JP3026957B2 - Preparation of polyimide with excellent thermal dimensional stability. - Google Patents

Description

Description: TECHNICAL FIELD [0001] The present invention relates to a heat-resistant resin.
It relates to a known polyimide resin. For more information,
Novel PO with both excellent dimensional stability and excellent tensile properties
It relates to a limide copolymer. 2. Description of the Related Art Polyimide has excellent heat resistance.
Well known as Ma. This polymer is
Excellent chemical resistance, electrical and mechanical properties
You. A typical polyimide is 4, 4 as is well known.
Without 4'-diaminodiphenyl ether and pyromellitic acid
Commercially produced on a large scale with polymers derived from water
ing. This polymer is used for flexible printed circuit boards
It is used as an electrical material that requires heat resistance. This port
Rimmer has excellent mechanical properties such as tensile properties,
Poor thermal dimensional stability (3 × 10 ^-Five ° C ^-1 Large line
Expansion coefficient). Thermal dimensional stability
One example of the problem caused by inferiority is the flexible print base.
The board is warped or curled. With flexible printed circuit boards
Is laminated with a polyimide film and metal.
Linear expansion coefficient is smaller than polyimide film
Due to temperature changes during processing and use of
This causes warpage and curl. [0003] The problem caused by poor thermal dimensional stability is
Other examples are warpage and curl of the magnetic recording material. Recent high
For density magnetic recording materials, metal is deposited on the base film.
And manufactured by. Metal deposition is done at high temperatures
Heat-resistant polymer such as polyimide is the base film
Is preferred. However, the linear expansion of polyimide film
The number is larger than the coefficient of linear expansion of metal, so warpage and curl
It will happen. [0004] Polyimide is heat-resistant and therefore large.
Often undergoes significant temperature changes. Therefore excellent thermal dimensions
A polyimide having stability is desired. Especially recent
With the development of electronics, these demands have increased
ing. Examples of polyimides having excellent thermal dimensional stability include:
JP-A-61-158025, 61-181828
Gazette, JP-A-61-241335, 61-26402
No. 8 discloses this. JP-A-61-158025
And JP-A-61-264028.
Polyimide is biphenyl as tetracarboxylic dianhydride.
Letetracarboxylic dianhydride and optionally pyromellitus
Para-diene diamine as diamine using acid dianhydride
Min and optionally 4,4'-diaminodiphenyl ether
This is a polyimide obtained by condensation polymerization using a polymer. Special
Polyi disclosed in Japanese Unexamined Patent Publication No. 61-181828
Mido is like 2,5-diaminopyridine as diamine
Aromatic tetracarboxylic acid using a specific heterocyclic diamine
It is a polyimide obtained by polycondensation with an anhydride. Special
The polyi disclosed in Japanese Unexamined Patent Publication No. 61-241325
The amide is 9,9-bis (4-aminophenyl) as the diamine
Le) using anthracene and paraphenylenediamine,
Biphenyltetracarbo as tracarboxylic dianhydride
Polyimide obtained by condensation polymerization using dianhydride
It is. All of these polyimides are biphenyltet
Lacarboxylic dianhydride, heterocyclic diamine or 9,9
-Bis (4-aminophenyl) anthracene
Yes, expensive compounds are used as raw materials. [0006] The object of the present invention is excellent.
Conventional with excellent thermal dimensional stability and excellent mechanical properties
It is to obtain a polyimide different from polyimide. Departure
Another purpose of Ming is to produce warpage and curl when laminated with metal.
Obtaining polyimide with excellent mechanical properties
It is in. Another object of the present invention is to obtain from ordinary inexpensive raw materials.
To obtain polyimide with excellent thermal dimensional stability.
And there. [0007] The present invention provides (a) to (c).
The general formula (I) and the general formula (I)
Formula (II): (Where R ₀ Is an aromatic tetracarboxylic acid residue
Of a copolymerized polyimide having a repeating unit represented by
Is the law. (A) 4,4'-diaminodiphenyl ether and / or
Represents paraphenylenediamine with the general formula (III) and
The total amount of the repeating unit represented by (IV) is polyamic acid content
Diamine contained so as to be 80% by weight or more on average
And 40 to 99 mol% of aromatic tet based on this diamine
The amino group is reacted by reacting lacarboxylic dianhydride.
A step of synthesizing a terminal amic acid prepolymer. (B) The amic acid prepolymer is prepared by adding 10 to 9
Formula (III) and Formula (IV) used at 0 mol%: A step of synthesizing a polyamic acid having a unit represented by the formula: (C) Dehydrating the polyamic acid to synthesize a polyimide
Process. DESCRIPTION OF THE PREFERRED EMBODIMENTS One of the copolymerized polyimides of the present invention
Is an example of excess equivalent to aromatic tetracarboxylic dianhydride.
