JPH03217452A - Heat-resistant film and stretched heat-resistant film - Google Patents

Abstract

PURPOSE:To obtain the subject heat-resistant film maintaining an excellent mechanical strength in a wide temperature range, excellent in heat stability, inflammability, etc., and suitable in the field of electronics, etc., by blending a specified polyether-based copolymer with a specified polyetherimide in a specified amount. CONSTITUTION:With (A) 40-90wt.% polyether-based copolymer composed of repeating units of formulae I and II, having 0.15-0.4 molar ratio of respective repeating units [I/(I+II)] and having 500-100000 poise melt viscosity at 400 deg.C, (B) 10-60wt.% polyetherimide having a repeating unit represented by formula III [Ar<1> and Ar<2> are formulae IV, V, etc.] is blended and the resultant blended polymers are formed into a film. The obtained film is uniaxially or biaxially stretched in 1.5-10 times stretch ratio at a temperature between glass transition temperature and crystalline melting point.

Description

[Detailed Description of the Invention] [Industrial Application Field] The present invention... # Regarding heat-resistant films and heat-resistant stretched films, in more detail, they have a high glass transition point and can be widely used in various applications in the electronics field, electrical and thermal insulation fields, and other general industrial fields. The present invention relates to a heat-resistant film and a heat-resistant stretched film that have excellent heat resistance.

[Prior art and invention or problem to be solved] In recent years, various resin films with excellent heat resistance and mechanical strength have been developed, and these have a wide range of uses as materials for parts of electrical and electronic equipment and machinery. It is served to.

On the other hand, as the range of uses for resin films has expanded, there has been an increasing demand for resin films that have even better properties than conventional ones, such as heat resistance, flame retardance, and mechanical strength. .

However, among the resin films currently used, even polyetherketone resin, which is said to have the best performance, has a low glass transition temperature, and there are temperature regions higher than this glass transition temperature150 ~20
At 0°C, the mechanical strength decreases. Furthermore, polyetherketone resins tend to contain kelp in their polymers due to their harsh manufacturing conditions, and therefore have difficulty in molding processability, and have not yet had properties that are satisfactory in all respects. In particular, the fact that these resins tend to contain gel is a problem when forming these resins into films.

The present invention has been made based on the above circumstances.

An object of the present invention is to provide a film that maintains sufficiently high mechanical strength and has excellent heat resistance over a wide temperature range.

[Means for Solving the Problem] The invention according to claim 1 for solving the problem includes a repeating unit represented by the following formula (I): (I) and a repeating unit represented by the following formula (■): 0 (II ) of the repeating unit represented by formula (I) above! g ratio [thousand ratio, (1/(I) +
(II)] or 0.15 to 0.40, and 40
40 to 90% by weight of a polyether copolymer having a melt viscosity of 500 to 100,000 at 0°C and the following formula (m) (m), where Ar' and Ar2 are However, R+ and R2 are an alkyl group, a cycloalkyl group, or a phenyl group, and may be the same or different from each other.) They may be the same or different from each other. ] A heat-resistant film characterized by containing 10 to 60% by weight of a polyether imite having a repeating unit represented by: A heat-resistant stretched film characterized in that the film is stretched at a stretching ratio of 1.5 to IO times, The heat-resistant stretched film according to claim 2, wherein the stretched film is uniaxially or biaxially stretched at a temperature between and the crystal melting point.

In the heat-resistant film of the present invention, the first important thing is that
It may contain a polyether copolymer having a specific structure and a polyether imite having a specific structure in a specific ratio.

Hereinafter, the explanation will be given in order.

-Boriether copolymer One of the important points in the film of the present invention is that the polyether copolymer is composed of a repeating unit represented by the formula (I) and a repeating unit represented by the formula (II). At the same time, the composition ratio of the repeating unit represented by the above formula (I) [molar ratio / (I) / (I) + DI]
] or 0.15 to 0.40, preferably 0.20 to 0.
There are some things that are within the range of 35.

If the composition ratio is less than 0.15, the glass transition temperature of the polyether copolymer will be low, resulting in a decrease in heat resistance, or the melting point will be high, leading to deterioration in moldability. On the other hand, if it exceeds 0.40, the polyether copolymer will lose its crystallinity and its heat resistance and solvent resistance will decrease.

