JP5027514B2 - Block copolymerized polyimide solution composition containing pyromellitic dianhydride and film thereof - Google Patents

Description

Industrial application fields

  The present invention relates to a solvent-soluble block copolymerized polyimide containing PMDA (pyromellitic dianhydride) and DADE (4,4'-diaminodiphenyl ether). The present invention relates to a PMDA / DAT-BTDA / DADE quaternary block copolymerized polyimide solution composition and a film thereof, which are degenerated by the action of a two component catalyst in a polar solvent and synthesized by a sequential polymerization reaction.

Conventional technology

  Polyimide is known as a material that can withstand high temperatures for a long time, has excellent electrical insulation, mechanical strength, and chemical resistance, and is widely used as a part of electrical and electronic equipment including the aerospace industry. In particular, it is an indispensable material for today's semiconductor industry.

  The first commercially available polyimide “KAPTON” by DuPont is a polyimide film composed of PMDA (pyromellitic dianhydride) and DADE (4,4′-diaminodiphenyl ether).

  In recent years, heat-resistant materials have been required due to miniaturization of semiconductor chips and high-temperature workability of lead-free plating. Polymer materials having a thermal decomposition starting temperature of 500 ° C. or higher and a glass transition temperature of 400 ° C. or higher are not commercially available as polyimides other than polyimide. The poor productivity of “KAPTON” has been a drag on mass production. Therefore, by improving the manufacturing method of “KAPTON”, that is, by using a solvent-soluble polyimide, productivity can be improved, and further, it can be used as a polyimide film suitable for mass production.

  Aromatic polyimide is generally poorly soluble in a solvent, and in particular, a polyimide composed of PMDA and DADE has low solubility in a solvent. Therefore, conventional polyimide is a polyamic acid (polyimide precursor) having a high molecular weight and high viscosity by polycondensing PMDA and DADE at a low temperature in a polar solvent (for example, N-methylpyrrolidone or N, N'-dimethylacetamide). , Then heated to form a film, and further heated to 350 ° C. or more to perform a dehydration / ring-closure reaction to form a polyimide film (Reference: Polyimide; D. Wilson, HD Steinberger, P.) M. Morgenroter; Blackie (New York) 1990).

  Polyamic acids are thermally unstable in solvents and are easily decomposed by small amounts of water. For this reason, storage stability is bad and it is necessary to store it frozen. Polyamic acid undergoes a fast intermolecular exchange reaction in a solvent, and even if other components are added to attempt modification, it becomes a random copolymer and has little modification effect. The polyamic acid changes at room temperature, and the reproducibility is poor in the measurement of molecular weight by GPC. Therefore, the end point of polyamic acid production is determined by measuring intrinsic viscosity instead of molecular weight measurement.

  Solvent-soluble polyimide is synthesized by performing dehydration and ring-closing reaction with a catalyst using acid dianhydride and aromatic diamine in a solvent. As an acid catalyst, sulfuric acid, phosphoric acid, toluenesulfonic acid or the like is used and heated to 160 to 200 ° C. to promote imidization.

  If the acid catalyst remains in the imide solution, it may cause discoloration or deterioration of the polymer product. Therefore, an insoluble solvent such as methanol or butanone is added to the resulting polyimide solution to precipitate the polyimide, which is separated and collected. The solution is re-dissolved to separate the polyimide and the catalyst (WH Miller, USP 4,927,736).

  In the present invention, a dehydrating imidization reaction is promoted by using a two-component acid-base catalyst utilizing an equilibrium reaction of lactone (USP 5502143). A two-component catalyst of γ-valerolactone and pyridine or N-methylmorpholine is used. As imidization proceeds, water is produced. The water participates in the lactone equilibrium, becomes an acid / base catalyst, and exhibits catalytic action;

  Water produced by the imidization reaction is removed out of the system by azeotropy with toluene or xylene present in the polar solvent. When the reaction is completed, water in the solution is removed, and the acid / base catalyst is removed from the system as γ-valerolactone and pyridine or N-methylmorpholine. Thus, a highly pure polyimide solution is obtained.