Amino acid-terminated amide prepolymer using diamine
The method of the present invention using the step (a) of synthesizing a
Is a copolymerized polyimide obtained by the above method. For example, organic solvents
Medium, 10 to 90 moles to diamine used in all processes
% Aromatic diamine (A) and this diamine (A)
40 to 99 mol% of aromatic tetracarboxylic acid
React with hydrate to form amino group-terminated amic acid prepolymer
And then add all the diamine to the amic acid prepolymer solution.
90 to 10 mol% of aromatic diamine (B)
After the addition, so as to be substantially equimolar to all diamines,
Addition of insufficient aromatic tetracarboxylic dianhydride
Thus, a copolymerized polyamic acid is obtained. This polyamide
The acid solution is cast into a film, for example, by casting or coating, and the film is formed.
And drying the copolymerized polyamic acid with heat or
Is chemically dehydrated and ring-closed (imidized).
Obtain copolymerized polyimide with both qualitative and mechanical properties
be able to. Diamines (A) and (B) are 4,4'-diamines
Aminodiphenyl ether, paraphenylenediamine
Or (A), (B)
Cannot be the same amine. (A) and (B)
Although it is preferable to use only these amines,
Other amines may be used in combination. Other a
When a min is used in combination, it is represented by the general formulas (I) and (II).
The total amount of the repeating units is 5 on average in the polyimide molecule.
0% by weight or more, preferably 80% by weight or more, more preferably
Or more preferably 90% by weight or more. Another example of the copolymerized polyimide of the present invention is
Aromatic tetracarboxylic dianhydride in excess equivalent to min
Amide acid prepolymer terminated with acid anhydride
Obtained by the process of the present invention using the step (a) of synthesizing.
Is a copolymerized polyimide. For example, aromatic diamine
(A) and an excess molar amount of aromatic tetracarboxylic acid
Reaction of acid dianhydride in organic polar solvent
Amide acid prepolymers having a functional group
Aromatic diamine (B) is converted to aromatic tetraca
Add so that it is substantially equimolar to rubonic dianhydride.
To give a copolymerized polyamic acid. This copolymerization
The polyamic acid is subjected to dehydration ring closure (imide
) To provide excellent dimensional stability and mechanical properties
It is possible to obtain a copolyimide having the same function. Zia
Min (A) and (B) are 4,4 'diaminodiphenyl ate
Ter, paraphenylenediamine or mixtures thereof
(A) and (B) are the same amine
And not. Only these amines are used as (A) and (B)
It is preferable to use other amines.
You can do that. If other amines are used together,
The total amount of the repeating units represented by the general formulas (I) and (II) is
50% by weight or more on average in the polyimide molecule, preferably
80% by weight or more, more preferably 90% by weight or more.
It is preferred that In the copolymer polyimide of the present invention, one
Based on paraphenylenediamine of the general formula (I)
And a 4,4′-dia represented by the general formula (II)
Repeat units derived from minodiphenyl ether in the molecular chain
Excellent thermal dimensional savings.
A polyimide having qualitative and mechanical properties is obtained. Departure
The light polyimide is paraphenylenediamine and 4,4'-
La using diaminodiphenyl ether as diamine
Diamine copolymerized polyimide or paraphenylenediamine
Amine homopolymer of polyimide and 4,4'-
Polyimide homo with diaminodiphenyl ether
Thermal dimensional stability and mechanical properties compared to polymer mixtures
Both quality is excellent. The polyimide of the present invention is
2.5 × 10 (at 50 ° C. to 300 ° C.) ^-Five / ℃
The elongation is 20% or more at below, and 2.0 × 10 ^-Five / ℃ or less
Lower than 40%, furthermore 1.5 × 10 ^-Five 50 / C or less
% Is obtained. In addition, this polyimide
It has a tensile modulus. Polyamide obtained by the present invention
Acids and polyimides have the next block as a repeating unit.
Polymer. Embedded image (Where R ₁ , R _Two Is 4,4'-diaminodiphenyle
-Diamines selected from ter, paraphenylenediamine
Residue, R ₀ Is a tetracarboxylic acid residue, and m and n are positive integers.
Number) The values of m and n are almost constant throughout the molecular chain.
Preferred, especially using acid anhydride terminated amic acid prepolymer
In this case, n can be obtained throughout the molecular chain.
