JP2002201272A - Process for preparing polyimide composite - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a process for preparing a polyimide composite having an excellent heat resistance, mechanical properties, gas barrier property, dimensional stability, etc. SOLUTION: The process for preparing a polyimide composite comprises a step wherein a diamine component which is the raw material monomer of the polyimide is polymerized with an acid anhydride component in an organic solvent in the presence of an intercalation compound wherein the diamine which is the raw material monomer of the polyimide and an organic onium ion are intercalated within a layered clay mineral to obtain a polyamic acid solution wherein the intercalation compound is dispersed, and a step wherein this polyamic acid is imidized to obtain a polyimide composite.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

The present invention relates to a method for producing a polyimide composite, and more particularly, to a method for producing a polyimide composite having excellent heat resistance, mechanical properties, gas barrier properties, dimensional stability, and the like.

[0002]

2. Description of the Related Art Conventionally, polyimide is excellent in heat resistance, mechanical properties, electrical insulation, chemical resistance, etc., so that flexible printed circuit boards, flat cables,
It is widely used as a material in the manufacture of electric and electronic products such as TAB. However, with the phenomenal development of electronics, the demand for smaller, lighter, more functional, more reliable, and lower cost electronic devices is increasing. Is strongly desired.

[0003] In order to respond to such demands by improving the performance of polyimide materials, an interlayer compound in which a layered clay mineral is used as a host and an ionic substance is intercalated with the host is used in the polyimide at the molecular level. A composite dispersed in the same has been proposed. For example, JP-A-4-3395
According to Japanese Patent Publication No. 5 and JP-A-11-349709,
It has been proposed to disperse an intercalation compound obtained by intercalating a layered viscosity mineral with an organic onium salt such as an alkylammonium ion as a guest in a polyimide to form a polyimide composite. However, in such a polyimide composite, since the guest in the intercalation compound is an organic onium salt that is a low molecular weight compound, even in a polyimide composite in which the intercalation compound is dispersed, improvement of properties such as heat resistance is sufficient. Therefore, the reinforcing effect is not satisfactory. Therefore, if the amount of intercalation of the organic onium salt is suppressed, there is a problem that a complex in which the interlayer compound is completely delaminated cannot be obtained.

[0004]

SUMMARY OF THE INVENTION The inventors of the present invention have conducted intensive studies to solve the above-mentioned problems in improving the performance of polyimide materials, and as a result, diamine, which is a raw material monomer of polyimide, was used as a part of the guest. , While reducing the amount of organic onium salts used as guests, these are intercalated into layered clay minerals to form intercalation compounds,
In the presence of such an interlayer compound, including a diamine as a guest, a polyamic acid is obtained by reacting a diamine component and an acid anhydride component, which are raw material monomers for polyimide,
It has been found that by imidizing this, it is possible to obtain a polyimide composite having significantly improved heat resistance, mechanical properties, gas barrier properties, and the like, and the present invention.

[0005] Accordingly, the present invention provides,
An object of the present invention is to provide a method for producing a polyimide composite having excellent mechanical properties, gas barrier properties, dimensional stability, and the like.

[0006]

According to the present invention, there is provided a diamine component which is a raw material monomer of polyimide in the presence of an interlayer compound obtained by intercalating a diamine which is a raw material monomer of a polyimide and an organic onium ion into a layered clay mineral. And a step of polymerizing the acid anhydride component in an organic solvent to obtain a polyamic acid solution in which the interlayer compound is dispersed, and a step of imidizing the polyamic acid to obtain a polyimide composite. And a method for producing a polyimide composite.

Further, according to the present invention, there is provided a polyimide composite produced by such a method.

[0008]

BEST MODE FOR CARRYING OUT THE INVENTION In the present invention, the first step comprises:
Layered clay mineral intercalated with diamine and organic onium ion, which is a raw material monomer of polyimide, that is, in the presence of an interlayer compound, a diamine component and an acid anhydride component which are raw material monomers of polyimide are polymerized in an organic solvent. And obtaining a polyamic acid solution in which the interlayer compound is dispersed.