  As another two-component catalyst, oxalic acid or malonic acid and pyridine or N-methylmorpholine are used. In the reaction solution at 160 to 200 ° C., oxalate or malonate promotes the imidization reaction as an acid catalyst. A catalytic amount of oxalic acid or malonic acid remains in the produced polyimide solvent. When this polyimide solution is applied and heated to 200 ° C. or higher for solvent removal and film formation, oxalic acid or malonic acid remaining in the polyimide is thermally decomposed and removed as a gas out of the system. Thus, a high purity polyimide product is obtained;

  Compared with the valerolactone-pyridine-based catalyst, the oxalic acid-pyridine-based catalyst is more active and produces a high molecular weight polyimide in a short time.

  Polyimide made of PMDA-DADE is hardly soluble in the solvent. It is an object of the present invention to make the solvent soluble by using a four-component block copolymer. Using a sequential polymerization reaction using a two-component catalyst, a solution composition of a PMDA-DADE-BTDA-DAT solvent-soluble quaternary block copolymerized polyimide is prepared. The polyimide composition showing a glass transition temperature of 350 ° C. or higher is specified.

  A problem in the polyimide manufacturing method including PMDA and DADE is that a precipitate or an insoluble gel is formed when PMDA and DADE are directly bonded in a solution. Therefore, a sequential polymerization reaction is employed, and PMDA and DADE are added to separate processes, and a process in which PMDA and DADE are not involved in direct bonding in a solution is employed.

  PMDA-DADE-BTDA (3,4,3 ', 4'-benzophenonetetracarboxylic dianhydride) and DAT (2,4-diaminotoluene) quaternary polyimides have the following problems in the production process. is there;

  A four-component polyimide composition is synthesized according to the method shown in Table 1 (d). In this case, the PMDA / BTDA molar ratio DADE / DAT molar ratio is changed for synthesis. However, PMDA + BTDA / DADE + DAT = 1.0 (molar ratio).

  A polyimide film was prepared from the soluble polyimide, and the physical properties were measured. The polyimide was classified into polyimides having glass transition temperatures of 300 ° C. or higher and 350 ° C. or higher.

  From a series of these experiments, it has been found that Tg is determined by the composition of the polyimide, as previously said, but the Tg is changed by changing the composition ratio of the polyimide. This is a characteristic of the block copolymer. As a result, in this study, the composition ratio was classified into two groups: the composition ratio in the range of Tg of 300 to 350 ° C, and the composition ratio of Tg in the range of 350 to 390 ° C.

FIG. 1 is a graph in which the molar ratio of PMDA / BTDA and the molar ratio of DADE / DAT are plotted for each example.

  Polyimides that dissolve in polar solvents have different solubility and properties depending on the type, combination, and composition of the acid dianhydride and aromatic diamine.

In the first step of the sequential reaction, PMDA and DAT are reacted to generate an imide oligomer having both ends as DAT. In the second shot, various imide compounds are synthesized by changing the composition of BTDA and DADE. As shown in the examples;
First throw reaction: Second throw reaction A) (PMDA + 2DAT); (n + 1) BTDA + nDADE
B) (2 PMDA+3DAT); (n + 2) BTDA + (n + 1) DADE
C) (3 PMDA+4DAT); (n + 3) BTDA + (n + 2) DADE
D) (4 PMDA+5DAT); (n + 4) BTDA + (n + 3) DADE
E) (5 PMDA+6DAT); (n + 5) BTDA + (n + 4) DADE
In many cases, the A, B, and C systems generate solvent-soluble polyimide, and the D system generates a gel. All E systems produce precipitates.