The mechanical properties of this product are particularly excellent. The present invention
There is no particular limitation on the molecular weight of the copolymerized polyimide
However, due to physical properties, the number average molecular weight is 50,000 or more, and
Above, especially 100,000 or more, further preferably 120,000 or more.
The molecular weight of the copolymerized polyimide is determined by the
It is an estimated value from the number average molecular weight of the mimic acid. Therefore the precursor
The molecular weight of the copolymerized polyamic acid corresponds to the above value
Is preferred. In the present invention, an essential aromatic diamine component is used.
And 4,4'-diaminodiphenyl ether and parafe
Nilendiamine is used. Usage ratio is 1 / 9-9 /
1, preferably 1/7 to 7/1, more preferably 1/4
４4/1 (molar ratio). Aromatic tetracarboxylic acid used in the present invention
As anhydrides, pyromellitic dianhydride, 3,3 ',
4,4'-biphenyltetracarboxylic dianhydride, 3,
3 ', 4,4'-benzophenonetetracarboxylic acid
Water, naphthalene-1,2,5,6-tetracarboxylic acid
And dianhydrides. These can be used alone or mixed
Can be used. These aromatic tetracarboxylic acids
Of the acid dianhydrides, pyromellitic dianhydride is preferred.
Pyromellitic dianhydride used in all processes
Weight of wholly aromatic tetracarboxylic dianhydride used in
% Or more, preferably 70% by weight or more, further 90% by weight
% Is desirably used. Diamine, etc.
Other than the above, a general formula: _Two NR-NH _Two [Wherein, R is a divalent organic group]
Compounds such as 4,4'-bis (4-aminophenoxy)
C) biphenyl, 4,4'-diaminodiphenylsulfo
, 3,3'-diaminodiphenylsulfone, bis [4
-(4-aminophenoxy) phenyl] sulfone, bis
[4- (3-aminophenoxy) phenyl] sulfone,
Bis [4- (2-aminophenoxy) phenyl] sulfo
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-a
Minophenyl) methane, bis (3-methyl-4-amino)
Phenyl) methane, bis (3-chloro-4-aminophen)
Nyl) methane, 3,3'-dimethoxy-4,4'-dia
Minodiphenyl, 3,3'-dimethyl-4,4'-dia
Minobiphenyl, 3,3'-dichloro-4,4'-dia
Minobiphenyl, 2,2 ', 5,5'-tetrachloro-
4,4'-diaminobiphenyl, 3,3'-dicarboxy
C-4,4'-diaminobiphenyl, 3,3'-dihydrido
Roxy-4,4'-diaminobiphenyl, 4,4'-di
Aminodiphenyl sulfide, 3,3'-diaminodiph
Phenyl ether, 3,4'-diaminodiphenyl ether
4,4'-diaminobiphenyl, 4,4'-diami
Nooctafluorobiphenyl, 2,4-diaminotolue
, Metaphenylenediamine, 2,2-bis [4- (4
-Aminophenoxy) phenyl] propane, 2,2-bi
[4- (4-aminophenoxy) phenyl] hexaf
Fluoropropane, 2,2-bis (4-aminophenyl)
Propane, 2,2-bis (4-aminophenyl) hexa
Fluoropropane, 2,2-bis (3-hydroxy-4
-Aminophenyl) propane, 2,2-bis (3-hydrido)
Roxy-4-aminophenyl) hexafluoropropa
9,9-bis (4-aminophenyl) -10-hydr
Low-anthracene, ortho-tolidine sulfone and 3,
3 ', 4,4'-biphenyltetraamine, 3,3',
Polyvalent compounds such as 4,4'-tetraaminodiphenyl ether
It is also possible to use a part of the min compound. In the present invention, a method of adding a monomer during polymerization
Method is important, and amino group-terminated amic acid prepolymer
When used as an intermediate, 1 to all diamine components
0-90 mol%, preferably 15-85 mol%, more preferably
Preferably, 20 to 80 mol% of 4,4'-diaminodiphene is used.
Contains nyl ether and / or paraphenylenediamine
Diamine (A) and 40 to
Reacts with 99 mol% of aromatic tetracarboxylic dianhydride
Thus, an amino group terminal amic acid prepolymer is obtained. Next
In this amino group-terminated amic acid prepolymer solution,
90 to 10 mol%, preferably 85 to 1 mol% based on the amine
5 mol%, more preferably 80 to 20 mol% of diamine
(B) has a unit represented by the general formulas (III) and (IV).
