JPH01131244A - Polyimide having excellent thermal dimensional stability - Google Patents

Abstract

PURPOSE:To obtain the title novel copolymer having a specific structure of regular sequence, both excellent thermal dimensional stability and mechanical properties, causing neither warpage nor curling in laminating to metal, producible from inexpensive raw materials. CONSTITUTION:The aimed copolymer having a repeating unit shown by formula I (R1 and R2 are group shown by formula II or III with the proviso that R1 and R2 are not the same group; R0 is tetrafunctional aromatic group; m is positive integer). The copolymer, for example, is obtained by suspending or dissolving pyromellitic dianhydride in an organic polar solvent, reacting pyromellitic dianhydride with 4,4'-diaminodiphenyl ether to give a prepolymer containing acid anhydride groups at both the ends, further reacting the prepolymer with pyromellitic acid dianhydride and 3,3'-dimethylbenzidine and subjecting the formed solution of a polyamic acid copolymer to thermal ring closure through dehydration.

Description

DETAILED DESCRIPTION OF THE INVENTION (Field of Industrial Application) The present invention relates to a polyimide resin known as a heat-resistant resin. Specifically, the present invention relates to a novel polyimide copolymer that has both excellent thermal dimensional stability and excellent tensile properties.

(Prior Art) Polyimide is well known as a polymer having excellent heat resistance. This polymer has even better chemical resistance,
A typical polyimide with electrical and mechanical properties is, as is well known, a polymer obtained from 4,4'-diaminodiphenyl ether and pyromellitic dianhydride, which is commercially available. It is produced on a large scale. This polymer is used as an electrical material that requires heat resistance, such as flexible printed circuit boards. Although this polymer has excellent mechanical properties such as tensile properties, it has the disadvantage of poor thermal dimensional stability (large coefficient of linear thermal expansion on the order of 3.times.10.sup.-5.degree. C.-1). An example of a problem caused by poor thermal dimensional stability is warping or curling of flexible printed circuit boards. Flexible printed circuit boards are made by laminating polyimide film and metal, and since the coefficient of linear thermal expansion of metal is smaller than that of polyimide film, warping and curling occur due to temperature changes during processing and use of flexible printed circuit boards.

Another example of a problem caused by poor thermal dimensional stability is warping or curling of magnetic recording materials. High density magnetic recording materials near fi may be produced by depositing metal onto a pace film. Since metal deposition is carried out at high temperatures, heat-resistant polymers such as polyimide are preferred as base films; however, polyimide films have a larger coefficient of linear thermal expansion than that of metals, which causes warping and curling.

Since polyimide has heat resistance, it is often subjected to large temperature changes, and therefore polyimide having excellent thermal dimensional stability is desired. In particular, such demands are increasing with the recent development of electronics.

An example of a polyimide film with excellent thermal dimensional stability is disclosed in JP-A-61-158025.61-181828.61-2.
No. 41335°61-264028. The polyimides disclosed in JP-A-61-158025 and JP-A-61-264028 use biphenyltetracarboxylic dianhydride as the tetracarboxylic dianhydride and, if necessary, pyromellitic dianhydride, and paraphenylene as the diamine. It is a polyimide obtained by polycondensation using a diamine and optionally 4,4°-diaminodiphenyl ether. The polyimide disclosed in JP-A-61-158025 is a polyimide obtained by polycondensation with an aromatic tetracarboxylic dianhydride using a specific heterocyclic diamine such as 2,5-diaminopyridine as the diamine. . The polyimide disclosed in JP-A-61-241325 uses 9゜9-bis(4-aminophenyl)anthracene and paraphenylenediamine as diamines, and biphenyltetracarboxylic dianhydride as aromatic tetracarboxylic dianhydride. It is a polyimide obtained by polycondensation using. All of these polyimides use special and expensive compounds such as biphenyltetracarboxylic dianhydride, heterocyclic diamine, or 9,9-bis(4-aminophenyl)anthracene as raw materials.

(Problems to be Solved by the Invention) The object of the present invention is to obtain a new polyimide having excellent thermal dimensional stability and excellent 81 mechanical properties.