Furthermore, in the polyether copolymer of the present invention, the melt viscosity (cello-shear viscosity) at a temperature of 400°C is 50°C.
0-100,000 voices, preferably 3,000-8
It is important that there are 0,000 voices.

This is because a low molecular weight polyether copolymer having a melt viscosity of less than 500 poise cannot achieve sufficient heat resistance and mechanical strength.

Furthermore, if the melt viscosity exceeds 100,000 voids, it becomes difficult to form a film.

The polyether copolymer used in the present invention has a polar group in its molecule and has excellent compatibility with polyether imite. Moreover, this polyether copolymer has a crystal melting point of, for example, about 330 to 400°C, has high crystallinity, has a sufficiently high molecular weight, exhibits sufficient heat resistance, and has excellent solvent resistance and Excellent mechanical strength. Therefore, a composition containing this polyether copolymer and the polyether imite described below has excellent properties without impairing the properties of both the polyether copolymer and the polyether imite. It is possible to suitably form the film into a film having the following properties.

Such a polyether copolymer can be produced as follows.

■Production method of polyether copolymer The polyether copolymer of the present invention is produced by reacting cyhalogenobenzonitrile and 4,4-biphenol in the presence of an alkali metal compound and a neutral polar solvent at a specific usage ratio. After that, the reaction product obtained and a specific amount of 4,4"
-It can be produced by carrying out a copolymerization reaction with cyhalogenobenzophenone.

Specific examples of the dihalogenobenzonitrile include the following formula: (In the formula, X represents a halogen atom, and two Xs may be the same or different.) 2 expressed as
, 6-cyhalogenobenzonitrile and 2,4-cyhalogenobenzonitrile represented by the following formula: X (wherein, X has the same meaning as above).

Among these, 2,6-cyclobenzonitrile, 2,6-cyfluorobensonitrile, 2.4
-cyclobenzonitrile, 2,4-difulpenzonitrile, and particularly preferred is 2,6-cyclobenzonitrile.

In the method of the present invention, the cyhalogenobenzonitrile and a 4,4'' monophenol represented by the following formula are reacted in the presence of an alkali metal compound and a neutral polar solvent.

The alkali metal compound to be used is
Any substance that can convert ゜-biphenol into an alkali metal salt may be used, and there are no particular limitations, but alkali metal carbonates and alkali metal hydrogen carbonates are preferred.

Examples of the alkali metal carbonates include lithium carbonate, sodium carbonate, potassium carbonate, rubidium carbonate,
Examples include cesium carbonate.

Among these, preferred are sodium carbonate and potassium carbonate.

Examples of the alkali metal bicarbonate include lithium bicarbonate, sodium bicarbonate, potassium bicarbonate,
Examples include rubicium hydrogen carbonate and cesium hydrogen carbonate.

Among these, preferred are sodium hydrogen carbonate and potassium hydrogen carbonate.

In producing the polyether copolymer of the present invention, among the various alkali metal compounds mentioned above, sodium carbonate and potassium carbonate can be particularly preferably used.

Examples of the neutral polar solvent include N,N-dimethylformamide, N,N-jethylformamide, and N,N-dimethylformamide.
-Simethylacetamide, N,N-shetylacetamito, N,N-cyprobylacetamide, N,N-dimethylbenzoic acid amide, N-methyl-2-pyrrolidone, N
1-ethyl-2-pyrrolitone, N-isobrobyl-2-pyrrolidone, N-isobutyl-2-pyrrolitone, N-n-
Proyl-2-pyrrolidone, Nn-butyl-2-virolitone, N-cyclohexyl-2-virolitone, tomethyl-3-methyl-2-pyrrolitone, N-ethyl-3-methyl-2-pyrrolitone, N-methyl-3. 4.5 - Trimethyl-2-pyrrolitone, N-methyl-2-biberitone, N-ethyl-2-biberitone, N-isobrobyl-
2-Biberitone, N-methyl-6-methyl-2-biberitone, N-methyl-3-ethylpiberitone, simethylsulfoxide, ethylsulfoxide, 1-methyl-I-
Oxosulfolane, 1-ethyl-1-oxosulfolane, ]-phenyl-1-oxosulfolane. NJ-simethylimidazovinone, cyphenylsulfone, and the like.

