JPS63175027A - Novel polyimide resin and production thereof - Google Patents

Abstract

PURPOSE:To obtain the titled novel resin having excellent thermal dimensional stability and mechanical properties, by separately dissolving two specific kinds of polyamic acids in organic solvents, mixing the solutions, forming a film from the mixture and drying and imidating the film. CONSTITUTION:Polyamic acids of formula I (m is positive integer) and formula II (n is positive integer) are separately dissolved in polar organic solvents at a concentration of 5-40wt.%. Both solutions are mixed together at a molar ratio (I:II) of 20:80-80:20 and the mixture is cast or coated to form a film. The film is dried and, at the same time, the polyamic acids are imidated by thermal or chemical dehydrative cyclization to obtain the objective resin.

Description

DETAILED DESCRIPTION OF THE INVENTION (Field of Industrial Application) The present invention relates to a novel polyimide resin known as a heat-resistant resin and a method for producing the same. Specifically, the present invention relates to a polyimide resin having both extremely excellent thermal dimensional stability and excellent mechanical properties, and a method for producing the same.

(Prior art) It has been known that polyimide resins have high heat resistance, chemical resistance, electrical properties, mechanical properties, and other excellent properties. -10999
Polyimide membranes made of polyimide resins made of 4,4'-diaminodiphenyl ether and pyromellitic dianhydride, as seen in , 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, rose phenylene diamine and pyromellitic acid 2
Although polyimide films obtained using polyimide resins made of anhydrides have a small coefficient of linear expansion and excellent thermal dimensional stability, they are extremely brittle and lack practical use as films, making them difficult to actually use industrially. It had the disadvantage that it could not be used.

On the other hand, in recent years, what has been achieved 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, JP-A No. 61-264028,
JP-A-61-241325, JP-A-61-18182
8, JP-A-81-158025, JP-A-58-185
[In i24, for example, rigid molecules such as phenylenediamine, dimethylbenzidine, and pyromellitic dianhydride are used for the purpose of improving thermal dimensional stability, and in some cases, the purpose is to improve mechanical properties such as elongation. 4. Using soft segments such as 4-diaminodiphenyl ether, benzophenonetetracarboxylic dianhydride, and biphenyltetracarboxylic dianhydride, polyimides were produced by copolymerization of these, and the objective described in [] was achieved. This is what I am trying to do. however,! - In the improved method using copolymerizability, for example, polyimide resins using dimethylbenzidine, benzophenonetetracarboxylic dianhydride, etc. have the disadvantage that their heat resistance is inhibited, and biphenyltetracarboxylic dianhydride Polyimide resins using such materials have problems such as a yield point occurring in a tensile test and stress distortion occurring.

Furthermore, according to such a copolymerization method, the arrangement of monomer units within one molecule becomes irregular, which is extremely difficult to control. As a result, the performance of the polyimide resin produced is extremely unstable.

(Problems to be solved by the invention) Polyimide resins that have been widely used in the past have a large coefficient of linear expansion of about 3 x 10''S°C-1, have poor thermal dimensional stability, and when laminated with metal etc. This eliminates problems such as so-called warping and curling.

In response, various attempts have been made to bring the coefficient of linear expansion closer to that of metals, but the polyimide films obtained in all cases have problems with mechanical strength, heat resistance, and chemical resistance. In the polymerization of polyamic acid, which is
The performance of the resulting polyimide resin was unstable because its molecular structure could not be controlled.

(Means for Solving the Problems) 1- As a result of intensive studies by the present inventors in order to solve the above problems, polyimide (A) mainly consisting of repeating position 711 represented by the general formula,
+: in the general formula, n is a positive integer] Polyimide (13) consisting of repeating position 111 represented by
Polyimide resins present in ratios from 0 to 80':20 were found. This polyimide resin has a small coefficient of linear expansion and excellent mechanical strength.