After additional addition to obtain copolymerized polyamic acid,
In order to be substantially equimolar to the diamine component,
Add aromatic tetracarboxylic dianhydride and react
The copolymerized polyamic acid of the present invention is obtained. Acid anhydride terminal
When a amic acid prepolymer is used as an intermediate,
For aromatic tetracarboxylic dianhydride and this acid anhydride,
50-90% mol%, preferably 50-87.5%, further
Preferably 50 to 80 mol% of 4,4'-diaminodi
Phenyl ether and / or paraphenylenediamine
Containing diamine (A), and acid anhydride group terminal amide acid
Obtain a repolymer. Then here the acid anhydride and all diamines
The diamine (B) is added so that the amount is substantially equimolar.
Copolymer having units represented by general formulas (III) and (IV)
Copolyamide acid is added to obtain polyamic acid.
Get. Amino acid-terminated prepolymers and acid anhydrides
Intermediates such as terminal amide acid prepolymers are, for example,
Such a compound. Embedded image (Where R ₀ Is the same as above.) This intermediate is a low-molecular compound having a terminal amino group or acid anhydride group.
The amount may be polyamic acid. Of this amic acid intermediate
The number average molecular weight is lower than that of the finally obtained copolymer polyamic acid.
As small as possible, but preferably 20,000 or less, especially 10,000 or less.
New Used for the production reaction of copolymerized polyamide
Examples of the organic solvent include dimethyl sulfoxide,
Sulfoxide solvents such as ethyl sulfoxide, N, N
-Dimethylformamide, N, N-diethylformamide
Solvent such as formamide, N, N-dimethylacetate
Acetoacetate such as amide, N, N-diethylacetamide
Amide solvent, N-methyl-2-pyrrolidone, N-vinyl
-2-Pyrrolidone solvents such as pyrrolidone, phenol
O, m- or p-cresol, xylenol,
Phenolic solvents such as halogenated phenols and catechol
Medium, or hexamethylphosphoramide, γ-butyro
Organic polar solvents such as lactones.
It is desirable to use them alone or as a mixture,
Is the addition of aromatic hydrocarbons such as xylene and toluene
It is possible. In addition, the copolymeric polyamic acid is as described above.
5 to 40% by weight, preferably 5 to 30% by weight in the organic solvent
%, More preferably 5 to 25% by weight
It is desirable from the viewpoint of handling. The reaction temperature is from 0 to 100 ° C., preferably from 5 to 100 ° C.
80 ° C, more preferably 5 to 50 ° C.
Used as an intermediate of acid anhydride group-terminated amic acid prepolymer
In some cases, the reaction temperature is 30 ° C or less, and further 10 ° C or less.
Is preferred. The reaction is performed within 10 hours, preferably 5 hours or less.
Of these, more preferably within 3 hours. From the copolymerized polyamic acid thus obtained
Copolymerized polyimide can be obtained.
And two generally known methods are possible. That is, there are (a) a method of thermally dehydrating a ring-closing (imidization) and (b) a method of chemically dehydrating a ring-closing (imidization). More specifically, (a) is, for example, a copolymer
Support plate, heated drum or endless polyamic acid solution
After casting and drying on a support such as a belt, a self-supporting film
Get. This is further heated, dried and imidized, and imidized.
This is a method for obtaining a film. The temperature at the time of heating is 200-50
A temperature in the range of 0 ° C. is preferred, more preferably 300-500.
° C, particularly preferably 400 to 500 ° C. Heating during heating
The heating rate is not particularly limited, but the temperature is gradually increased and the maximum temperature is
Preferably, the temperature is reached. Heating time is the highest temperature
It depends on the temperature, and you can heat for the time corresponding to the temperature
However, the range from 10 seconds to 1 minute after reaching the maximum temperature is preferable.
Good. In (b), for example, a copolymerized polyamic acid solution
Dehydrating agents such as acetic anhydride and pyridine, picolines,
After mixing tertiary amines such as norins,
Thus, a polyimide film is obtained. Heat self-supporting membrane
The membrane may remain on the support when
It may be peeled off from the support,
Then, when the end is fixed and heated, the linear expansion coefficient
Is preferable since a copolymer having a small particle size can be obtained. Also thermally
Comparison of imidization method and chemically imidization method
Then, the chemical method produces mechanical polyimide
Both strength and coefficient of linear expansion are excellent. The copolymerized polyimide thus obtained
Has excellent thermal dimensional stability and
Excellent in mechanical properties such as elongation, similar to polyimide resin sold
Have been. Specifically, the coefficient of linear expansion is 2.5 × 10 ^-Five Less than
And has an elongation of 20% or more.
Polyimide or copolymer having (I) or (II) repeating unit
Better thermal dimensional stability and mechanical properties than polyimide
They have. The polyimide copolymer of the present invention has excellent thermal properties.