Polyimide is a resin obtained by obtaining a polyamic acid by a condensation reaction between a tetracarboxylic dianhydride and a diamine, and subjecting the polyamic acid to an imidization reaction (dehydration reaction). Components include p-phenylenediamine, 4,4'-diaminodiphenylether, 4,4'-diaminodiphenylmethane, 4,4'-bis (4-aminophenoxy) biphenyl,
1,4'-bis (4-aminophenoxy) benzene, 4,4'-
Diaminodiphenyl sulfone and the like can be mentioned.
On the other hand, examples of the acid anhydride component include pyromellitic dianhydride, biphenyltetracarboxylic dianhydride, and benzophenonetetracarboxylic dianhydride.

In order to intercalate a diamine which is a raw material monomer of a polyimide and an organic onium ion (hereinafter, these may be referred to as an organic component) into a layered clay mineral, for example, the layered clay mineral is dissolved in an appropriate solvent. And a solution of the above-mentioned organic component, preferably an aqueous solution, is added thereto, and if necessary, mixed and stirred under heating to obtain exchangeable inorganic ions (typically, sodium ions) of the layered clay mineral. ) Is ion-exchanged with the above organic component. Then
The precipitate thus obtained is filtered off, washed, dried,
By crushing, an intercalation compound obtained by intercalating the above organic component into a layered clay mineral can be obtained as a powder.

In the present invention, as described above, when intercalating a diamine and an organic onium ion into a layered clay mineral, a solvent is preferably used. As this solvent, the dispersibility of the layered clay mineral is good,
Protic solvents such as water and alcohol are preferably used. The above-mentioned organic onium ion and diamine are also used as a solution using the above-mentioned protic solvent such as water and alcohol.

Examples of the organic onium ion include an ammonium ion, a phosphonium ion, a sulfonium ion, and an onium ion derived from a heteroaromatic system.

In particular, in the present invention, it is easy to purify when intercalating into a layered clay mineral,
From the viewpoint of the abundance of the target substance, ammonium ions are preferably used. The ammonium ion is preferably an alkylammonium ion having a main chain composed of a linear or branched carbon chain, but may have a cyclic structure in a part of the main chain.

However, according to the present invention, an alkylammonium ion having 6 to 18 carbon atoms in the main chain is preferred from the viewpoint of the polarity of the organic solvent used during the synthesis of the polyimide.
Specific examples of such alkyl ammonium ions include, for example, hexylamine ion, octylamine ion, decylamine ion, dodecylamine ion, tetradecylamine ion, hexadecylamine ion,
Octadecylamine in and the like can be mentioned.

In order to intercalate the diamine component into the layered clay mineral, a part or all of the amine side chain is protonated with an acid from the viewpoint of solubility in the protic solvent used for the intercalation. Things are used.

In the present invention, the layered clay mineral as a host for forming an interlayer compound using the above organic component as a guest includes smectite-based clay minerals such as montmorillonite, saponite and hectorite, vermiculite, halloysite, and swellable mica. And the like. The cation exchange amount of these layered clay minerals is preferably in the range of 50 to 200 meq / 100 g from the viewpoint of the affinity of the obtained interlayer compound for the solvent or polyimide.

When the exchangeable inorganic ion of the layered clay mineral is ion-exchanged with the diamine component and the organic onium ion, it is preferable to use an equivalent of the cation exchange amount of the layered clay mineral.

According to the present invention, the ratio of the diamine component to the organic onium ion is preferably in the range of 8/2 to 2/8 in terms of molar ratio. When the diamine / organic onium ion molar ratio exceeds 8, the organic onium ions in the organic components to be intercalated become relatively small, and the dispersibility of the intercalation compound obtained by the intercalation in the solvent decreases. I do. On the other hand, when the diamine / organic onium ion molar ratio is smaller than 2, the interaction at the interface between the polyimide and the layered clay mineral is weakened, and a polyimide composite having desired physical properties cannot be obtained.

In the intercalation of the above-mentioned organic component into the layered clay mineral, the exchangeable inorganic ions of the layered clay mineral may be ion-exchanged sequentially with a diamine and an organic onium ion. Ion exchange may be performed simultaneously with a mixture with onium ions.

According to the present invention, the diamine, which is a raw material monomer of polyimide, and the organic onium ion are intercalated into a layered clay mineral to form an interlayer compound, and in the presence of an organic solvent, A diamine as a raw material monomer of the polyimide is polymerized with a tetracarboxylic dianhydride, including a diamine as a guest in the interlayer compound, to obtain a polyamic acid solution.