Another object of the present invention is to obtain a polyimide that does not warp or curl when laminated with metal and has excellent mechanical properties.

Another object of the invention is to obtain polyimides with excellent thermal dimensional stability obtained from common and inexpensive raw materials.

(Means for solving the problem) The above purpose is to have a repeating unit represented by the general formula: Achieved by polyimide copolymer.

The polyimide copolymer of the present invention has excellent heat resistance, mechanical properties such as tensile properties, thermal dimensional stability, and also has excellent alkali hydrolysis resistance.

The copolymer of the present invention can have a linear thermal expansion coefficient of 2.5X10-5°C-1 or less in the temperature range from 50°C to 300°C and an elongation of 30% or more as a tensile property. It is also possible to have a value of 2.0×10 −5° C. −1 or less and a value of 40% or more, particularly a value of 1.5×10 −5° C. −1 or less and a value of 50% or more. Furthermore, it has excellent alkali hydrolysis resistance and does not dissolve during etching treatment, etc., so it can be suitably used for printed circuit boards. For example, the weight loss rate after 5 minutes at 50°C in a 5% sodium hydroxide aqueous solution was 4.0% or less, which is smaller than conventional polyimide resins. The reason why this polyimide copolymer has the above characteristics is not clear, but the polyimide copolymer of the present invention has a block unit [where RO, R1, m are the same as above] and one repeating unit [ In the formula, RO and R2 have the same regularly arranged structure connected by C as described above, so that the retardation units are extremely homogeneously dispersed in the molecular chain, that is, hard segments. Alternatively, the soft segments are homogeneously dispersed at the molecular level. Therefore, it is assumed that thermal dimensional stability and elongation are simultaneously significantly improved.

The polyimide of the present invention is a random copolymer polyimide using 3,3'-dimethylbenzidine and 4,4°-diaminodiphenyl ether as a diamine, a homopolymer of a polyimide using 3,3''-dimethylbenzidine as a diamine, and 4. Compared to a mixture of homopolymers of polyimides using 4°-diaminodiphenyl ether as diamine.

Both thermal dimensional stability and mechanical properties are excellent.

In the polymers of the present invention - Shipman (1) and (III>).

RO is a tetravalent aromatic group in which the carbon atoms forming the aromatic ring participate in bonding, and representative examples include the following. Among these, preferred are those for obtaining )]r.

- The repeating units represented by Shipman (1) and (■) may contain other repeating units as long as they are contained in the polymer chain to an extent that achieves the effects of the present invention.

Preferred examples of other repeating units include general formula (II) (
n) [In the formula, R1 and R3 are -(D- group or -ζD-0-
ζ)-group, R1 and R3 cannot be the same group, RO
lm is the same as above, ] 0Usually, the repeating unit represented by the general formula (Riya (U)) is the main component, i.e. A polymer in which the repeating unit constitutes 50 or more repeating units on average, preferably 80% or more, more preferably 90% or more is preferable, and the repeating number m in the block unit is 1 to 9, preferably 1 to 7.
, more preferably 1-4. This is because if the repetition number m exceeds 9, the copolymerization ratio will be biased and the effect of copolymerization will be reduced. Although units with different values of m may exist in one polymer molecule, it is preferable that the value of m is constant.The molecular weight of this copolymer is not particularly restricted, but To maintain the strength of polyimide resin.

The number average molecular weight is 50,000 or more, further 80,000 or more, especially 10
10,000 or more, more preferably 120,000 or more.

The molecular weight of polyimide copolymers is often difficult to measure directly; in such cases, it is estimated by indirect methods.1 For example, when a polyimide copolymer is synthesized from polyamic acid, Let the value corresponding to the molecular weight of the polyimide be the molecular weight of the polyimide.

The polyimide copolymer of the present invention can be obtained by various methods, including -m formula (III) or -funerin (■) and (
Polyamic acid copolymer general formula (III) having a repeating unit represented by It is preferable that m is the same as above.

Next, an example of a method for producing this polyimide copolymer or polyamic acid copolymer will be explained.