Has dimensional stability, mechanical properties and moderate tensile modulus,
Flexible printed circuit board with film shape, general magnetic
Magnetic tape, magnetic disk, etc. for recording and perpendicular magnetic recording
Throat for magnetic recording materials, ICs, LSIs, solar cells, etc.
It is extremely useful for a passivation film of a conductor element. Next, the present invention will be described based on examples. Reference Example 1 In a 500 ml four-necked flask, 4,4'-diaminodife
Collect 10.31 g of nil ether (hereinafter referred to as ODA)
And 145.00 g of N, N-dimethylacetamide
Added and dissolved. On the other hand, Piromeri was placed in a 50 ml eggplant flask.
16.90 g of citrate dianhydride (hereinafter referred to as PMDA)
Collected and added in solid form to the ODA solution. More
PMD remaining on the wall in a 50 ml eggplant flask
A with 10.00 g of N, N-dimethylacetamide
Pour into the reaction system (four-neck flask) and stir for an additional hour.
Subsequently, an acid anhydride group-terminated amic acid prepolymer was obtained. one
One, paraphenylenediamine in a 50 ml Erlenmeyer flask
2.79 g (hereinafter referred to as p-PDA) was collected, and
Add and dissolve 00 g of N, N-dimethylacetamide
Was. This solution is added into a reaction system (four-neck flask),
A copolymerized polyamic acid solution was obtained. In the above reaction operation
The reaction temperature is 5-10 ° C, PMDA and p-PD
The handling of A and the inside of the reaction system are performed under a stream of dry nitrogen.
Was. Next, these polyimide acid solutions were added to a glass plate.
And then dried at about 100 ° C for about 60 minutes.
Peel the amic acid coating from the glass plate and use the coating as a support frame
Fix, then at about 100 ° C for about 30 minutes, at about 200 ° C
Heat for about 60 minutes at about 300 ° C for about 60 minutes to close the dehydration ring
After drying, a polyimide film of 15 to 25 microns was obtained. This film had a coefficient of linear expansion and a draw ratio shown in Table 1.
The tensile elongation and tensile modulus were shown. The linear expansion coefficient in Table 1
The numbers are values at 200 ° C. Reference Example 2 8.07 g of ODA, 17.58 g of PMDA, p-P
Except using 4.35 g of DA, follow the method of Reference Example 1,
A copolymerized polyimide film was obtained. This film is shown in Table 1.
Showed properties. REFERENCE EXAMPLE 3 4.35 g of p-PDA was placed in a 500 ml four-necked flask.
110.00 g of N, N-dimethylacetamide
Was added and dissolved. On the other hand, PMD
17.58 g of A was collected and solidified in the p-PDA solution.
Added in form. Furthermore, the wall in this 50 ml eggplant flask
10.00 g of N, N-diethyl PMDA remaining on the surface
Flow into the reaction system (four-necked flask) with methylacetamide
And continue stirring for another 1 hour.
A repolymer was obtained. On the other hand, O
8.07 g of DA was collected and 50.00 g of N, N-dimethyl
Tylacetamide was added and dissolved. This solution is
(Four-necked flask)
A solution was obtained. In the above reaction operation, the reaction temperature is 5 to 1
0 ° C, PMDA and ODA handling and reaction system
Was performed under a stream of dry nitrogen. Next, the method of Reference Example 1 was used.
Accordingly, a copolymerized polyimide film was obtained. This film is shown in Table 1.
The properties shown in Table 1 were shown. Reference Example 4 12.02 g of ODA, 16.36 g of PMDA, p-
Except that 1.62 g of PDA was used, the method of Reference Example 1 was followed.
Thus, a copolymerized polyimide film was obtained. This film is listed in Table 1.
The properties shown are shown. Reference Example 5 6.06 g of p-PDA, 18.33 g of PMDA, O
Except when using 5.61 g of DA, the method of Reference Example 3 was followed.
Thus, a copolymerized polyimide film was obtained. This film is listed in Table 1.
The properties shown are shown. Reference Example 6 The polyimide acid solution obtained by the method of Reference Example 2
33.88 g of aqueous acetic acid and 5.32 g of pyridine were added. Next, this polyamic acid solution composition is
After casting on a plate and drying at about 100 ° C for about 10 minutes,
Peel the semi-cured coating film from the glass plate and use the coating film as a support frame
Fix, then at about 200 ° C for about 10 minutes, at about 300 ° C
Heat for about 20 minutes and apply 15-25 micron polyimide
A membrane was obtained. This film exhibited the properties shown in Table 1. Example 1 2.43 g of p-PDA was placed in a 500 ml four-necked flask.