  In order to produce a practically stable polyimide film, no amine remains at the end. Therefore, the molar ratio of acid dianhydride to aromatic diamine is 1: 1 to 0.95. In this experiment, PMDA + BTDA / DADE + DAT = 1.0 (molar ratio) is used in order to investigate the relationship between the composition and properties of polyimide.

The molar ratios of the compounds shown in the examples are as follows:
[M • PMDA + (m + 1) DAT] [(n + 1) BTDA + n • DAT]
m = 1, 2, 3, 4 (5 or more becomes precipitation)
n = 0, 0.5, 0.6, 1, 2, 3, 4, 5
In the synthesis experiment, a glass three-necked flask was used, and a stainless steel vertical stirrer, a ball-mounted cooling tube equipped with a water separation trap, and a nitrogen introducing tube were attached thereto. It was placed in a silicon bath through nitrogen and heated and stirred.

  In the first reaction, calculated amounts of PMDA and DADE and catalytic amounts of oxalic acid and pyridine were used. NMP was added to obtain a polyimide solution having a concentration of 13 to 15%, and an amount of toluene corresponding to the capacity of the trap was added. The reaction is carried out at 180 ° C. and 170 to 200 rpm for 1 to 1.5 hours. Then air cool and slowly add the calculated amount of BTDA and DADE powder (mix well). NMP was added at the end, or half at the beginning and half at the end.

  After stirring at room temperature at 150 to 180 rpm for 10 to 30 minutes, it was immersed in an oil bath at 180 ° C. and reacted for 3 to 7 hours.

  The end point of the reaction was determined by measuring the viscosity of the solution or looking at the state of the film obtained by taking a polyimide solution on a glass plate and heating at 90 ° C. for 30 minutes. After the reaction, molecular weight and molecular weight distribution by GPC were measured. A part of the produced polyimide solution was cast on a glass plate, and thermal analysis was performed using a film dried at 90 ° C., 1 hour, 200 ° C., 1 hour. Tg (glass transition temperature) and Tm (thermal decomposition start temperature) by DSC method were measured. Tg is a value obtained by scanning again at 40 to 420 ° C. after scanning at 40 to 400 ° C. The polyimide showing the melting point showed the value of the first scan and the value of the second scan.

  The elongation at break and elastic modulus were measured using a sample having a length of 50 mm and a width of 20 mm after drying a film dried at 200 ° C. in nitrogen at 300 ° C. for 90 minutes.

  Table 2 shows the polyimide reaction product composition shown in the examples, and the molar ratio of PMDA / BTDA and DADE / DAT.

  FIG. 1 is a graph in which the molar ratio of PMDA / BTDA and the molar ratio of DADE / DAT are plotted for each example. The plot corresponds to each example, and the number corresponds to the example number. A preferred composition of the present invention is in the wavy line in the graph, and a particularly preferred composition is in the solid line.

  FIG. 1 and Table 2 show preferred quaternary polyimide compositions. A preferable range in Table 2 corresponds to the inside of the wavy rectangle in FIG. 1, and a particularly preferable range in Table 2 corresponds to the inside of the solid line rectangle in FIG.

  The polyimides shown in Examples 3, 6, 7, 8, 11, and 12 are preferable, and show film properties, production methods, and compositions.

  Examples 5 and 17 are examples of polyimide showing a melting point.

The following points need to be considered when selecting a polyimide solution:
1) There are few troubles in the manufacturing process of the polyimide solution. Can be stored at room temperature for a long time. Not producing a gel,
2) Tg is 350 ° C. or higher and the thermal decomposition start temperature is 490 ° C. or higher.
3) Specify a polyimide with a melting point,
4) The smaller the molar ratio of PMDA / BTDA and DADE / DAT, the larger the elastic modulus.

  From these results, the preferred range of the polyimide composition is 0.5 to 1.5 for PMDA / BTDA, 0.1 to 1.0 for DADE / DAT, more preferably 0.6 to 1 for PMDA / BTDA. .3, DADE / DAT is 0.2 to 0.8.

