JPS63175026A - Novel polyamic acid copolymer - Google Patents

Abstract

PURPOSE:To provide the titled polymer containing a recurring unit having p-phenylenediamine as diamine component and a recurring unit having diaminodiphenyl ether as diamine component and giving a polyamide resin having excellent thermal dimensional stability, mechanical strength, etc. CONSTITUTION:The objective polymer contains the recurring units of formula I and formula II. The copolymer can be produced by using (A) an aromatic diamine component composed of 30-70mol.% p-phenylenediamine and 70-30mol.% 4,4'-diaminodiphenyl ether and (B) pyromellitic dianhydride of an amount equimolar to the component A as raw materials and polymerizing the materials in a polar organic solvent such as dimethyl sulfoxide under anhydrous condition at 5-50 deg.C.

Description

DETAILED DESCRIPTION OF THE INVENTION (Industrial Application Field) The present invention relates to a novel polyamic acid copolymer which is a precursor of a polyimide resin known as a heat-resistant resin. In particular, the present invention relates to a novel polyamic acid copolymer used as a precursor for producing polyimide resins having excellent thermal dimensional stability and excellent tensile properties.

(Prior art) Polyimide resins have conventionally been known to have a high degree of heat resistance, chemical resistance, electrical properties, mechanical properties, and other excellent properties. 36-1099
Polyimide membranes obtained using polyamic acid consisting of 4゜4'-diaminodiphenyl ether and pyromellitic dianhydride, as shown in Figure 9, have been widely used and have excellent mechanical properties such as elongation. However, it is known that it generally has a large coefficient of linear expansion and poor thermal dimensional stability. On the other hand, polyimide films obtained using polyamic acid consisting of phenylene diamine and pyromellitic dianhydride have a small coefficient of linear expansion and excellent thermal dimensional stability, but are extremely brittle and cannot be used for practical use as films. It had the disadvantage that it lacked properties and could not be used industrially.

However, in recent years, with better thermal dimensional stability,
Moreover, there is an increasing demand for polyimide resins having excellent mechanical properties such as elongation, and various studies are being conducted for this purpose. For example, in JP-A-61-158025, an attempt was made to improve mechanical properties such as elongation by using a biphenyltetracarboxylic acid component; Properties are improved. However, the resulting polyimide resin suffers from thermal softening, which impairs the excellent heat resistance of conventional polyimides.Furthermore, the yield point occurs during tensile tests, and the stress-strain resistance is high. It has problems such as deformation. This polyimide resin also has the disadvantage that it is insoluble in alkali and has extremely poor processability in post-treatment or post-processing steps such as alkali etching.

For example, as seen in JP-A-58-185624, a method has been proposed in which dimethylbenzine is introduced as a diamine component to improve thermal dimensional stability, but in this case, the methyl group in the side chain is It is known that this impairs the heat resistance of the polyimide resin produced, and that the polyimide film thus obtained has poor mechanical strength and becomes brittle.

(Problems to be Solved by the Invention) Polyimide resins that have been widely used in the past have a large linear expansion coefficient of about 3 x 105°C-1, have poor thermal dimensional stability, and when laminated with metal etc. It had problems such as warping and curling.

In response, various attempts have been made to bring the coefficient of linear expansion closer to that of metals, but the resulting polyimide films have problems with mechanical strength, heat resistance, chemical resistance, etc., and have not been put to practical use. not present.

(Means for Solving the Problems) In order to solve the problems described in -1-, the present inventors have conducted intensive studies, and as a result, a polyamic acid copolymer containing repeating units represented by the general formula It has been found that polyimide can reduce the linear expansion coefficient and improve thermal dimensional stability while maintaining properties such as heat resistance and mechanical strength of conventionally widely used polyimides.

To explain in detail the structure of this polyamic acid copolymer, the repeating unit A) and the repeating unit (B) are
(A):(B) in the copolymer in a molar ratio of 10:90
It is desirable that they be present in a ratio of from 30:70 to 70:30, preferably from 30:70 to 70:30.