Take 135.00 g of N, N-dimethylacetamide
Was added and dissolved. On the other hand, PM
3.92 g of DA was collected and solidified in the p-PDA solution.
And continue stirring for 1 hour.
A amic acid prepolymer solution was obtained. Then, 50ml eggplant
18.03 g of ODA was collected in a flask and this amino group was
Add in solid form to terminal amic acid prepolymer solution and add
After stirring thoroughly until the dissolved ODA is completely dissolved, separate
The shortage of PMDA 20.
62g was collected and solidified into the reaction system (four-necked flask)
Was added. Continue stirring for 1 hour
A amic acid solution was obtained. The reaction temperature was kept at 5-10 ° C. However
After the above operation, handle PMDA and dry the inside of the reaction system.
Placed under a stream of nitrogen. Next, according to the method of Reference Example 1, the copolymer
A copolymerized polyimide film was obtained from the liamic acid solution. This file
The film exhibited the properties shown in Table 1. Example 2 15.47 g of ODA was collected in a 500 ml four-necked flask
And 255.00 g of N, N-dimethylacetamide
Added and dissolved. On the other hand, PMD
A16.01 g was collected in solid form in the ODA solution.
Add the mixture and continue stirring for 1 hour.
An acid prepolymer solution was obtained. Then, 50ml eggplant fra
4.19 g of p-PDA was collected in a sco and the amino group powder was collected.
Add in solid form to the terminal amic acid prepolymer solution and add
After sufficiently stirring until the p-PDA is completely dissolved,
Separately, supply PMDA to the 100 ml eggplant flask.
Collect 34 g and solid into the reaction system (four-necked flask)
Was added. Continue stirring for 1 hour
A dodic acid solution was obtained. The reaction temperature was kept at 5-10 ° C. However
By the above operation, the handling of PMDA and the inside of the reaction system
It was placed under a stream of air. Further, the copolymer polyamic acid solution was treated with anhydrous
47.39 g of acetic acid and 9.17 g of pyridine are added and mixed well
After that, according to the method of Reference Example 1, the copolymer polyamide
A copolymerized polyimide film was obtained from the acid solution. This film is
The properties shown in Table 1 were shown. Example 3 12.11 g of ODA was collected in a 500 ml four-necked flask.
And 255.00 g of N, N-dimethylacetamide
Added and dissolved. On the other hand, PMD
A11.88 g was collected in the ODA solution as a solid.
Add the mixture and continue stirring for 1 hour.
An acid prepolymer solution was obtained. Then, 50ml eggplant fra
6.53 g of p-PDA was collected in a sco, and the amino group
Add in solid form to the terminal amic acid prepolymer solution and add
After sufficiently stirring until the p-PDA is completely dissolved,
Separately, a short PMDA1 into a 100 ml eggplant flask
4.49 g was collected and solidified into the reaction system (four-necked flask).
Added in form. Continue stirring for 1 hour.
An amic acid solution was obtained. The reaction temperature was kept at 5-10 ° C.
However, with the above operation, the handling of PMDA and the inside of the reaction system dry.
It was placed under a stream of dry nitrogen. The resulting copolyamic acid mixed solution is
Cast on a lath plate and dry at about 100 ° C for about 60 minutes
After that, the copolymeric polyamic acid coating film was peeled off from the glass plate,
Fix the coating on the support frame, then at about 150 ℃ for about 30 minutes
For about 60 minutes at about 300 ° C.
A 5 to 25 micron copolymerized polyimide film was obtained. This file
The film exhibited the properties shown in Table 1. Example 4 6.53 g of p-PDA was placed in a 500 ml four-necked flask.
Take 255.00 g of N, N-dimethylacetamide
Was added and dissolved. On the other hand, PM
11.86 g of DA was collected and solidified in the p-PDA solution.
Add in the form and continue stirring for 1 hour
An amic acid prepolymer solution was obtained. Then, 50ml
12.11 g of ODA was collected in a flask, and this amino
Add to the terminal-terminal amic acid prepolymer solution in solid form and add
After thoroughly stirring until the added ODA is completely dissolved,
Separately, a short PMDA1 into a 100 ml eggplant flask
4.51 g was collected and solidified into the reaction system (four-necked flask).
Added in form. Continue stirring for 1 hour
A liamic acid solution was obtained. Keep the reaction temperature at 5-10 ° C
Was. However, handling of PMDA and the reaction system
Was placed under a stream of dry nitrogen. The resulting copolyamic acid mixed solution is
Cast on a lath plate and dry at about 100 ° C for about 60 minutes
After that, the copolymeric polyamic acid coating film was peeled off from the glass plate,
Fix the coating on the support frame, then at about 150 ° C for about 10 minutes
About 200 ° C for about 60 minutes, about 300 ° C for about 60 minutes
After heating and dehydrating and ring-closing and drying, the copolymer
A polyimide film was obtained. This film has the properties shown in Table 1.
did. Example 5 8.42 g of ODA was collected in a 500 ml four-necked flask.