The organic solvent used for preparing the above polyamic acid solution may be any aprotic polar solvent generally used for the synthesis of polyimide, such as N, N-dimethylacetamide, N-methylpyrrolidone, N, N-methylpyrrolidone. Examples include, but are not limited to, N-dimethylformamide, dimethyl sulfoxide, diglyme, and the like. In addition, any other solvent that can be mixed with these can be used in combination.

In order to obtain a polyamic acid solution in the presence of the above-mentioned intercalation compound, first, the above-mentioned intercalation compound is uniformly dispersed in the above-mentioned organic solvent using an appropriate dispersing means such as a disperser or an ultrasonic disperser. Prepare a dispersion. In this case, it is preferable to disperse the intercalation compound in the organic solvent under heating so as not to exceed the boiling point of the organic solvent used.

Next, the dispersion of the interlayer compound thus prepared is diluted with an appropriate organic solvent, and then charged into a reactor. A diamine component, which is a raw material of polyimide, is added thereto and dissolved. Furthermore, by adding an acid anhydride component,
By mixing and stirring, the diamine in the interlayer compound is also reacted with the acid anhydride component as a diamine component as a raw material monomer of the polyimide, and thus a polyamic acid solution in which the interlayer compound is uniformly dispersed can be obtained.

As described above, in the present invention, the first
In the step, the diamine in the intercalation compound also reacts with the acid anhydride component as a diamine component, so that the ratio of the diamine component and the acid anhydride used is, including the diamine component contained in the intercalation compound, the diamine component and the acid anhydride. It is adjusted so that the substance component is substantially equivalent (equimolar amount).

According to the present invention, the second step is a step of imidizing the polyamic acid from the polyamic acid solution thus obtained to obtain a polyimide composite. To obtain a polyimide composite from the polyamic acid, for example, heating the polyamic acid solution, causing a dehydration reaction of the polyamic acid, a thermal method of imidization, and adding a dehydrating agent to the polyamic acid solution, May be used by any of the chemical methods for imidizing the compound.

In the case of the above-mentioned thermal method, the organic solvent is removed from the polyamic acid solution by drying under conditions that do not cause imidization, and then heat treatment is appropriately performed at a temperature in the range of 150 to 400 ° C. to obtain the polyamic acid. Imidation by the dehydration reaction proceeds, and a polyimide composite can be obtained. On the other hand, when using a chemical method, a solution containing a stoichiometric or more dehydrating agent and a catalytic amount of a tertiary amine may be mixed with the polyamic acid solution. As the dehydrating agent, for example, aliphatic or aromatic acid anhydrides such as acetic anhydride and phthalic anhydride are used. Examples of the catalyst include an aliphatic tertiary amine such as triethylamine and a heterocyclic tertiary amine such as pyridine, picoline and isoquinoline.

According to the present invention, the blending ratio (content) of the intercalation compound in the polyimide composite is usually in the range of 2 to 7% by weight of the composite, preferably 2 to 5% by weight.
Range. When the compounding ratio of the intercalation compound is less than 2% by weight, the resulting polyimide composite is poor in the effect of improving the elastic modulus, the coefficient of linear expansion, the tensile strength, the moisture permeability and the like, and when it exceeds 7% by weight. However, since the composite is extremely embrittled and the elongation is significantly reduced, it becomes difficult to handle the film, for example.

According to the present invention, a diamine which is a raw material monomer of polyimide is intercalated into a layered clay mineral to form an interlayer compound, and polyamic acid is obtained in the presence of the interlayer compound. The diamine component also participates in the polymerization reaction. Thus, the polymerization reaction between the diamine component and the acid anhydride component between the layers of the layered clay mineral causes separation (dispersion) of the layer, and the polyimide obtained by this polymerization reaction. Is ionically bonded to the surface of the layered clay mineral via the terminal diamine component,
A polyimide composite having excellent thermal properties, mechanical properties, gas barrier properties, dimensional stability, and the like can be obtained by strengthening the inorganic interaction.

Depending on the purpose, the polyimide composite obtained by the method of the present invention may contain pigment components such as carbon, titanium oxide and boron nitride, a heat stabilizer, an antioxidant, an ultraviolet absorber, and a light stabilizer. Agents, lubricants, plasticizers, antistatic agents, flame retardants and the like can be added.

[0030]

The present invention will be described below with reference to examples together with comparative examples, but the present invention is not limited to these examples.