The molar ratio of the cyhalogenobenzonitrile to the total amount of cyhalogenobenzonitrile and 4,4'-dihalogenobenzophenone is usually 0615 to +1.40, preferably 0. The ratio of the alkali metal compound used is usually 1.01 to 2.50 equivalents, preferably 1.02 to 1, per hydroxyl group of the 4,4°-biphenol. The ratio is 20 equivalents.

There are no particular restrictions on the amount of the neutral polar solvent used, but it is usually the same amount as the cyhalogenobenzonitrile and 4.
The total amount of 4'-biphenol and the alkali metal compound is 1 (10 parts by weight), and 20 (1 to 2.000 parts by weight) is selected.

In order to produce the polyether copolymer of the present invention, the cyhalogenobenzonitrile and the 4.4'-
A reaction is carried out with biphenol, and the reaction product obtained by the reaction is reacted with the 4.4' cyhalogenobenzophenone.

The 4.4''-cyhalogenobenzophenone to be used is a compound represented by the following formula; Preferred are penzophenone and 4,4°-cyclopenzophenone.

In producing the polyether copolymer of the present invention, the 4,4°-dihalogenobenzophenone is
The molar ratio of the total amount of , 4°-cyhalogenobenzophenone and cyhalogenobenzonitrile to the amount of 4.4°hyphenol used is 0.98 to 1.02, preferably 1.00 to 1.01. Adjust the amount used so that it is used.

When producing the polyether copolymer of the present invention, for example, the cyhalogenobenzonitrile, the 4,4'-biphenol, and the alkali metal compound are simultaneously added to the neutral polar solvent. , After the reaction of the dihalogenobenzonitrile and the 4,4゛-biphenol, the 4,4゜-cyhalogenobenzophenone is further added, and the temperature is usually 150 to 380°C, preferably 180 to 330°C. A series of reactions are carried out at a range of temperatures. If the reaction temperature is less than 150°C, the reaction rate is too slow to be practical, and if it exceeds 380°C, side reactions may occur.

Moreover, the reaction time of this series of reactions is usually 0.1 to I
O hours, preferably 1 hour to 5 hours.

After the reaction is complete, the polyether copolymer is separated and purified from the resulting neutral polar solvent solution containing the polyether copolymer according to a known method. You can get it.

In this way, the polyether copolymer of the present invention can be efficiently produced through a simple process.

The polyether copolymer of the present invention can also be produced by a method other than the above-mentioned method (first method). 4,4゛-biphenol is reacted in the presence of an alkali metal compound and a neutral polar solvent (first stage reaction), and the resulting reaction product is copolymerized with 4.4゛-biphenone. It can also be produced by performing (second stage reaction) (second method).

The cyhalogenobenzonitrile, the 4,4°-cyclobenzophenone, the 4,4°-cyfluorobenthophenone, the alkali metal compound, and the neutral polar solvent are as described in the first method. It is similar to.

In this second method, the proportions of the cyhalogenohenzonitrile and the alkali metal compound used in the first method are as follows.
The same is true for the method.

Further, the cyhalogenobenzonitrile and the 4,4°-
The total usage amount of cyclobenzophenone and the above-mentioned 4,4'-difulpenzophenone is the usage amount of the above-mentioned 4,4゜-biphenol which is the total usage amount of 4,4''-dihalogenobenzophenone and dihalogenobenzonitrile. The molar ratio to is usually 0.98 to 1.02, preferably 1
．． The ratio is set to be between 00 and 1.01.

The molar ratio of the amount of 4,4°-cyclobenzophenone used in the first stage reaction and the amount of 4,4°-cyclobenzophenone used in the final polymer synthesis is 60-95:5-40. Is it desirable to do so?

The proportion of the alkali metal compound used and the amount of the neutral polar solvent used are the same as explained in the first method. The reaction temperature, reaction time, etc. in this method are also the same as in the first method. After the reaction is completed, the polyether copolymer can be isolated by treating the resulting reaction solution in a conventional manner.