When the molar ratio of the repeating unit (A) exceeds 90%, it is difficult to obtain a polymer, or the resulting polyimide film has little improvement in thermal dimensional stability.

On the other hand, it is also possible for the repeating 1' position (B) to exist in a molar ratio of 80% or more, but the resulting polyimide film is fragile and it is difficult to form a substantially -1 film. There are cases where Also, repeat position 111 (A).

If the chain length of (B), that is, the number of repeats, are m and n,
The values of m and n can take various values in the polymer chain and are not restricted in any way. Regarding the molecular weight of the polyamic acid copolymer, a weight average molecular weight of 20,000 or more, more preferably 100,000 or more is preferable from the viewpoint of the strength of the polyimide.

Next, to explain the manufacturing method of this polyamic acid copolymer, 20 to 90% of the total amount of aromatic diamine components is
The total amount of the aromatic diamine component consisting of paraphenylenediamine, preferably 30 to 70 mol%, and 4,4'-diaminodiphenyl ether, preferably 30 to 70 mol%, and pyromellitic dianhydride. Using substantially equimolar amounts of ir:? It will be done.

To explain in more detail, the molar ratio of 4,4'-diaminodiphenyl ether and P-phenylenediamine is 10.
:90 to 80:20, preferably 30:70
Using an aromatic diamine mixture mixed in a ratio of 70:30 and pyromellitic dianhydride in an amount substantially equimolar to the total amount of this mixture, a substantially anhydrous system was formed in a nail machine polar solvent. 0~100℃, preferably 5~80℃
, preferably at a temperature of 5 to 500C.

However, when obtaining the polyamic acid copolymer of the present invention, it is most desirable to use pyromellitic dianhydride alone as the aromatic tetracarboxylic dianhydride in order to obtain the effects of the present invention. 3゜3', 4.4'-biphenyltetracarboxylic dianhydride, 3.3', 4.4
It is also possible to use some of the tetrabasic acids such as -benzophenonetetracarboxylic dianhydride and naphthalene-1,2°5.6-dianhydride. Acid anhydrides other than pyromellitic dianhydride can be used within the range that achieves the practical effects of the present invention, but the amount does not exceed 5 mol %, preferably 3 mol % based on the total acid anhydride. A width meter that does not exceed % is appropriate.

Further, it is most desirable to use only two types of diamines, 4゜4'-diaminodiphenyl ether and para-phenylene diamine, as aromatic diamine components in order to obtain the effects of the present invention. (wherein R is a divalent organic group) A diamine compound represented by, for example, 4.4'-bis(4-aminophenoxy)biphenyl, 4°4'-diaminodiphenylsulfone, 3.3'-diaminodiphenyl Sulfone, bis[4-(4-aminophenoxy)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)phenylconythyl, 4,4'-diaminodiphenylmethane,
Bis(3-ethyl-4-aminophenyl)methane, bis(3-methyl-4-aminophenyl)methane, bis(3
-chloro-4-aminophenyl)methane, 3.3' -
Diaminodiphenylsulfone, 4.4'-diaminodiphenylsulfone, 3.3'-dimethoxy-4゜4'-
Diaminodiphenyl, 3,3'-dimethyl-4,4'
-diaminobiphenyl, 3,3'-dichloro-4,4'
-diaminobiphenyl, 2°2', 5,5'-tetrachloro-4,4'-diaminobiphenyl, 3,3'
-dicarboxy-4°4'-diaminobiphenyl, 3.
3'-dihydroxy-4,4'-diaminobiphenyl, 4,4'-diaminodiphenyl sulfide, 3.3
'-diaminodiphenyl ether, 3.4'-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-screw (
4-aminophenyl)-10-hydro-anthracene,
It is also possible to partially use orthotolidine sulfone, 3°3', 4,4'-biphenyltetraamine, 3°3', 4,4'-tetraaminodiphenyl ether, and the like.

4. Polyvalent amines other than 4'-diaminodiphenyl ether and phenylenediamine may be used within the range that achieves the objectives and effects of the present invention, but preferably in an amount not exceeding 10 mol% based on the total amines. It is appropriate that the subtotal does not exceed 5 mol%.