- Saito [in the formula, RO is the same as above] An organic tetracarboxylic dianhydride (A>) represented by the general formula [in the formula, R1 is Same as above, ] An organic diamine compound (B) represented by [ [In the formula, R2 is the same as above] General formula % Formula % [In the formula, R3 is the same as above for the organic diamine compound (C) represented by 0 to the total organic diamine amount ((B) + (C) ) is added and reacted with the organic tetracarboxylic dianhydride (A) in substantially equimolar amounts, and has a repeating unit represented by the general formula (m) or - formulas (I [I) and (IV)] A polyamic acid copolymer is obtained.

A polyimide copolymer can be obtained by thermally or chemically dehydrating and ring-closing this copolymer.For example, by suspending and dissolving pyromellitic dianhydride in an organic polar solvent, 50 to 90 mol%, preferably 50 to 87.5 mol%, more preferably 50
~80 mol % of 4.4°-diaminodiphenyl ether is added and reacted to obtain a prepolymer having acid anhydride groups at both ends.

However, in the reaction to obtain this prepolymer, the order of addition of pyromellitic dianhydride and 4.4'-diaminodiphenyl ether may be reversed. Add 3.3°-dimethylbenzidine to make equimolar amounts.

After 4+ stirrings, a polyamic acid copolymer solution is obtained.

The concentration of polyamic acid copolymer in organic polar solvent is 5 to 3
When heating 5% by weight, 10 to 25% by weight is recommended. In order for the above polymerization reaction to proceed stably, the temperature should be 60°C or less in a substantially anhydrous system, preferably 30°C. Hereinafter, it is desirable to complete the reaction within 10 hours, preferably within 5 hours, and even more preferably within 3 hours at a temperature of 10°C or lower. Because it goes through the prepolymer at the end of the chemical group,
This is because this acid anhydride group may react with moisture in the system and become a dicarboxylic acid, inhibiting the growth of the polymer chain length.
Next, i8 of this precursor polyamic acid copolymer
? To obtain a polyimide copolymer from α, thermal dehydration ring-closing method or chemical dehydration ring-closing method can be used.
Next, an example will be given and explained.

In the method of thermally dehydrating and ring-closing (imidization), a solution of the above-mentioned polyamic acid copolymer is cast or coated onto a support such as a support plate, drum, or endless belt to form a film, which is self-supporting after drying. obtain a film of Drying is preferably carried out at a temperature of 150 DEG C. or lower for about 5 to 90 minutes.Next, this is heated to dry imide, and after cooling, it is removed to obtain a polyimide film made of the polyimide copolymer of the present invention. The temperature during heating is preferably in the range of 200 to 500°C, more preferably 300 to 500°C, particularly 400 to 500°C.
is preferable, and there is no particular restriction on the heating rate during heating, but
It is preferable to heat gradually so that the maximum temperature reaches the above temperature.The heating time varies depending on the film thickness and maximum temperature, but for -a, it is 10 seconds or more after reaching the maximum temperature.
When heating a self-supporting membrane, which is preferably within a range of 5 minutes, the membrane may be kept on the support or peeled off from the support; It is preferable to heat the copolymer with the end portion fixed in place because a copolymer having a small coefficient of linear thermal expansion can be obtained.

In the method of chemically dehydrating and ring-closing (imidization), a stoichiometric or higher dehydrating agent and a tertiary amine as a catalyst are added to the solution of the polyamic acid copolymer, and the same method as in the case of thermal dehydration is performed. A polyimide film is obtained by the method. When heating a self-supporting membrane, the membrane can be kept on the support or it can be peeled off from the support, but it can be peeled off from the support and the ends fixed in that state. Comparing the thermal imidization method and the chemical imidization method, which is preferable because it yields a copolymer with a small coefficient of linear thermal expansion, the chemical method has a higher mechanical strength of the polyimide. Moreover, the coefficient of linear thermal expansion becomes small.

Next, to explain the raw materials used in the present invention, when obtaining the polyamic acid copolymer which is the precursor of the polyimide copolymer of the present invention, pyromellitic dianhydride is used as the aromatic tetracarboxylic dianhydride. It is most preferable to use it alone to obtain the effects of the present invention, but for example, 3.3
°, 4.4'-biphenyltetracarboxylic dianhydride,
3.3°.