  A composition having a PMDA / BTDA molar ratio of 0.5 to 1.5 and a DADE / DAT molar ratio of 0.1 to 1.0 has a Tm of 490 ° C. or higher and a Tg of 300 ° C. or higher. A composition with DADE / DAT = 1.0 exhibits a melting point.

  A composition having a PMDA / BTDA molar ratio of 0.6 to 1.3 and a DADE / DAT molar ratio of 0.2 to 0.8 is a heat-resistant polyimide having a Tm of 490 ° C. or higher and a Tg of 350 ° C. or higher. In the present invention, a low-cost polyimide can be produced in a large amount by adopting a direct imidization process by using a raw material which is inexpensive and easily available by a sequential polymerization reaction using a two-component catalyst.

  The polyimide solution is defined by viscosity and molecular weight, but the molecular weight and molecular weight distribution by GPC measurement can be reproduced within a range of 10% error in production.

  A four-component block copolymerized polyimide solution is cast, heated, and the solvent is scattered to obtain a polyimide film having excellent characteristics. The film can be formed at a temperature of 350 ° C. or less, and the film forming speed is relatively fast.

  In the conventional film formation using polyamic acid, since dehydration and imidization reactions are performed, a high-temperature treatment at 350 to 500 ° C. is performed, and the film formation speed is very slow.

  This four-component polyimide has the advantage that it can be manufactured using inexpensive and readily available raw materials. As a use, it can be used as a polyimide film, an insulating varnish, a sealant, a polyimide solution for a jet printer, and the like. Furthermore, by providing a function as a five-component block copolymer, it can be used as an electrodeposition polyimide, a photosensitive polyimide, a polyimide for composite materials, and the like.

  The polyimide having a melting point can be used as an adhesive, a polyimide for a copper substrate, or the like.

  Hereinafter, the present invention will be described in detail with some examples. In addition, since the polycondensate having various characteristics can be obtained depending on the combination and composition ratio of two kinds of acid dianhydrides and two kinds of aromatic diamines, the present invention is limited only to these examples. is not.

(Measurement of molecular weight)
A part of the reaction solution was diluted with dimethylformamide, and the molecular weight and molecular weight distribution were measured with a high performance liquid chromatograph (Tosoh product). The molecular weight in terms of polystyrene indicates the ratio of the highest molecular weight (M), number average molecular weight (Mn), weight average molecular weight (Mw), Z average molecular weight (Mz), Mw / Mm, and Mz / Mn.

(Thermal analysis)
The thermal decomposition starting temperature (Tm) was measured by using a TGA-50 manufactured by Shimadzu Corporation and raising the temperature to 600 ° C. at a temperature raising rate of 10 ° C./min. The glass transition temperature (Tg) was measured using a DSG-50 manufactured by Shimadzu Corporation, the temperature was raised to 400 ° C at 10 ° C / min, the sample was air-cooled, and the temperature was raised again to 420 ° C at 10 ° C / min. It was calculated from the measured value.

Examples are described below, but the present invention should not be construed as being limited to the examples. In addition, Examples 1-16 are the synthesis examples of block copolymerization polyimide, and Examples 17-20 are the synthesis examples for reference of random copolymerization polyimide.
[Example 1]
(PMDA + 2DAT) and (2BTDA + DADE) having the following molar ratios were used.

  A glass separable three-necked flask fitted with a stainless steel vertical stirrer, and a ball condenser equipped with a water separation trap are attached to the flask. did.