- Polyether imite One of the other important points in the film of the present invention is that the main component is the polyether imite or a polymer having a repeating unit represented by the formula (m). be.

The polyetherimide in the present invention has a repeating unit represented by the general formula (m) and N-methyl-2
-Reduced viscosity [ηsp/
c] or Ol~2.0 di/g.

The polyether imite in the present invention may contain repeating units other than the repeating unit (m) as long as the object of the present invention is not impaired.

Examples of other repeating units include repeating units with the following structure.

(IV) (In the formula, Ar' and Ar2 have the same meaning as above.) The repeating unit (IT) of the above structure can be easily dehydrated by heating to form a repeating unit represented by the above formula (III). Can be changed into units.

(2) Method for producing polyether imite The polyether imite in the present invention can be produced, for example, as follows.

That is, it can be obtained by reacting a dicarboxylic acid anhydride represented by the following formula (V) with a cyamine compound represented by the following formula (VI) in a neutral polar solvent.

(V) [Tatashi, Ar” have the same meaning as above.]H
t N A r'- N H 2 (VI) [However, Ar' represents the same meaning as above. Examples of the neutral polar solvent include dimethylformamide, dimethylacetamide, N-methylpyrrolitone, dimethylsulfoxide, sulfolane, cyphenylsulfone, and simethylimitazolicinone. These neutral polar solvents may be used alone, or two or more may be used in combination as a mixed solvent, or other inert organic solvents, such as water can be retained outside the reaction system. It may also be used as a mixed solvent with an aromatic hydrocarbon solvent such as benzene, toluene, xylene, etc., which is an azeotropic solvent for removal.

The usage ratio of the cycarboxylic acid anhydride represented by the formula (V) to the diamine compound represented by the formula (VI) is:
substantially equimolar amounts.

The reaction temperature in carrying out the polymerization reaction is usually 0 to 5
The reaction time is usually 5 minutes to IO time, preferably 30 minutes to 1 hour.

The reaction product liquid obtained after the polymerization reaction is treated by a normal method.
For example, a polyetherimide having a repeating unit represented by the formula (m) can be isolated by precipitating a polymer using a solvent, collecting it, and subjecting it to a purification operation.

In addition, when the cyamine compound represented by the above formula (W) and the cyclocarboxylic acid anhydride represented by the above formula (V) are reacted, some of the repeating units represented by the above formula (ff) are contained in the polymer. However, this does not impede the purpose of the present invention in the slightest.

Heat-resistant film and heat-resistant stretched film - The heat-resistant film of the present invention can be produced by molding a composition formed by blending the polyether copolymer and polyetherimide in a specific ratio. .

The said group I & thing is composed of 40 to 90% by weight of the polyether copolymer and 10 to 10% of the polyether imite, when the total of the polyether copolymer and the polyether imite is 100. 60% by weight. In the composition, it is not preferable to use less than IO weight percent of polyetherimite because the glass transition temperature (Tg) decreases and the heat resistance deteriorates. On the other hand, if the content of polyether imite exceeds 60% by weight, the product becomes unfavorable and the crystallization rate becomes extremely slow, which is not preferable.

Note that this composition may contain ultraviolet absorbers, antistatic agents, antioxidants, lubricants, colorants, etc., within a range that does not impede the object of the present invention.

The present composition can be obtained by using a commonly used resin mixer. Among these, melt kneading using an extruder or a kneader is preferred.

The heat-resistant film of the present invention can be produced by lO to 100' below the crystal melting point using a conventional method such as press molding or extrusion.
It can be obtained by forming the composition into a film at a high temperature, preferably 30-70°C above the crystalline melting point, and rapidly cooling it. The film thus obtained is amorphous and has good transparency. This film exhibits sufficient mechanical strength at room temperature, but because it is amorphous, its mechanical strength, solvent resistance, and chemical resistance at high temperatures are not necessarily sufficient, so it must be heat-treated. By doing so, it is possible to obtain a crystalline film that overcomes the above-mentioned difficulties. This solidified heat-resistant film has improved mechanical properties, especially tensile strength and tensile modulus, compared to a non-grade heat-resistant film before heat treatment, and has improved mechanical properties at high temperatures such as 200°C. The heat treatment conditions for the above-mentioned defective heat-resistant film are usually a heating temperature of 200 DEG to 370 DEG C. and a heating time of 0.1 to 30 minutes.