Example 1 (Preparation of Intercalation Compound Dispersion) 20 g of Kunipia F (montmorillonite, cation exchange capacity: 119 meq / 100 g, manufactured by Kunimine Industries Co., Ltd.) was added to 400 g of distilled water, and the mixture was stirred and dispersed to obtain a clay dispersion. Was prepared. Separately, 2.2 g of dodecylamine, 1.2 mL of concentrated hydrochloric acid and 50 g of water were uniformly mixed, added to the above-mentioned clay dispersion, and stirred at 80 ° C. for 1 hour. Thereafter, 1.1 g of 4,4'-diaminodiphenyl ether (ODA), 0.6 mL of concentrated hydrochloric acid and 50 g of water were uniformly mixed, and the mixture was added to the above clay dispersion.
For 1 hour.

After the precipitated solid was separated by filtration, the solid was sufficiently washed with warm water. The obtained cake-like solid was freeze-dried to remove water, and then crushed in a mortar to obtain a powdery intercalation compound. 3 g of this intercalation compound was added to dimethylacetamide (DM
Ac) in 90 g, dispersed by stirring at 90 ° C. for 1 hour,
A paste-like interlayer compound dispersion was obtained.

(Preparation of polyamic acid solution) 16.9 g of the above intercalated compound dispersion, 47.1 g of DMAc and 7.66 of ODA
g was uniformly dispersed and dissolved. This was charged into a glass reactor equipped with a stirrer, and then 8.34 g of pyromellitic dianhydride (PMDA) was added and polymerized at room temperature for 3 hours to obtain a viscous polyamic acid solution.

(Preparation of Polyimide Composite) Using an applicator, the above polyamic acid solution was manually applied on a glass substrate, and this was dried in a dryer under a nitrogen stream at 100 ° C. for 1 hour, and then at 150 ° C. for 1 hour. Time, then 2 minutes at 300 ° C
Time, heat drying, heat imidization, thickness 50μ
m was obtained as a polyimide composite film.

Comparative Example 1 (Preparation of Intercalation Compound Dispersion) 20 g of Kunipia F was added to 400 g of distilled water, stirred and dispersed to prepare a clay dispersion. Separately, 4.4 g of dodecylamine, 2.4 mL of concentrated hydrochloric acid and 100 g of water were uniformly mixed, added to the clay dispersion, and stirred at 80 ° C. for 1 hour.

After the precipitated solid was separated by filtration, the solid was sufficiently washed with warm water. The obtained cake-like solid was freeze-dried to remove water, and then crushed in a mortar to obtain a powdery intercalation compound. 3 g of this intercalation compound was stirred and dispersed in 90 g of DMAc at 90 ° C. for 1 hour to obtain a paste-like intercalation compound dispersion.

(Preparation of Polyamic Acid Solution) A polyamic acid solution was obtained in the same manner as in Example 1 using the above-mentioned interlayer compound dispersion. (Polyimide composite) Using the above polyamic acid solution,
In the same manner as in Example 1, a polyimide composite film was obtained.

Comparative Example 2 (Preparation of Intercalation Compound Dispersion) 20 g of Kunipia F was added to 400 g of distilled water, stirred and dispersed to prepare a clay dispersion. Separately, 2.19 g of ODA, 1.2 mL of concentrated hydrochloric acid and 1 of water
00g was mixed uniformly and added to the clay dispersion.
Stirred at 80 ° C. for 1 hour.

After the precipitated solid was separated by filtration, the solid was sufficiently washed with warm water. The obtained cake-like solid was freeze-dried to remove water, and then crushed in a mortar to obtain a powdery intercalation compound. 3 g of the intercalated compound was stirred in 90 g of DMAc at 90 ° C. for 1 hour, but the dispersion of the clay was poor, and an intercalated compound dispersion was obtained in which the clay remained partially as a lump.

(Preparation of Polyamic Acid Solution) A polyamic acid solution was obtained in the same manner as in Example 1 by using the above-mentioned interlayer compound dispersion. (Polyimide composite) Using the above polyamic acid solution,
In the same manner as in Example 1, a polyimide composite film was obtained.

Comparative Example 3 (Preparation of Polyamic Acid Solution) ODA was added to 150 g of DMAc.
After dissolving 23.9 g, this was charged into a glass reactor equipped with a stirrer, 26.1 g of PMDA was added, and polymerized at room temperature for 3 hours to obtain a viscous polyamic acid solution.