And 855.00 g of N, N-dimethylacetamide
Added and dissolved. On the other hand, PMD
A4.59 g was collected and added as a solid to the ODA solution.
And continue stirring for 1 hour.
A prepolymer solution was obtained. Then, 50ml eggplant frus
9.09 g of p-PDA was collected in
Added in solid form to the amic acid prepolymer solution and added
After stirring thoroughly until the p-PDA is completely dissolved, separate
The shortage of PMDA 22.
91 g were collected. Continue stirring for 1 hour
A liamic acid solution was obtained. Keep the reaction temperature at 5-10 ° C
Was. However, handling of PMDA and the reaction system
Was placed under a stream of dry nitrogen. Next, according to the method of Reference Example 1, the copolymer
A copolymerized polyimide film was obtained from the liamic acid solution. This file
The film exhibited the properties shown in Table 1. Example 6 6.45 g of ODA was collected in a 500 ml four-necked flask
And 255.00 g of N, N-dimethylacetamide
Added and dissolved. On the other hand, PMD
A. 6.32 g was collected and added as a solid to the ODA solution.
And continue stirring for 1 hour.
A prepolymer solution was obtained. Then, 50ml eggplant frus
10.44 g of p-PDA was collected in
Add in solid form to the terminal amic acid prepolymer solution and add
After sufficiently stirring until the p-PDA is completely dissolved,
Separately, supply the insufficient PMDA2 to a 100 ml eggplant flask.
1.79 g was collected and solidified into the reaction system (four-necked flask).
Added in form. Continue stirring for 1 hour.
An amic acid solution was obtained. The reaction temperature was kept at 5-10 ° C.
However, with the above operation, the handling of PMDA and the inside of the reaction system dry.
It was placed under a stream of dry nitrogen. Next, according to the method of Reference Example 1, the copolymer
A copolymerized polyimide film was obtained from the liamic acid solution. This file
The film exhibited the properties shown in Table 1. Comparative Example 1 21.54 g of ODA was collected in a 500 ml four-necked flask.
And 245.00 g of N, N-dimethylacetamide
Added and dissolved. On the other hand, PMD
Collect A23.46g and add it to ODA solution in solid form
did. Furthermore, it is attached to the wall in this 100 ml eggplant flask.
10.00 g of N, N'-dimethyl
Pour into the reaction system (four-necked flask) with lufusetamide
Was. Further, stirring was continued for 1 hour, and the
A liamic acid solution was obtained. Keep the reaction temperature at 5-10 ° C
Was. However, handling of PMDA and the reaction system
Was placed under a stream of dry nitrogen. Next, according to the method of Reference Example 1, the polyamide
A polyimide film was obtained from the doric acid solution. This film is shown in Table 1.
The properties shown in Table 1 were shown. Comparative Example 2 In a 500 ml four-necked flask, p-PDA (4.35 g) and
8.07 g of ODA was collected and 160.00 g of N, N-
Dimethylacetamide was added and dissolved. Method of Comparative Example 1
17.58 g of PMDA was reacted in accordance with
Was obtained. However, it remains on the final wall
PMDA present is 10.00 g of N, N-dimethylacetate.
Pour into the toamide reaction system (four-necked flask) and run
Copolyamide acid was obtained by dam copolymerization. Next, according to the method of Example 1, these poly
A polyimide film was obtained from the amic acid solution. These fills
The film had the properties shown in Table 1. Comparative Example 3 6.96 g of p-PDA and 500 ml four-necked flask
4.30 g of ODA was collected and 160.00 g of N, N-
Dimethylacetamide was added and dissolved. Method of Comparative Example 1
18.73 g of PMDA was reacted according to
A polyamic acid solution was obtained by random copolymerization of However
10.00 g of PMDA remaining on the final wall
N, N-dimethylacetamide reaction system (four-neck flask)
Ko). Next, according to the method of Reference Example 1, these poly
A polyimide film was obtained from the amic acid solution. These fills
The film had the properties shown in Table 1. Comparative Example 4 21.54 g of ODA was collected in a 500 ml four-necked flask.