If the heating temperature is less than 200°C, crystallization may not occur sufficiently, and if it exceeds 370°C, deformation may occur. Further, if the heating temperature is less than 0.1 minute, the heat treatment effect is insufficient, and if it exceeds 30 minutes, no further effect can be obtained.

Furthermore, what should be noted in the present invention is that by further stretching the heat-resistant film, a heat-resistant stretched film with greater mechanical strength can be formed.

When stretching the heat-resistant film, the stretching ratio is L
．． Is it preferable that the stretching ratio is S to IO times, especially 2 to 5 times, or that if it is less than 1.5 times, sufficient stretching effect (improving effect on film physical properties such as tensile strength and tensile modulus) may not be achieved? However, even if the film is stretched by more than 10 times, the stretching effect may not be further improved.

The heat-resistant stretched film is preferably formed uniaxially or biaxially at a temperature between Tg (glass transition temperature) and Tm (crystalline melting point).

Furthermore, this heat-resistant stretched film can be stretched under tension or without tension as required. It is preferable to carry out the heat treatment at a temperature higher than Tcc (crystallization temperature 2, the temperature at which the amorphous polymer in the above-mentioned film formation crystallizes by heat treatment (temperature elevation)) and lower than Tm (crystalline melting point).

The heat-resistant film and heat-resistant stretched film thus obtained are: (1) In the electronics field, base films for flexible printed circuit boards, backing materials for flexible printed circuit boards, electrode plates for membranes, and backing materials for membranes. It can be used for base films for transparent electrodes, film cells for liquid crystals, IC carrier tables, optical cards, base films for perpendicular magnetization, etc. (2) Base films for planar heating elements in the electrical and thermal insulation fields. and its surface Kahar film, such as insulation tape used in motors, generators, transformers, etc.; capacitors:
Wire coating: Shielding plate for microwave ovens and other heat equipment: Speaker diaphragm: Can be used for lighting equipment, instrument display panels, etc.; It can be used for interior materials, nuclear power-related equipment, solar collectors, ultrafiltration membranes, etc. (4) In addition, it can be used for heat-resistant labels, heat-resistant nameplates, aviation/vehicle/defense-related composites, etc. It comes.

[Example] Next, an example of the present invention will be shown and the present invention will be explained in more detail.

(Example 1) (1) Production of polybiphenylene ether ketone copolymer In a reactor with an internal volume of 5 cm and equipped with a Dean-Starck trap filled with toluene, a stirring device, and an argon gas blowing tube, a 2,6-cyclo Benzonitrile 32.34 g
(0.188 mol), 4,4'-biphenol 1:l
9.66g (0.75mol), potassium carbonate 1241
9 g (0.9 mol) and 1.5 N-methylpyrrolitone
The temperature was raised from room temperature to 195°C over 1 hour while blowing argon gas.

After the temperature was raised, a small amount of toluene was added and the resulting water was removed by azeotropy.

Next, after carrying out the reaction at 195°C for 30 minutes, 4,4°-cyfluoropenzophenone 122.85
g (0.563 mol) of N-methylpyrrolidone 1.5
A solution of 1 was added to the mixture, and the reaction was further carried out for 1 hour.

After the reaction is complete, the product is transferred to a flender (manufactured by Warninck).
When crushed, washed with acetone, methanol, water and acetone in that order, and dried, the bulk density was
g/cm' white powder 259. :l6
g was obtained.

When IR measurement was performed on this white powder, 2
, 220 cm-' absorption by nitrile group,
Absorption due to a carboxyl group at a position of 1,650 cm-' and absorption due to an ether bond at a position of 1,240 cm-' were confirmed.

From this result and the elemental analysis results, the white powder was confirmed to be a polyether copolymer having the following structure. Therefore, the yield of this polyether copolymer was 98%.