4,4°-benzophenonetetracarboxylic dianhydride,
It is also possible to use acid dianhydrides such as naphthalene-1,2,5,6-tetracarboxylic dianhydride, and mixtures thereof may also be used.
It is most preferable to use two types of diamines, -diaminodiphenyl ether and 3.3'-dimethylbenzidine, in order to obtain the effects of the present invention. Other diamine compounds represented, such as 4.4°-bis(4-aminophenoxy)biphenyl, 4°4′-diaminodiphenylsulfone, 3.3°-diaminodiphenylsulfone, bis[4-<4-amino phenoxy)phenyl]sulfone, bis[4-(3-aminophenoxy)phenyl]sulfone, bis[4-(2-aminophenoxy)phenyl]sulfone, 1,4-bis(4-aminophenoxy)benzene, 1,3 -bis(4-aminophenoxy)benzene, 1,3-bis(3-aminophenoxy)benzene, 1,4-bis(4-aminophenyl)benzene, bis[4-(4-aminophenoxy)phenyl]ether, 4.4°-diaminodiphenylmethane, bis(3-ethyl-4-aminophenyl)methane, bis(3-methyl-4-aminophenyl)methane, bis(
3-chloro-4-aminophenyl)methane, 3.3°-
Dimethoxy-4,4°-diaminodiphenyl, 3゜3゛-dichloro-4,4°-diaminodiphenyl, 2.2'
, 5,5'-tetrachloro-4,4'-diaminodiphenyl, 3,3'-dicarboxy-4,4'-diaminobiphenyl, 3,3'-dihydroxy-4,4'-diaminobiphenyl, 4'4'-diaminodiphenyl sulfide, 3,3°-diaminodiphenyl ether, 3,4
゛-Diamino diphenyl ether, 4.4'-diaminobiphenyl, 4.4'-diaminooctafluorobiphenyl, 2.4-diaminotoluene, metaphenylenediamine, 2,2-bis[4-(4-aminophenoxy)phenyl] Propane, 2.2-bis[4-(4-aminophenoxy)phenyl]hexafluoropropane, 2.2
-bis(4-aminophenyl)propane, 2.2-bis(4-aminophenyl)hexafluoropropane, 2.
2-bis(3-hydroxy-4-aminophenyl)propane, 2,2-bis(3-hydroxy-4-aminophenyl)hexafluoropropane, 9,9-bis(4-aminophenyl)-10-hydroxy -anthracene, orthotolidine sulfone, and 3.3'.

4.4°-Biphenyltetraamine, 3.3'.

It is also possible to partially use polyvalent amine compounds such as 4.4'-tetraaminodiphenyl ether.

When using three or more of these diamine compounds, 4.
A system using 4°-diaminodiphenyl ether, 3,3′-dimethylbenzidine and paraphenylenediamine is suitable for exerting the effects of the present invention. The organic solvents used in the production reaction of polyamic acid copolymers include:
For example, sulfoxide solvents such as dimethyl sulfoxide and diethyl sulfoxide, formamide solvents such as N,N-dimethylformamide, N,N-diethylformamide, N,N-dimethylacetamide, and N.

Acetamide solvents such as N-diethylacetamide,
Pyrrolidone solvents such as N-methyl-2-pyrrolidone and N-vinyl-2-pyrrolidone, phenol, o-, m
- or p-cresol, xylenol, halogenated phenol, phenolic solvents such as catechol, hexamethylphosphoramide, γ-butyrolactone, etc., and it is preferable to use these alone or as a mixture. It is also possible to use aromatic hydrocarbons such as xylene and toluene.

Chemical dehydration ring closure (imidization) of polyamic acid copolymer
Examples of dehydrating agents used in this process include aliphatic acid anhydrides such as acetic anhydride, aromatic acid anhydrides, and the like. Examples of catalysts include aliphatic tertiary amines such as triethylamine, aromatic tertiary amines such as dimethylaniline,
Examples include heterocyclic tertiary amines such as pyridine, picoline, and inquinoline.