(Preparation of Polyamide Alone) A polyimide film was obtained in the same manner as in Example 1 using the above polyamic acid solution.

Example 2 (Preparation of Intercalation Compound Dispersion) 20 g of Kunipia F was added to 400 g of distilled water, stirred and dispersed to prepare a clay dispersion. Separately, 0.88 g of dodecylamine and 4.8 mL of concentrated hydrochloric acid
And 50 g of water were uniformly mixed, and this was added to the clay dispersion, followed by stirring at 80 ° C. for 1 hour. Then, ODA 1.76
g, concentrated hydrochloric acid (0.96 mL) and water (50 g) were uniformly mixed and added to the above dispersion, followed by stirring at 80 ° C. for 1 hour.

After the precipitated solid was separated by filtration, the solid was sufficiently washed with warm water. The obtained cake-like solid was freeze-dried to remove water, and then crushed in a mortar to obtain a powdery intercalation compound. 3 g of this intercalation compound was stirred and dispersed in 90 g of DMAc at 90 ° C. for 1 hour to obtain a paste-like intercalation compound dispersion.

(Preparation of Polyamic Acid Solution) A polyamic acid solution was obtained in the same manner as in Example 1 using the above-mentioned interlayer compound dispersion. (Polyimide composite) Using the above polyamic acid solution,
In the same manner as in Example 1, a polyimide composite film was obtained.

Example 3 (Preparation of Intercalation Compound Dispersion) 20 g of Kunipia F was added to 400 g of distilled water, stirred and dispersed to prepare a clay dispersion. Separately, 3.52 g of dodecylamine, 1.92 m of concentrated hydrochloric acid
L and 50 g of water were uniformly mixed, added to the clay dispersion, and stirred at 80 ° C. for 1 hour. After that, ODA 0.4
4 g, 0.25 mL of concentrated hydrochloric acid and 50 g of water are uniformly mixed,
After this was added to the above dispersion, the mixture was stirred at 80 ° C. for 1 hour.

After the precipitated solid was separated by filtration, the solid was sufficiently washed with warm water. The obtained cake-like solid was freeze-dried to remove water, and then crushed in a mortar to obtain a powdery intercalation compound. 3 g of the interlayer compound was stirred and dispersed in 90 g of DAMc at 90 ° C. for 1 hour to obtain a paste-like interlayer compound dispersion.

(Preparation of Polyamic Acid Solution) A polyamic acid solution was obtained in the same manner as in Example 1 using the above-mentioned interlaminar compound dispersion. (Polyimide composite) Using the above polyamic acid solution,
In the same manner as in Example 1, a polyimide composite film was obtained.

Example 4 (Preparation of Interlayer Compound Dispersion) 20 g of Kunipia F was added to 400 g of distilled water, stirred and dispersed to prepare a clay dispersion. Separately, 2.2 g of dodecylamine, 1.2 mL of concentrated hydrochloric acid and 50 g of water were uniformly mixed, added to the above-mentioned clay dispersion, and stirred at 80 ° C. for 1 hour. Thereafter, 0.64 g of p-phenylenediamine (PDA), 0.6 mL of concentrated hydrochloric acid and 5 parts of water
After 0 g was uniformly mixed and added to the clay dispersion, the mixture was stirred at 80 ° C. for 1 hour.

After the precipitated solid was separated by filtration, the solid was sufficiently washed with warm water. The obtained cake-like solid was freeze-dried to remove water, and then crushed in a mortar to obtain a powdery intercalation compound. 3 g of this intercalation compound was added to N-methylpyrrolidone (NM
P) The mixture was stirred and dispersed in 90 g for 1 hour to obtain a paste-like interlayer compound dispersion.

(Preparation of Polyamic Acid Solution) 25 g of the above-mentioned intercalation compound, 65.5 g of NMP and 6.08 g of PDA were uniformly dispersed and dissolved, and this was charged into a glass reactor equipped with a stirrer. 16.54 g of 4'-diphenylethertetracarboxylic dianhydride (BPDA) was added and polymerized at room temperature for 3 hours to obtain a viscous polyamic acid solution.

(Preparation of Polyimide Composite) The above polyamic acid solution was manually applied on a glass substrate using an applicator, and this was dried in a dryer under a nitrogen stream at 100 ° C. for 1 hour and at 150 ° C. for 1 hour. Next, it was heated and dried at 300 ° C. for 2 hours, and thermally imidized to obtain a polyimide composite film having a thickness of 50 μm.