When the properties of this polyether copolymer were measured, the melt viscosity (zero shear viscosity) at a temperature of 400°C
]: 1,000 voids, glass transition temperature 182°C,
The crystal melting point was 379°C, and the starting temperature of thermal decomposition was 562°C (5% weight loss in air).

(2) Production of heat-resistant film 50 parts by weight of the polyether copolymer produced in (1) above and 2,2-his(4
- (2,:l-Cycarboxyphenoxy) monophenylcopropane anhydride and m-phenylenecyamine having the following structural unit [Ultem IO
OOJ■ (manufactured by GE) and 50 parts by weight of the resin composition were supplied to Labo Plast Mill (manufactured by Toyo Seiki Seisakusho) and melted and kneaded at 400°C to produce pellets of resin composition.

This pellet was press-formed at 400°C, then put into water and rapidly cooled to a thickness of 200°C.
, Bm was obtained.

When the physical properties of this non-quality film were measured at 25°C, the tensile strength was 10 kg/sm2, and the tensile modulus was 2.
80 kg/school ■2, breaking elongation 150% (more than AST
MD882), oxygen index: I8 (ASTMD
2863).

In addition, this non-quality film has a glass transition temperature (T
g) was 204°C, and the thermal decomposition onset temperature was 553°C.

From these results, it is recognized that this non-quality film can maintain sufficient practical mechanical properties at relatively high temperatures, but not exceeding 200°C.

(Example 2) A film with a thickness of 2004 m was produced in the same manner as in Example 1, and this film was heat-treated at 240''C for 2 minutes to crystallize it.

When the physical properties of this crystallized film were measured, the tensile strength was +tkg/g+■2, and the tensile modulus was 300 k
g/am2, and the elongation at break was 110%. In addition, when the physical properties of this crystallized film at 200°C were measured, the tensile strength was 7.5 kg/ygw+2, the tensile modulus was 200 kg/-12, and the elongation at break was 160%, making it suitable for practical use even at 200°C. It was confirmed that it is possible to maintain mechanical strength.

Regarding the thermal properties of this crystallized film, the glass transition temperature is 204℃, the crystal melting point is 360℃, and the crystallization temperature is 204℃.
The thermal decomposition initiation temperature was 35°C and 553°C, and it was confirmed that it had sufficiently high thermal stability.

Next, when the limiting oxygen index of this crystallized film was measured, it was found to be 38, indicating that it had a sufficiently high flame retardancy for practical use. In addition, this crystallized film swells when immersed in concentrated sulfuric acid for a long time, but it can also be used with strong acids such as hydrochloric acid, nitric acid, cycloacetic acid, and trifluoroacetic acid, strong alkalis such as caustic soda and caustic potash, acetone, and dimethyl ether. It was completely stable without being attacked by organic solvents such as , methyl ethyl ketone, benzene, toluene, ethyl acetate, dimethyl formamide, N-methyl pyrrolidone, and methylene chloride, and hot water.

(Comparative Example 1) The polyether copolymer produced in Example 1 was
It was press-molded at 00°C and swung into ice water to obtain a transparent non-grade film. The thickness of the film was 200 Bm. This film was heat treated at 250℃ for 1 minute,
When the physical properties of Yuko's film, which had been made into a crystallized film, were measured at 25°C,
The tensile strength is llkg/■■2, and the tensile modulus is 25
0 kg/■■2, and the elongation at break was 130%.

In addition, when the physical properties of this film at 200°C were measured, the tensile strength was 3 kg/■■2, and the tensile modulus was 60 kg/
ms2, and the elongation at break was 300%, which was a significantly lower physical property than at 25°C. Next, the limiting oxygen index of this film was measured and found to be 31.5. In addition, this crystallized film will swell if immersed in concentrated sulfuric acid for a long time, or it will swell when exposed to strong acids such as hydrochloric acid, nitric acid, dichloroacetic acid, and trifluoroacetic acid, strong alkalis such as caustic soda and caustic potash, acetone, dimethyl ether, methyl ethyl ketone, etc. It was completely stable without being attacked by organic solvents such as benzene, toluene, ethyl acetate, dimethylformamide, N-methylpyrrolidone, and methylene chloride, and by hot water.