The polyimide copolymer of the present invention has excellent thermal dimensional stability,
It has mechanical properties and appropriate tensile modulus, and can be used in the form of a film for flexible printed circuit boards, magnetic tapes for general magnetic recording and perpendicular magnetic recording, bases for magnetic recording materials such as magnetic disks, IC1LSI, solar cells, etc. It is extremely useful as a passivation film for semiconductor devices.

Example 1 10.31 g of 4.4'-diaminodiphenyl ether (hereinafter referred to as ODA and Iu) was collected in a 500 ml four-loop flask, and 145. OOg of N,N-dimethylacetamide was added and dissolved. On the other hand, pyromellitic dianhydride (hereinafter referred to as PMDA) 16.90 ml was placed in a 50 ml eggplant flask.
g was collected and added to the ODA solution in solid form. Furthermore, P remaining on the wall of this 50m1 eggplant flask
M
Continuing with stirring for a period of time, an acid anhydride group amic acid prepolymer was obtained.

On the other hand, 5.48 g of 3.3°-dimethylbenzidine (referred to as DMB) was collected in a 501 Erlenmeyer flask.
24g of N,N-dimethylacetamide was added and dissolved. This solution was added into the reaction system (four-bottle flask) to obtain a copolymerized polyamic acid solution.
The handling and reaction system were carried out under a stream of dry nitrogen.

Next, these polyamic acid solutions were cast onto a glass plate, dried at about 100"C for about 60 minutes, the polyamic acid coating was peeled off from the glass plate, and the coating was fixed on a support frame.
After that, it was heated at about 100°C for about 30 minutes, about 200°C for about 60 minutes, and about 300°C for about 60 minutes, and after dehydration and ring-closing drying,
A polyimide film with a thickness of 0-25 microns was obtained.

This film has a 11m tensile modulus, tensile elongation, and
and alkali resistance weight loss rate. The coefficient of linear expansion in Table 1 is the value at 200°C, and the alkali resistance weight ff
The weight loss rate is the weight loss rate after 5 minutes of immersion in a 5% NaOH aqueous solution at 50°C.

Example 2 8.07g ODA, 17.58g PMDA, DMB
A copolymerized polyimide film was obtained according to the method of Example 1, except that 2.85 g was used. This film exhibited the properties shown in Table 1.

Example 3 8.54 g of DMB was collected in a 500 ml four-loop flask, and 110. OOg of N,N-dimethylacetamide was added and dissolved. ll! ! Meanwhile, 17.58 g of PMDA was collected in a 50 ml eggplant flask and added in solid form to the DMB solution. Furthermore, the PMDA remaining on the wall of this 50m1 eggplant flask was removed by adding 1000g of N and N.
- Dimethylacetamide was poured into the reaction system (four-walled flask) and stirred for an additional hour to obtain an acid anhydride group-terminated amide acid polymer. On the other hand, 8°07g of OD A was collected in a 100ml Erlenmeyer flask, and 50. OOg's N,N
-Dimethylacetamide 3 was added and dissolved. In one or more reaction operations, this solution was added into the reaction system (four-loaf flask) to obtain a polyamic acid copolymer solution.

The reaction temperature was 5 to 10°C, and the handling of PMDA and ODA and the reaction system were carried out under a stream of dry nitrogen.
According to the method of Example 1, a copolymerized polyimide membrane was obtained. This film exhibited the properties shown in Table 1.

Example 4 12.02g ODA, 16.36g PMDA, DM
A copolymerized polyimide film was obtained in accordance with the method of Example 1, except that 3.18 g of Be was used. This film exhibited the properties shown in Table 1.

Example 5 11.90g DMB, 318.33g PMDA, OD
A copolymerized polyimide film was obtained in accordance with the method of Example 3, except that 5.61 g of A was used. This film exhibited the properties shown in Table 1.

Example 6 Add anhydrous acid to the boamic acid solution obtained by the method of Example 2! 33.88 g and 5.32 g of pyridine were added.

Next, this polyimide solution composition was cast onto a glass plate and dried at about 100°C for about 10 minutes, and then the semi-cured coating film was peeled off from the glass to obtain a polyimide film of 15 to 25 microns. This film exhibited the properties shown in Table 1.

