ
An m-thick film was obtained. Table 2 shows the characteristic values of the obtained film.

(Examples 29 to 31) A liquid was prepared by dispersing and swelling glass beads "Toshiba glass beads (MB-10)% (manufactured by Toshiba Barotini Co., Ltd.)" in DMF (dispersion concentration: 15% by weight).

A polyamic acid solution prepared in the same manner as in Examples 22 to 25 (solid content: 15%, solution viscosity: 3,000
0 poise), 5.5 g of a dispersion of 10.9 parts per 100 g of a polyamic acid solution.
g and 21.9 g were added, and kneaded with three rolls. Before casting the obtained dope into a film, acetic anhydride / isoquinoline was added and mixed in an amount of 20 g / 2.5 g, and then cast on a film.
6 minutes, heat treated at 300 ° C / 1 minute, 450 ° C / 2 minutes, 75
A μm thick film was obtained. Table 2 shows the characteristic values of the obtained film.

(Examples 31 to 33) 4,4-diaminodiphenyl ether and paraphenylenediamine were used as aromatic diamines in a molar ratio of 3: 7, and pyromellitic dianhydride was used as aromatic tetracarboxylic dianhydride. , 3 ', 4,4'-
Benzophenone tetracarboxylic dianhydride in a molar ratio of 5:
A film having a thickness of 75 μm was obtained in the same manner as in Examples 22 to 25, except that a DMF solution of a polyamic acid (solid content: 15%, solution viscosity: 3,000 poise) obtained as Sample No. 5 was used. Table 2 shows the characteristic values of the obtained film.

(Examples 34 to 36) As an aromatic diamine, 4,4-diaminodiphenyl ether and paraphenylenediamine were used in a molar ratio of 5: 5, and as an aromatic tetracarboxylic dianhydride, p-phenylenebis (trimellitic acid) was used. NMP solution (solid content 15%, solution viscosity 3,000) of polyamic acid obtained using monoester anhydride)
A film having a thickness of 75 μm was obtained in the same manner as in Examples 22 to 25 except that poise was used. Table 2 shows the characteristic values of the obtained film.

Comparative Example 3 As an aromatic diamine, 4,4-
Synthetic smectite was prepared by using a polyamino acid DMF solution (solid content 15%, solution viscosity 3,000 poise) obtained by using diaminodiphenyl ether as pyromellitic dianhydride as aromatic tetracarboxylic dianhydride. 75 μm in the same manner as in Example 22 except that no
An m-thick film was obtained. Table 2 shows the characteristic values of the obtained film.

Comparative Example 4 As an aromatic diamine, 4,4-
The molar ratio of diaminodiphenyl ether and paraphenylenediamine is 3: 7, and pyromellitic dianhydride and 3,3 ', 4,4'-benzophenyltetracarboxylic dianhydride are used as aromatic tetracarboxylic dianhydrides. DMF solution of polyamic acid obtained at a ratio of 5: 5 (solids concentration 15
% And a solution viscosity of 3,000 poise), and a film having a thickness of 75 μm was obtained in the same manner as in Example 31 except that no synthetic smectite was added. Table 2 shows the characteristic values of the obtained film.

[0110]

As described above, when solid additives such as synthetic viscous minerals, synthetic mica and glass beads are added as shown in Examples 1 to 21, the thermal conductivity increases and the volume resistivity decreases. It can be seen that the thermal conductivity and the conductivity were improved. This effect is more remarkable when the amount of the solid additive is large. Further, as shown in Examples 22 to 36, even when a solid additive was added, the total light transmittance did not decrease so much and the thermal conductivity was improved, as compared with the polyimide resin not added. The present invention can be sufficiently applied to fields requiring transparency in addition to conductivity. As described above, the improved polyimide resin and the heat-resistant resin film comprising the same according to the present invention can greatly improve the thermal conductivity and conductivity without significantly impairing the original properties such as mechanical properties and transparency. Accordingly, it is possible to cope with recent high-density packaging such as FPC and IC packaging around semiconductors, and can be suitably used as a base material or an insulating material.

Claims (12)

[Claims] 1. An improved polyimide resin composition characterized in that at least one solid additive selected from the group consisting of synthetic clay minerals, synthetic mica, and glass beads is dispersed and contained in the polyimide resin. . 2. The improved polyimide resin composition according to claim 1, wherein the thermal conductivity is 0.25 W / mK or more. 3. The improved polyimide resin composition according to claim 1, wherein the relative total light transmittance is 50% or more. 4. The polyimide resin composition according to claim 1, wherein at least one of solid additives selected from the group consisting of synthetic clay minerals, synthetic mica, and glass beads is contained in an amount of 5% by weight or more. The improved polyimide resin composition according to claim 3. 5. A polyimide resin composition comprising a solid additive selected from the group consisting of synthetic clay minerals, synthetic mica, and glass beads in an amount of 5 to 50% by weight. Item 6. An improved polyimide resin composition according to any one of Items 4. 6. The polyimide resin composition according to claim 1, wherein a solid additive selected from the group consisting of synthetic clay minerals, synthetic mica, and glass beads is contained in an amount of 5 to 20% by weight. Item 6. An improved polyimide resin composition according to any one of Items 5. 7. The improved synthetic clay mineral according to claim 1, wherein the synthetic clay mineral is a powder having a particle size of 20 μm or less, and is a hydrophilic or lipophilic synthetic clay mineral. Polyimide resin composition. 8. The synthetic clay mineral according to claim 1, wherein said synthetic clay mineral is swellable in water or an organic solvent.
An improved polyimide resin composition according to any one of the above. 9. The improved polyimide according to claim 1, wherein the synthetic mica is a powder having a particle size of 20 μm or less, and is a hydrophilic or lipophilic synthetic mica. Resin composition. 10. The improved polyimide resin composition according to claim 1, wherein the synthetic mica is swellable in water or an organic solvent. 11. The method according to claim 1, wherein the glass beads are powder having a particle size of 20 μm or less.
An improved polyimide resin composition according to any one of the above. 12. A heat-resistant resin film comprising the improved polyimide resin composition according to any one of claims 1 to 11.