Examples of the HFab solvent used in the production reaction of the polyamic acid copolymer include sulfoxide solvents such as dimethyl sulfoxide and diethyl sulfoxide;
Formamide solvents such as N,N-dimethylformamide and N,N-diethylformamide, acetamide solvents such as N,N-dimethylacetamide and N,N-diethylacetamide, N-methyl-2-pyrrolidone, N-
Pyrrolidone solvents such as vinyl-2-pyrrolidone, phenol, 0-1m-1 or p-cresol, xylenol, halogenated phenols, phenolic solvents such as catechol, or hexamethylphosphoramide, γ
-butyrolactone, etc., and these
Although it is preferable to use them as hydrocarbons or as a mixture, it is also possible to use aromatic hydrocarbons such as xylene and luene.

Further, it is desirable from the viewpoint of handling that each of the polyamic acid copolymers is dissolved in the above-mentioned polar polar solvent from 5 to 40% by weight, preferably from 10 to 30% by weight.

The thus obtained polyamic acid polymer solution is cast or coated to form a film, and the film is dried and the polyamic acid is thermally or chemically dehydrated and ring-closed (imidized). A polyimide film can be formed. The polyimide film obtained from the polyamic acid copolymer of the present invention has extremely excellent thermal dimensional stability and, like conventionally known polyimide resins, has excellent mechanical properties such as elongation. .

(Examples) Hereinafter, the present invention will be specifically explained with reference to Examples, but the present invention is not limited only to these Examples.

Comparative Example 1 21.549 of 4.4'-diaminodiphenyl ether was collected in a 5υOml four-eye flask, and 245.009
of N,N-dimethylacetamide was added and dissolved. other/
23.469 pyromellitic dianhydride was collected in a 100 ml eggplant flask and added in solid form to the 4,4'-diaminodiphenyl ether solution. Furthermore, the pyromellitic dianhydride remaining attached to the wall of this 100 ml eggplant flask was poured into the reaction system (four-sided flask) with 10.009 N,N'-dimethylacetamide. Continuing with history, we continued to katahan for 1 hour, and 15 ff'
,' kkL 96 polyamic acid solution was obtained. The reaction temperature was kept at 5-10°C. However, in the second operation, the handling of pyromellitic dianhydride and the inside of the reaction system were placed 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 glued onto the glass plate, the coating was fixed to a support frame, and then about 100'C for about 30 minutes, about 200'C for about 60 minutes
After heating at about 300°C for about 60 minutes, dehydrating and ring-closing drying, a polyimide film of 15 to 25 microns is formed. l? is. This film exhibited the following properties.

Linear expansion coefficient (at 200℃) 3.5 Xl05 (
'C-') Elongation
85.7% Comparative Example 2 Paraphenylenediamine 1 in a 500m1 four-way flask
4.91 g was collected, 245.009 N,N-dimethylacetamide was added and dissolved, and 30.099 g of romellitic dianhydride was reacted according to the method of Comparative Example 1.
Add 1 cup of 5% by weight polyamic acid solution.

However, the pyromellitic dianhydride remaining on the final wall surface can be reacted with 10 g of N,N-dimethylacetamide (
Pour the mixture into a Yotsuro flask).

Next, polyimide films were obtained from these polyamic acid solutions according to the method of Comparative Example 1, but these films were so brittle that their properties could not be measured.

Example 1 Paraphenylenediamine 2 was placed in a 500ml four-way flask.
．． 79g and 4,4'-diaminodiphenyl ether I
Q, 319 was collected, 1G0. Add and dissolve N,N-dimethylacetamide of Ql, and add 16% according to the method of Comparative Example 1.
．． 90 g of pyromellitic dianhydride was reacted and 15
A polyamic acid solution having a weight of 06 was obtained.

However, the remaining pyromellitic dianhydride attached to the final wall was poured into the reaction system (four-eye flask) with 10.009 N,N-dimethylacetamide.

Next, according to the method of Comparative Example 1, polyimide films were obtained from these polyamic acid solutions. These films exhibited the following properties.