Example 7 25.13 g of ODA was collected in a 5001 four-loop flask, and 336.0 g of N,N-dimethylacetamide was added thereto to dissolve it. PMDA36 in the other 50m1 eggplant flask
．． 49g was collected and added in solid form to the ODA solution. Furthermore, 10 g of N was added to remove the PMDA remaining on the wall of this 501 eggplant flask.

Reaction system with N-dimethylacetamide (four-bottle flask)
The mixture was poured into a container and stirred for an additional 30 minutes to obtain an acid anhydride group-terminated amic acid prepolymer.

On the other hand, 2.26 g of p-PDA and 4.44 g of DMB were collected in a 501 Erlenmeyer flask, and 23.3 g of N, N
-Dimethylacetamide was added and dissolved.

Add this solution to the reaction system (four-necked flask).

In the 0 or more reaction operations to obtain the copolymerized polyamic acid solution, the reaction temperature was 5 to 10°C, and PMDA and p-PD
Handling and reaction operations of A, ODA, and DMB were carried out under a stream of dry nitrogen.
A polyimide film was produced.

This film exhibited the properties shown in Table 1.

Comparative Example 1 21.54 g of 0DA was collected in a 5001 four-loop flask, and 245. OOg of N,N-dimethylacetamide was added and dissolved. On the other hand, put PM into a 100m1 eggplant flask.
23.46 g of DA was collected and added in solid form to the ODA solution. Furthermore, the PMDA remaining on the wall of this 100 ml eggplant flask was poured into the reaction system (four-bottle flask) with 10.0 g of N,N-dimethylacetamide. Continue stirring for 1 hour (continue stirring, add 15% by weight)
The reaction temperature of the obtained polyamic acid solution was kept at 5-10°C.

However, by repeating the above steps, PMDA was removed and the reaction system was placed under a stream of dry nitrogen. Next, according to the method of Example 1, a polyimide film was obtained from this polyamic acid solution. This film exhibits the properties shown in Table 1.

Comparative Example 2 4.29 g of DMB and 0D in a 500 m four-bottle flask
8.07 g of A was collected and 161.5 g of N was collected.

N-dimethylacetamide was added and dissolved, and 17.58 g of PMDA was reacted according to the method of Comparative Example 1 to obtain a 15% by weight polyamic acid solution. However, the PMDA remaining on the final wall surface was poured into 10.00 g of N,N-dimethylacetamide reaction system (four-bottle flask), and the method of Example 1 was used to obtain a copolyamic acid by random copolymerization. Accordingly, a polyimide film was obtained from this polyamic acid solution. This film exhibited the properties shown in Table 1.

Comparative Example 3 3.70 g of DMB and 0DA in a 5001 four-loop flask
4.30g was collected and 148.70g of N.

N-dimethylacetamide was added and dissolved, and 18.73 g of PMDA was reacted according to the method of Comparative Example 1 to obtain a 15% by weight polyamic acid solution by random copolymerization. However, the PMDA attached to the final wall is 10. N of OOg
, and poured into the N-dimethylacetamide reaction system (four-neck flask).

Next, according to the method of Example 1, a polyimide film was obtained from this polyamic acid solution. This film exhibited the properties shown in Table 1.

Comparative Example 4 21.54 g of 0DA was collected in a 500-liter four-loaf flask, and 245.0 g of 0DA was collected. OOg of N,N-dimethylacetamide was added and dissolved. Fl! ! On the other hand, 23.46 g of PMDA was collected in a 100 ml eggplant flask and added in solid form to the ODA solution. Continue stirring for another hour,
A 15% by weight polyamic acid solution (1) was obtained.

Meanwhile, 454 g of DMBll is placed in the 5001 four-roof flask.
was collected, 224.50 g of N,N-dimethylacetamide was added and dissolved, and 30.
09g PMDA was reacted to obtain a 15% by weight polyamic acid solution (II). However, PMDA remaining attached to the wall surface at the end of fk is 10. OOg of N,N-dimethylacetamide was poured into the reaction system (four-neck flask). In either case, the reaction temperature was maintained at 5 to 10° C., and the PMDA was collected and the reaction system was placed under a stream of dry nitrogen.