(Comparative Example 2) GE's polyether imite [Ultem IOOOJ■] was press-molded at 350° C. to obtain a transparent film with a thickness of 200 μLm.

When the physical properties of this film were measured, the tensile strength was 1 1
kg/Peng 2, tensile modulus 305 kg/am”
．． The elongation at break was 80%.

In addition, when the physical properties of this film at 200°C were measured, the tensile strength was 4 kg/am2, and the tensile modulus was 1.
40kg/s Oboro 2, elongation at break 150%, 25℃
A significant decrease in physical properties was observed compared to the physical properties in .

Regarding the thermal properties of this film, the glass transition temperature is 217°C, and the thermal decomposition temperature is 510°C.
High thermal stability was observed.

Furthermore, the limiting oxygen index of this film was 41, indicating that it had excellent flame retardancy.

In addition, this film is resistant to strong acids such as concentrated sulfuric acid, strong alkalis such as caustic sorter and caustic potash, and organic solvents such as acetone, methylene chloride, and N-methylbiloliton.
It was unstable due to dissolution and decomposition.

(Examples 3 and 4) The non-quality film prepared in Example 1 was subjected to 1, Stretching was carried out at a stretching speed of 0.000%/min. The physical properties of the obtained stretched film are shown in Table 1. Measurements were based on ASTM D882.

(Examples 5 and 6) The composition ratio of the polyether copolymer produced in (1) of Example 1 and polyether imite [Ultem+000 J] was determined by weight ratio of the former. Example 3 A non-quality film obtained in the same manner as Example 1 except that the latter = ao:zo
Stretching was carried out using the same stretching machine and the same stretching speed as in 4. The physical properties of the obtained stretched film were similarly measured.
Shown in the table.

From the above Examples and Comparative Examples, the heat-resistant film of the present invention has a higher mechanical strength in a high temperature range than a film formed from a raw material resin alone, and therefore can be used in a wider range of fields of application. It can be seen that it has the advantage that it can be used. In addition, within the composition range of the material for the heat-resistant film of the present invention, by heat-treating and crystallizing the formed film, high chemical resistance and solvent resistance, which cannot be obtained with polyether imite, can be obtained. In addition, it can be seen that the flame retardant properties of the raw resin are maintained.

Furthermore, it has been observed that mechanical properties are improved by stretching.

[Effect of the invention] The heat-resistant film and heat-resistant stretched film of the present invention have the following properties:
In addition to maintaining excellent mechanical strength over a wide temperature range, it also has excellent thermal stability, flame retardance, and chemical resistance, and has excellent physical properties, making it suitable for a wide range of applications. There are things you can do.

Claims (3)

[Claims] (1) The following formula (I): ▲There are mathematical formulas, chemical formulas, tables, etc.▼The repeating unit represented by (I) and the following formula (II); ▲Mathematical formula,
There are chemical formulas, tables, etc. ▼It consists of repeating units represented by (II), and the composition ratio [molar ratio; (I) / (I) + (II)] of the repeating units represented by formula (I) is 0.1
5 to 0.40 and a melt viscosity at 400° C. of 500 to 100,000 poise, 40 to 90% by weight of a polyether copolymer, and the following formula (III); ▲ Numerical formula, chemical formula, table, etc. Yes▼(III) [However, in the formula, Ar^1 and Ar^2 are ▲mathematical formula,
There are chemical formulas, tables, etc. ▼, ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼, ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼, ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼, or ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼, (However, R^1 and R^2 are an alkyl group, a cycloalkyl group, or a phenyl group, and may be the same or different.), even if they are the same as each other. It's okay to be different. ] A heat-resistant film characterized by containing 10 to 60% by weight of polyetherimide having a repeating unit represented by the following. (2) A heat-resistant stretched film obtained by stretching the heat-resistant film according to claim 1 at a stretching ratio of 1.5 to 10 times. (3) The heat-resistant stretched film according to claim 2, wherein the stretching is performed uniaxially or biaxially at a temperature between the glass transition temperature and the crystal melting point.