And 245.00 g of N, N-dimethylacetamide
Added and dissolved. On the other hand, PMD
A. Collect 23.46 g of A as a solid in the ODA solution.
Was added. Furthermore, the wall surface in this 100 ml eggplant flask
PMDA adhering to the residue is 10.00 g of N, N-dimethyl
Pour into the tilacetamide reaction system (four-neck flask)
Was. Further, stirring was continued for 1 hour, and the
A liamic acid solution (I) was obtained. On the other hand, p-P was placed in a 500 ml four-necked flask.
14.91 g of DA was collected and 245.00 g of N, N-
Add dimethylacetamide, dissolve, and proceed as above
React with 30.09 g PMDA in accordance with
A liamic acid solution (II) was obtained. However, it adheres to the final wall
The remaining PMDA was 10.00 g of N, N-dimethylamine.
Pour into the reaction system (four-necked flask) with cetamide
Was. In each case, the reaction temperature was maintained at 5 to 10 ° C, and
By the above operation, the handling of PMDA and the inside of the reaction system
It was placed under elementary flow. Next, separately, the po
112.35 g of the liamic acid solution (I) was placed in 500 nl
The sample was collected in a neck flask, and the polyamic acid solution (II) 8
7.65 g and about 1 at 5-10 ° C under dry nitrogen flow.
Stirred for 0 minutes. Next, according to the method of Reference Example 1,
A polyimide film was obtained from the amic acid mixed solution. This fill
The film had the properties shown in Table 1. [Table 1] The copolymer polyimide of the present invention has excellent heat
Dimensional stability and mechanical properties.

──────────────────────────────────────────────────続 き Continued on the front page (31) Priority claim number Japanese Patent Application No. 62-8947 (32) Priority date January 20, 1987 (1987. 1.20) (33) Priority claim country Japan (JP) (31) Priority claim number Japanese Patent Application No. 62-174126 (32) Priority date July 13, 1987 (July 13, 1987) (33) Priority claim country Japan (JP) (31) Priority claim number Japanese Patent Application No. 62-174128 (32) Priority Date July 13, 1987 (July 13, 1987) (33) Countries claiming priority Japan (JP) (56) References JP-A-1-131242 (JP, A) JP-A-61-181827 (JP, A) JP-A-60-210629 (JP, A) JP-A-63-166287 (JP, A) JP-A-63-254131 (JP, A) JP-A-1 -131242 (JP, A) JP-A-61-141734 (JP, A) JP-A-59-164328 (JP, A) JP-B-36-10999 (JP, B1) (58) t.Cl. ⁷ , DB name) C08G 73/10 C08J 5/18 CFG C08L 77/10

Claims (1)

(57) [Claims] General formulas (I) and (II), comprising the steps of (a) to (c): (Wherein R ₀ is an aromatic tetracarboxylic acid residue) A method for producing a copolymerized polyimide having a repeating unit represented by the following formula: (A) 4,4'-diaminodiphenyl ether and / or paraphenylenediamine are represented by the general formulas (I) and (I)
Reaction of a diamine containing 40% to 99% by mole of an aromatic tetracarboxylic dianhydride with respect to this diamine so that the total amount of the repeating units represented by I) is at least 80% by weight in the polyimide molecule Synthesizing an amino group-terminated amic acid prepolymer. (B) The amic acid prepolymer is prepared by adding 10 to 9
A step of synthesizing polyamic acid using 0 mol%. (C) a step of synthesizing a polyimide by dehydrating the polyamic acid. 2. (A) The diamine used in the step is 4,4′-
Claim 1 which is diaminodiphenyl ether
Manufacturing method described in the item. 3. The method according to claim 1, wherein the diamine used in the step (a) is paraphenylenediamine. 4. The total amount of the units represented by the general formula (I) and the general formula (I
The molar ratio of the total amount of the units represented by I) is from 1/9 to 9/1
The method according to claim 1, wherein 5. The method according to claim 1, wherein the aromatic tetracarboxylic dianhydride is an aromatic tetracarboxylic dianhydride containing at least 70% by weight of pyromellitic dianhydride. 6. 2. The method according to claim 1, wherein the dehydration in the step (c) is thermal or chemical dehydration. 7. General formulas (III) and (IV), comprising the steps of (a) and (b): (Wherein R ₀ is a residue of an aromatic tetracarboxylic acid). (A) 4,4′-diaminodiphenyl ether and / or paraphenylenediamine have a total amount of repeating units represented by formulas (III) and (IV) of 80% by weight or more in polyamic acid molecules on average A step of synthesizing an amino group-terminated amic acid prepolymer by reacting the diamine thus contained with 40 to 99 mol% of an aromatic tetracarboxylic dianhydride to the diamine. (B) The amic acid prepolymer is prepared by adding 10 to 9
A step of synthesizing polyamic acid using 0 mol%.