Next, separately, 112.35 g of the polyamic acid solution (1) obtained by the above method was collected in a 500 ml four-bottle flask, and further 87.65 g of the polyamic acid solution (■) was mixed therein. About 10 minutes at 10℃ 1 stirred.

Next, according to the method of Example 1, a polyimide film was obtained from this polyamic acid solution. This film exhibited the properties shown in Table 1.

(Effects of the Invention) The copolyimide of the present invention has excellent thermal dimensional stability and mechanical properties.

1. Indication of '11 Patent Application No. 1983-10154 2. Name of the invention Polyimide with excellent thermal dimensional stability 3. Relationship with the person making the amendment 11 Patent applicant (094) Kanebuchi Chemical Industry Co., Ltd. Company 4, Agent UBE Building 6, 3-7-2 Kasumigaseki, Chiyoda-ku, Tokyo.
Specification subject to amendment 7 Contents of amendment
``Engraving of the specification (no changes to the contents) As shown in the attached sheet ``-Nojin ζ,--'' 1. Patent Application No. 10154/1983 showing the incident.

3. Relationship with the case of the person making the amendment Patent applicant (094) Kanebuchi Chemical Industry Co., Ltd. 7. Contents of the amendment (1) Five lines from the bottom of page 14 of the specification, "and (■)" are deleted.

(2) On page 15, 10 lines from the bottom, delete "ya (■)".

(3) The description of Example 2 on page 29, lines 3-7 is amended as follows.

“Example 2 ODA 8.07 g, PMDA 17.58 g%D
A copolymerized polyimide film was obtained according to the method of Example 1, except that 11.54 g of M81 was used. This film exhibited the properties shown in Table 1. (4) Comparative Examples 2 to 4 on page 33, line 4 to page 35, line 14
amend the description as follows.

Comparative Example 2 87.58 g of DM and ODA in a 5001 four-loop flask
7.15 g was collected, and 1.5 g of 1B of N,N-dimethylacetamide was added and dissolved, and 15.58 g of PMDA was reacted according to the method of Comparative Example 1 to obtain a polyamic acid solution with a weight of 15 and a weight of 96. However, PMDA remaining on the final wall surface was poured into 10.00 g of N,N-dimethylacetamide reaction system (four-bottle flask) to obtain a copolyamic acid by random copolymerization. Next, Example 1
A polyimide film was obtained from this polyamic acid solution according to the method described in . This film exhibited the properties shown in Table 1.

Comparative Example 3 DM83.53g and 0DA9 in 5001 four flasks
．． 98 g was collected, 148.70 g of N,N-dimethylacetamide was added and dissolved, and 14.49 g of PMDA was reacted according to the method of Comparative Example 1 to obtain a polyamic acid solution by random copolymerization of 15% by weight. I got it.

However, the PMDA attached to the final wall is 10. The mixture was poured into an OOg N,N-dimethylacetamide reaction system (four-neck flask). Next, according to the method of Example 1, a polyimide film was obtained from this polyamic acid solution. This film exhibited the properties shown in Table 1.

Comparative Example 4 OD A 20.70 in 500 rAI four-loop flask
245.00 g of ON,N-dimethylacetamide was added and dissolved. On the other hand, 22.54 g of PMDA was collected in a 1001 eggplant flask and added in solid form to the ODA solution. Continue stirring for another hour,
A 15% by weight polyamic acid solution (1) was obtained.

On the other hand, DM 820.
41 g was collected, 224.50 g of N,N-dimethylacetamide was added and dissolved, and 2
0.97 g of PMDA was reacted to prepare a 15% by weight polyamic acid solution (II). However, PMDA remaining on the final wall surface was poured into the reaction system (fourth flask) with 10.00 g of N,N-dimethylacetamide.

In all cases, the reaction temperature was maintained at 5 to 10°C, and in the above operations, PMDA was handled and the reaction system was placed under a stream of dry nitrogen.