Comparative Example 4 (Preparation of Interlayer Compound Dispersion) 20 g of Kunipia F was added to 400 g of distilled water, and the mixture was stirred and dispersed to prepare a dispersion. Separately, 4.4 g of dodecylamine, 2.4 mL of concentrated hydrochloric acid and 100 g of water are uniformly mixed, and this is added to the above dispersion,
Stirred at 80 ° C. for 1 hour. After separating the precipitated solid by filtration 1,
Washed thoroughly with warm water. The obtained cake-like solid was freeze-dried to remove water, and then crushed in a mortar to obtain a powdered organically-organized clay mineral. 3 g of this organically modified clay mineral is NMP
In 90 g, the mixture was stirred and dispersed at 90 ° C. for 1 hour to obtain a paste-like organically-organized clay mineral dispersion.

(Preparation of Polyamic Acid Solution) A polyamic acid solution was obtained in the same manner as in Example 4 using the above-mentioned organically modified clay mineral dispersion. (Polyimide composite) Using the above polyamic acid solution,
In the same manner as in Example 4, a polyimide composite film was obtained.

Example 5 In Example 1, 28.7 g of the intercalation compound dispersion was added to DMA.
A polyimide composite film was obtained in the same manner as in Example 1 except that c5.3 g was used.

Example 6 In Example 1, 11.1 g of the intercalation compound dispersion was added to DMA.
A polyimide composite film was obtained in the same manner as in Example 1 except that 52.9 g of c was used.

Comparative Example 5 In Example 1, 47.5 g of the intercalation compound dispersion and DMA
A polyimide composite film was obtained in the same manner as in Example 1, except that 16.5 g of c was used.

The properties of the polyimide (composite) films obtained in Examples 1 to 6 and Comparative Examples 1 to 5 were evaluated as follows. The results are shown in Tables 1 and 2. These tables also show the molar ratio of the diamine component and the organic onium ion used in each of the examples and comparative examples.

(Storage Elastic Modulus) Using a dynamic viscoelasticity spectrum meter DMS210 (manufactured by Seiko Instruments Inc.), the temperature dispersion was measured in the tensile mode in the range of 30 to 480 ° C. The frequency is 10 Hz and the rate of temperature rise is 5 ° C./min. The storage modulus at 50 ° C. and 400 ° C. was read from the spectrum.

(Glass Transition Temperature) The temperature dispersion of tan δ was measured with a dynamic viscoelasticity spectrometer, and the temperature at which the maximum value was obtained was taken as the glass transition temperature Tg.

(Tensile elongation and tensile strength) A polyimide (composite) film is formed into a strip shape (width 5 mm, length 50 mm).
And measured at a temperature of 22 ° C. using Tensilon UTM-5000 (manufactured by Toyo Baldwin Co., Ltd.).
The distance between the chucks was 50 mm, and the pulling speed was 5 mm / min.

(Coefficient of linear expansion) Using TMA / SS100 (manufactured by Seiko Denshi Co., Ltd.), evaluation was made by the TMA method. The linear expansion coefficient in a temperature range of 50 to 250 ° C. was evaluated at a heating rate of 20 ° C./min.

(Moisture Permeability) A temperature of 60 was determined by a moisture-permeable cup method.
The moisture permeability coefficient under a constant temperature and humidity condition of 90 ° C. and a humidity of 90% was measured.

[0064]

[Table 1]

[0065]

[Table 2]

[0066]

According to the method of the present invention, as a guest,
In part, by using diamine which is a raw material monomer of polyimide, while reducing the amount of organic onium salt to be intercalated to the layered clay mineral, compared to the conventional one, other than thermal properties, mechanical properties, Gas barrier properties,
A polyimide composite having excellent dimensional stability and the like can be obtained.

Claims (2)

[Claims] 1. A diamine component and an acid anhydride component, which are monomer materials of polyimide, in an organic solvent in the presence of an intercalation compound obtained by intercalating a diamine, which is a material monomer of polyimide, and an organic onium ion into a layered clay mineral. Polymerizing to obtain a polyamic acid solution in which the interlayer compound is dispersed, and imidizing the polyamic acid,
A process for obtaining a polyimide composite. 2. A polyimide composite produced by the method of claim 1.