To explain in detail the composition of this polyimide resin,
Polyimide (A) and polyimide (1'3) are mixed in a molar ratio of 20:80 to 80:20, preferably 30:0 to 80:20. It is desirable that the proportion of

If polyimide (A) is present in a molar ratio of 80% or more, aging polyimide films have a small negative effect on thermal dimensional stability, while polyimide (B)
) is present in a molar ratio of 80% or more.
This is because, although the polyimide film obtained is fragile, it does not substantially take the form of a 1-film. In addition, the number of repeats of polyimide (A) and (13), that is, m
, n is not restricted to 161, etc. However, if high mechanical strength of polyimide is required, polyamic acid (A
o) and polyamic acid (Bo) iri Q 'l' equal proportion The weighted average value considering the mixture 1ILkk of the combination (Ao) and (Bo) is 20,000 or more 1-1 or even 100,000 The following 1- is preferable.

Next, to explain the manufacturing method of this polyimide resin, pyromellitic dianhydride is used as the aromatic tetracarboxylic dianhydride, and 4,4° is used as the aromatic diamine component.
-Using diaminodiphenyl ether, these two components are used in substantially equimolar amounts, and the number of molecules is 0 to 100 in a polar solvent.
°C1 preferably 5-80 °C1 more preferably 5-5
Polyamic acid (8°) is obtained by polymerization at a temperature of 0'C.

In one direction, pyromellitic dianhydride is used as the aromatic tetracarboxylic dianhydride, paraphenylene diamine is used as the aromatic diamine component, and these two components are used in substantially equal moles, and the polarity is 0-100℃ in solvent
, preferably at a temperature of 5 to 80°C, more preferably 5 to 50°C, to obtain polyamic acid (Bo).

When obtaining polyamic acid (Ao) or polyamic acid (Bo), it is most desirable to use pyromellitic dianhydride alone as the aromatic tetracarboxylic dianhydride in order to obtain the effects of the present invention, but for example, , 3.3", 4.4"
-Biphenyltetracarboxylic dianhydride, 3.3', 4
It is also possible to use tetrabasic acid anhydrides such as , 4'-benzophenone tetracarboxylic dianhydride, and naphthalene-1,2,5'6-dianhydride. Any acid anhydride other than pyromellitic dianhydride can be used as long as the purpose and effect of the present invention are achieved.
10 mol % or less, preferably 5 mol % or less, more preferably 3 mol % or less based on the total acid anhydride components in ). In addition, when obtaining polyamic acid (Ao), 1 4,4-diaminodiphenyl ether is added as a diamine component.
9 is most commonly used in Germany! Indeed, polyamic acid (B
When obtaining o), it is most desirable to use paraphenylene diamine alone as the diamine component, but when obtaining either polyamic acid (Ao) or polyamic acid (Bo), the general formula, H2N-R-NH2 ( In the formula, R is a divalent organic I and a diamine compound represented by ), for example, 4,4-bis(4
-aminophenoxy)biphenyl, 4,4-diaminodiphenylsulfone, 3,3°-diaminodiphenylsulfone, bis[4-(4-aminophenoquine)phenylcosulfone, bis[4-(3-aminophenoxy)phenyl] Sulfone, bis[4-(2-aminophenoxy)phenyl]sulfone, 1,4-bis(4-aminophenoxy)benzene, 1,3-bis(4-aminophenoxy)
Benzene, ■, 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'-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'-diaminodiphenyl, 4,4'-diaminodiphenyl ether, 4,4'-diaminodiphenyl sulfide, 3,3'-diaminodiphenyl ether, 3,
4°-diaminodiphenyl ether, 4,4°-diaminodiphenylmethane, 4.4°-diaminobiphenyl,
4.4°-Diaminooctafluorobiphenyl, 2.4
-diaminotoluene, paraphenylenediamine, 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)-IO-hydro-anthracene, orthotolidine sulfone and 3,3°,4,4'
It is also possible to use some of the tetramines, such as -biphenyltetraamine, 3,3°, 4,4°-tetraaminodiphenyl ether. Polyvalent amines other than 4,4'-diaminodiphenyl ether and para-phenylene diamine can be used in any amount as long as the desired effect of the present invention is achieved, but based on the total amine components in the polymer (Ao) or (Bo). It is appropriate to use 10 mol % or less, preferably 5 mol % or more, and more preferably 3 mol % or less.