Next, separately, 112.35 g of the polyamic acid solution (1) obtained by the above method was collected in a 5001 four-loop flask, and further 115.58 g of the polyamic acid solution (n) was collected.
was mixed in and allowed to stand at 5 to 10°C for about 10 minutes under a stream of dry nitrogen.

Next, according to the method of Example 1, a polyimide film was obtained from this polyamic acid solution. This film exhibited the properties shown in Table 1. (5) Table 1 on page 36 of the same is amended as follows.

Claims (1)

[Claims] 1. General formula ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼ (I) [In the formula, R1 and R2 are ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼
There are groups or ▲mathematical formulas, chemical formulas, tables, etc.▼ groups, and R1 and R2 cannot be the same group. R0 is a tetravalent aromatic group, and m is a positive integer. ] A polyimide copolymer having a repeating unit represented by: 2. The polyimide copolymer according to claim 1, wherein R0 is ▲a numerical formula, a chemical formula, a table, etc.▼. 3. Claim 1 describes where R1 is ▲There are mathematical formulas, chemical formulas, tables, etc.▼, R2 is ▲There are mathematical formulas, chemical formulas, tables, etc.▼ and R0 is ▲There are mathematical formulas, chemical formulas, tables, etc.▼ polyimide copolymer. 4. Claim 1 states that R1 is ▲There are mathematical formulas, chemical formulas, tables, etc.▼, R2 is ▲There are mathematical formulas, chemical formulas, tables, etc.▼ and R0 is ▲There are mathematical formulas, chemical formulas, tables, etc.▼ polyimide copolymer. 5. The polyimide copolymer according to claim 1, which contains repeating units represented by formula (I) in an average amount of 50% by weight or more in one polymer molecule. 6. General formula ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼ (II) [In the formula, R1 and R2 are ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼
There are groups or ▲mathematical formulas, chemical formulas, tables, etc.▼ groups, and R1 and R3 cannot be the same group. R0 and m are the same as above. ] The polyimide copolymer according to claim 1, further comprising a repeating unit represented by the following. 7. The polyimide copolymer according to claim 1, wherein m is an integer of 1 to 9. 8. The polyimide copolymer according to claim 1, which has a number average molecular weight of 50,000 or more when converted to the molecular weight of the corresponding polyimide copolymer. 9. General formula ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼ (III) [In the formula, R1 and R2 are ▲ There are ▲ mathematical formulas, chemical formulas, tables, etc. ▼ R2 is ▲ There are ▲ mathematical formulas, chemical formulas, tables, etc. ▼ Group or ▲ There are mathematical formulas, chemical formulas, tables, etc. In the ▼ group, R1 and R2 cannot be the same group. R0 is a tetravalent aromatic group, and m is a positive integer. ] A polyamic acid copolymer having a repeating unit represented by: 10. The polyamic acid copolymer according to claim 9, wherein R0 is ▲a numerical formula, a chemical formula, a table, etc.▼. 11. Claim 9 describes where R1 is ▲There are mathematical formulas, chemical formulas, tables, etc.▼, R2 is ▲There are mathematical formulas, chemical formulas, tables, etc.▼ and R0 is ▲There are mathematical formulas, chemical formulas, tables, etc.▼ polyamic acid copolymer. 12. Claim 9 states that R1 is ▲There are mathematical formulas, chemical formulas, tables, etc.▼, R2 is ▲There are mathematical formulas, chemical formulas, tables, etc.▼ and R0 is ▲There are mathematical formulas, chemical formulas, tables, etc.▼ polyamic acid copolymer. 13. General formula ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼ (IV) [In the formula, R1 and R3 are ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼
There are groups or ▲mathematical formulas, chemical formulas, tables, etc.▼ groups, and R1 and R3 cannot be the same group. R0 and m are the same as above. ] The polyamic acid copolymer according to claim 9, further comprising a repeating unit represented by the following. 14. The polyamic acid copolymer according to claim 9, wherein m is an integer of 1 to 9. 15. Claim 9 whose number average molecular weight is 50,000 or more when converted to the molecular weight of the corresponding polyimide copolymer
The polyamic acid copolymer described in .