Coefficient of linear expansion (at 200°C) 2. OXIO'
C-1) Elongation
25.0% Example 2 Paraphenylenediamine 4 in 5υυm 1 four-eye flask
．． 359 and 4,4'-diaminodiphenyl ether 8
．． 07g was collected, 180.009 N,N-dimethylacetamide was added and dissolved, and 17g was collected according to the method of Comparative Example 1.
．． 589 pyromellitic dianhydride is reacted, 15
A polyamic acid solution containing iTi,'Q% was obtained.

However, the pyromellitic dianhydride remaining on the final wall was poured into the reaction system (four-eye flask) with 10.00 g of N,N-dimethylacetamide.

Next, according to the method of Comparative Example 1, polyimide films were obtained from these polyamic acid solutions. These films exhibited the following properties.

Linear expansion coefficient (a [200℃) 0.9 Xl05('
C-') Nakao
20,096 Example 3 Paraphenylenediamine G in a 500ml four-way flask
, OGg and 4,4'-diaminodiphenyl ether 5
．． etg was collected and L60. OOg of N,N-dimethylacetamide was added and dissolved, and according to the method of Comparative Example 1, 18
．． 33'J of pyromellitic dianhydride is reacted, 1
A polyamic acid solution having a market weight of 5% was obtained.

However, the remaining pyromellitic dianhydride was poured into the reaction system (four-eye flask) with to, oo g of N,N-dimethylacetamide.

Next, according to the h' method of Comparative Example 1, a polyimide film was prepared from these polyamic acid solutions. 1) It was. These films exhibited the following properties.

Linear expansion coefficient (at 200°C) 0.3 xlOJ
5 (“C-1) Elongation
20.0% Example 4 Paraphenylenediamine 0 in a 500m 1 four-eye flask
．． 9G9 and 4,4'-diaminodiphenyl ether 4
．． 309 was collected, 1[io, 009 N,N-dimethylacetamide was added and dissolved, and 1
8.04 g of pyromellitic dianhydride was reacted and 1
A 5% by weight polyamic acid solution was obtained.

However, the pyromellitic dianhydride remaining on the final wall was poured into the reaction system (four-eye flask) with to, oo g of N,N-dimethylacetamide.

Next, according to the method of Comparative Example 1, polyimide films were obtained from these polyamic acid solutions. These films exhibited the following properties.

Coefficient of linear expansion (at 200°C) 3. OxlO′5
（℃'）Chinese melon
30.0% Example 5 To the polyamic acid solution obtained by the method of Example 2, 33.11 fi';j of acetic anhydride and 5.329 % of pyridine were added.
added.

Next, these polyamic acid solution compositions were cast-coated onto a glass plate, dried at about 100°C for about 10 minutes, and then this semi-cured coating film was peeled off from the glass plate, and the coating film was fixed to a support frame. , then at about 200℃ for about 10 minutes, and at about 300℃ for about 20 minutes.
Heating was performed for a minute to obtain a polyimide film of 15 to 25 microns. These films exhibited the following properties.

Linear expansion coefficient (at 200℃) 0.9 XIO'
(℃1) Naka degree 3
The results of 0.0% or more are summarized in the table below.

As is clear from the table, the polyimide film obtained from the polyamic acid copolymer of the present invention has both a small coefficient of linear expansion and excellent elongation properties.

(Effects of the Invention) The polyimide film obtained from the polyamic acid copolymer of the present invention has a smaller linear expansion coefficient than known polyimide films, has excellent thermal dimensional stability, and has further improved the known linear expansion coefficient to a smaller value. This polyimide film has unprecedented flexibility, heat resistance, and workability.

Claims (2)

[Claims] (1) General formula (A) ▲Contains mathematical formulas, chemical formulas, tables, etc.▼ and (B) ▲Contains mathematical formulas, chemical formulas, tables, etc.▼ A polyamic acid copolymer containing a repeating unit represented by: (2) The repeating unit (A) and the repeating unit (B) are in a molar ratio (
The polyamic acid copolymer according to claim 1, wherein A):(B) is present in a ratio of 10:90 to 80:20.