Here, polyamic acid (8°) and polyamic acid (13°
Examples of the polar solvent used in the production reaction include sulfoxide-based solvents such as dimethyl sulfoxide and diethyl sulfoxide, formamide-based solvents such as N,N-dimethylformamide, N,N-diethylformamide, and N,N-dimethylformamide. - Acetamide solvents such as dimethylacetamide, N,N-diethylacetamide, pyrrolidone solvents such as N-methyl-2-pyrrolidone, N-vinyl-2-pyrrolidone, phenol, 0-1l-1 or p
-cresol, xylenol, halogenated phenol,
Examples include phenolic solvents such as catechol, hexamethylphosphoramide, γ-butyrolactone, etc., and it is desirable to use these alone or as a mixture; Partial use is also possible. Further, polyamic acid (Ao) and polyamic acid (Bo) are each dissolved in the above-mentioned 6-unit polar solvent by 5 to 40 ton%, preferably 5 to 30 ton%, more preferably 5 to 25 ton%. It is desirable from the viewpoint of handling.

A polyamic acid solution in which polyamic acid (A") is dissolved in a polar polar solvent and a polyamic acid solution in which a polyamic acid (Bo) is dissolved in a polar solvent in a repeating unit molar ratio ( A'): (Bo) is 20: 80
to 80:20, preferably 30:0 to 80+20, to obtain a solution of the polyamic acid composition which is a precursor for obtaining the polyimide resin of the present invention. There are no particular restrictions on the method of mixing this polyamic acid solution. Next, the polyimide resin of the present invention can be obtained by thermally or chemically dehydrating and ring-closing (imidizing) the solution of the polyamic acid composition as a precursor.

First, to explain the method of thermally dehydrating and ring-closing (imidization), a solution of the polyamic acid composition is cast or coated on a drum or endless belt-F to form a film,
The membrane is dried at crystallinity below 150° C. for about 3Q to 90 minutes to obtain a self-supporting membrane. Next, this is peeled off from the support, the ends are fixed, and then gradually heated to about 100 to 500°C, and after cooling, removed to obtain a polyimide resin.

Next, to explain the method of chemically dehydrating and ring-closing (imidization), add the dehydrating agent described above and a catalytic amount of tertiary amine to the solution of the polyamic acid composition mentioned above, and pour this into a drum. Alternatively, the endless belt 1- is cast or coated to form a film, and the film is heated at a temperature of 150°C or less for about 5 to 30 minutes.
Dry for 0 minutes to obtain a self-supporting membrane. Next, after peeling it off from the support and fixing the end, it was
It is gradually heated to 0° C., and after cooling, it is removed to obtain a polyimide resin. Examples of the dehydrating agent used at this time include aliphatic acid anhydrides and aromatic acid anhydrides.

Examples of catalysts include aliphatic tertiary amines such as triethylamine, aromatic tertiary amines such as dimethylaniline, and cyclic tertiary amines such as pyridine, picoline, and isoquinoline. .

(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 Examples 1 to 3 21.549 of 4,4°-diaminodiphenyl ether was collected in a 500 ml four-way flask, and 845.9.
009.245.009.95.00 g of N,N-dimethylacetamide was added and dissolved. On the other hand, 100m1
Pyromellitic dianhydride 23.46' in an eggplant flask
;i was collected and added in solid form to the 4,4°-diaminodiphenyl ether solution. Furthermore, this 100+
The pyromellitic dianhydride remaining attached to the wall of the nl round bottom flask was poured into the reaction system (four-eye flask) with 1'0.00 g of N, +'J-dimethylacetamide. Continuing from the history, we continued to accumulate for 1 hour and each 5.
A 15.30% by weight polyamic acid solution was obtained. The reaction temperature was kept at 5-10°C. However, in the following procedure, 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 peeled off from the glass plate, the coating was fixed on a support frame, and then about Heated at 100°C for about 30 minutes, at about 200°C for about 60 minutes, and at about 300°C for about 60 minutes, and after dehydration and ring closure drying,
A 25 micron polyimide film was obtained from the above. These films exhibited the following properties.

Linear expansion coefficient 1B (at 200℃) 3.5X 1
O-5 (cm/ca+/'C) elongation
85.7% Comparative Examples 4 to 6 14.919 paraphenylenediamine was collected in a 500+nl four-way flask, and 845.00 g and 24
5.00 g, 95.009 N,N-dimethylacetamide was added and dissolved, and 30.0 g was added according to the method of Comparative Examples 1 to 3.
99 pyromellitic dianhydrides were reacted to give 5.15% each
．． 30! A polyamic acid solution of fiu% was obtained. However, the pyromellitic dianhydride remaining on the final wall surface of the mother tube is to
,oog of N,N-dimethylacetamide in the reaction system (
into a four-eye flask).

Next, polyimide films were obtained from these polyamic acid solutions according to the methods of Comparative Examples 1 to 3, but these films were so fragile that their properties could not be measured.

Example 1 158.729 of the polyamic acid solution obtained according to the method of Comparative Example 2 was collected in a 500 ml four-way flask, and 158.729 W9 of the 15 W9 obtained according to the method of Comparative Example 5 was collected.
6 polyamic acid solution was added thereto, and the mixture was stirred at 5 to 10° C. for about 10 minutes under a stream of dry nitrogen. Next, Comparative Example 1
A polyimide film was obtained from this 15% by weight polyamic acid mixed solution according to the method described in the following.

The second film showed the following properties.

Linear expansion coefficient (at 200℃) 1.72X10'
(cm/c+n/”C) Elongation 32,
8% Example 2 112.35 g of the 15% polyamic acid solution obtained according to the method of Comparative Example 2 was collected in a 5001 four-piece flask, and the 15% polyamic acid solution was further prepared according to the method of Comparative Example 5. 87.859 was mixed in and stirred for 5 to 10°C under a stream of dry nitrogen. Next, according to the method of Comparative Examples 1 to 3, a polyimide film was obtained from this 15% polyamic acid mixture. This film exhibited the following properties.

Coefficient of linear expansion (at 200°C) 0. [i9X IQ
-5 (cm/cm/'C) stretch 14
．． 796 Example 3 176.98 g of the 5% by weight polyamic acid solution obtained according to the method of Comparative Example 1 was collected in a 500 ml four-eye flask, and 30 tons of the 96 polyamic acid solution obtained according to the method of Comparative Example 6 was added to the 500 ml four-eye flask. 0.02 g was mixed in and stirred for about 10 minutes at 5 to 10°C under a stream of dry nitrogen. Next, Comparative Example 1~
A polyimide film was obtained from this polyamic acid mixed solution according to method 3. This film exhibited f/lE quality of JJ.

Coefficient of linear expansion (at 200°C) 0. G9x 10'
(am/c+n/'C) Elongation 1
4.7% Example 4 A 35.219% polyamic acid solution obtained according to the method of Comparative Example 3 was collected in a 500 ml four-walled flask, and a 5 mm% polyamic acid solution IG4. 79 g was mixed in, and the mixture was incubated at 5 to 10° C. for about 10 minutes under a stream of dry nitrogen.

Next, according to the Knob method of Comparative Examples 1 to 3, a polyimide film was obtained using this polyamic acid mixed solution. This film exhibited the following properties.

0! Expansion coefficient (at 200℃) 0.69x [0-
5 (cm/c+n/℃) Elongation 14.
796 Example 5 Into a 500 ml four-eye flask, 59.877 tons of the 15-tonne 96-volume polyamic acid solution obtained according to the method of Comparative Example 1 was collected, and 96 tons of the 15-tonne solution obtained according to the method of Comparative Example 2 was further collected.
Polyamic acid solution 140.137 was mixed therein and allowed to stand at 5 to 10°C for about 10 minutes under a stream of dry nitrogen. Next, according to the methods of Comparative Examples 1 to 3, this 15! A polyimide film was removed from the J′i Melon 06 polyamic acid mixed solution. This film had the following properties.

To wire 11g 5J (at 20 mouths C) 0.23
X 1O-5 (cm/cm/'C) Elongation
5.096 Example 6 A 15 I = 96 polyamic acid solution obtained according to the method of Comparative Example 1 was placed in a 500 ml four-eye flask, 59.8
77 was collected, and further 15 obtained according to the method of Comparative Example 2
140.13 g of heavy weight 06 polyamic acid solution was mixed therein, and the mixture was allowed to stand for about 10 minutes at 5 to 10° C. in a drying room under an atmosphere of jf+ε. Next, 35.009 acetic anhydride and 5.009 pyridine were added, and this solution was cast onto a glass plate and dried at about 80°C for about 10 minutes. Peel it off from the board, fix the coating on a support frame, then heat it at about 100°C for about 30 minutes, about 200°C for about 60 minutes, and at about 300°C for about 60 minutes, and after drying it A 25 micron polyimide film was obtained. This film exhibited the following properties.

Linear expansion coefficient (at 200°C) 0.23X 10'
(cm/cm/'C) Nakajo 7.
596 Example 7 Four 500 m1 [30-weight 96-weight polyamide acid solution obtained according to the method of Comparative Example 3 35.219 was collected in a coffin flask, and also 5-weight polyamide acid solution obtained according to the method of Comparative Example 4]0
6 polyamic acid solution IG4.799 was mixed therein, and the mixture was stirred for about 10 minutes at 5 to 10°C in a dry nitrogen stream.

Next, prepare 35.00 g of acetic anhydride and 5.00 g of pyridine, and cast this solution onto a glass plate to form a coating of approximately 8.0 g.
After drying at 0°C for about 10 minutes, this self-supporting coating film was peeled off from the glass plate, the coating film was fixed on a support frame, and then dried at about 100°C for about 30 minutes11 (1, about 2 (1) Approximately 60 at 0℃
After heating at about 300° C. for about 60 minutes and drying, a 15 to 25 micron polyimide film was removed. This film exhibited the following properties.

Coefficient of linear expansion (at 200°C) O, [i9X 101
0-5(/em/'C) Elongation 19,
5°6 The results of Comparative Examples 1 to 3 and Examples 1 to 7 are summarized in Table 1 Polyamic acid Polyamic acid Linear expansion coefficient Elongation molar ratio Solution concentration (at 200°C) (%)
(A):(B) (weight%) (am/cm/
'C) Comparative example 1 100:0 5.0 3.49 X
l0-5 85.7 Comparative Example 2 +00 :0 15.
0 3.49 Xl0-5 85.7 Comparative example 3 100
:Oao, o 3.49 Xl0-5 85.7 Example 1 75 :2515.0 1.72XIO-
'32.8 Example 2 50: 5015.0
0.69 X 10' 14.7 Example 3 50
:50 7.9 0.69 xlO-514,7 Example 4 50 :50 9.4 0. +39 xlO'
14.7 Example 5 25: 7515.0 0.
23 x 10' 5.0 Example 6 25:
75 f5.0 0123 XIO″57.5 Example 7
50:5o 9.4 0. G9 XLO-'
19.5 (Effects of the Invention) The polyimide film obtained from the polyimide resin of the present invention has a smaller linear expansion coefficient than known polyimide films, and has a thermal
It has excellent legal stability, and has the effect of combining flexibility, heat resistance, and processability, which previously known polyimide films with improved coefficients of linear expansion have not been able to have.

Furthermore, by controlling the structure of repeating units in one molecule of polyimide, which has not been possible with modification by conventional copolymerization methods, the performance of the resulting polyimide film can be made constant.

Claims (2)

[Claims] (1) Mainly general formula ▲ Numerical formulas, chemical formulas, tables, etc. ▼ [In the formula, m is a positive integer] Polyimide (A) consisting of a repeating unit represented by ▼ [In the formula, n is a positive integer] Polyimide (B) consisting of repeating units represented by (A):(B) has a molar ratio of 20:80 to 80:
Polyimide resin present in proportions up to 20. (2) There are mainly general formulas ▲ mathematical formulas, chemical formulas, tables, etc. ▼ [In the formula, m is a positive integer] Polyamic acid (A') consisting of repeating units represented by 5 to 40% by weight in an organic polar solvent % dissolved polyamic acid solution, and mainly the general formula ▲ mathematical formula, chemical formula, table, etc. A polyamic acid solution having 5 to 40% by weight dissolved in a solvent is prepared in a molar ratio of repeating units (A'):(B') of 2.
A polyamic acid solution mixed in a ratio of 0:80 to 80:20 is cast or coated to form a film,
A method for producing a polyimide resin, which comprises drying the film and thermally or chemically dehydrating and ring-closing (imidizing) the polyamic acid to produce polyimide.