  Pyromellitic dianhydride (hereinafter referred to as PMDA) 5.45 g (25 mmol), 2,4-diaminotoluene (hereinafter referred to as DAT) 6.11 g (50 mmol), oxalic anhydride 0.5 g, pyridine 1.5 g, 100 g of N-methylpyrrolidone (hereinafter referred to as NMP) and 30 g of toluene were added to a three-necked flask, and heated and stirred at a silicon bath temperature of 180 ° C. and a rotation speed of 200 rpm for 1 hour while passing nitrogen. Remove 20 ml of water-toluene fraction. Air-cooled and stirred for 20 minutes. Next, 5.00 g (25 mmol) of 4,4'-diaminodiphenyl ether (hereinafter referred to as DADE) and 16.11 g (50 mmol) of 3,4,3,4'-benzophenonetetracarboxylic dianhydride (hereinafter referred to as BTDA) The powder was mixed well and gradually put into the reactor. Next, 120 g of NMP and 20 g of toluene were added, and the mixture was stirred at room temperature for 30 minutes, then heated in a silicon bath, and heated and stirred at 180 ° C. and 175 rpm in nitrogen.

  After 3 hours and 30 minutes, a 12% by weight polyimide solution was obtained after stopping the reaction. A portion thereof was placed on a glass plate and heated at 90 ° C. for 1 hour and then at 200 ° C. for 1 hour to confirm a strong polyimide film.

Results of molecular weight measurement
M 32.300
Mn 13.400
Mw 31.600
Mz 55.000
Mw / Mn 2.35
Mz / Mn 4.09
Thermal analysis results
Tm 506 ° C
Tg 342-357 ° C
[Example 2]
(PMDA + 2DAT) and (3BTDA + 2DADE) having the following molar ratios were used.

  The same operation as in Example 1 was performed.

PMDA 6.54 g (30 mmol), DAT 7.33 g (60 mmol), oxalic anhydride 0.9 g, pyridine 1.9 g, NMP 150 g, and toluene 30 g are charged into the reactor. The mixture was heated and stirred at 180 ° C. and 200 rpm in a nitrogen stream at the silicon bath temperature. After 30 minutes of air cooling and stirring, 29.00 g (90 mmol) of BTDA, 12.01 g (60 mmol) of DADE, and 188 g of NMP were added, and the mixture was stirred at room temperature for 15 minutes and then in a silicon bath at 180 ° C. and 185 rpm for 3 hours 15 The reaction was stopped by heating and stirring for a minute to obtain a 13% polyimide solution. The polyimide solution was placed on a glass plate and heated and dried at 90 ° C. for 1 hour and 200 ° C. for 1 hour, and then thermal analysis was performed.
[Example 3]
(PMDA + 2DAT) and (1.5BTDA + 0.5DADE) having the following molar ratios were used.

  The same operation as in Example 1 was performed.

  PMDA 10.91 g (50 mmol), DAT 12.22 g (100 mmol), oxalic anhydride 0.9 g, pyridine 1.9 g, NMP 200 g, and toluene 30 g are charged. After reacting at 180 ° C. and 175 rpm for 2 hours, cooling and stirring for 20 minutes, 24.17 g (75 mmol) of BTDA, 5.00 g (25 mmol) of DADE and 120 g of NMP were added, and after stirring for 20 minutes at room temperature, the temperature was raised. And reacted at 180 ° C. and 175 rpm for 4 hours and 45 minutes to obtain a 13 wt% polyimide solution.

(Molecular weight measurement)
M 76.400
Mn 37.000 Mw / Mn 4.15
Mw 154.000
Mz 449.000 Mz / Mn 12.0
(Thermal analysis)
Tm 491 ℃
Tg 360-374 ° C
[Example 4]
(2 PMDA+3DAT) and (5BTDA + 4DADE) having the following molar ratios were used.

  The same operation as in Example 1 was performed.

  PMDA 6.83 g (16 mmol), DAT 5.86 g (24 mmol), oxalic anhydride 0.9 g, pyridine 1.9 g, NMP 200 g, and toluene 30 g are charged. The reaction was carried out at 180 ° C. and 180 rpm for 1 hour. After air cooling, 25.78 g (40 mmol) of BTDA, 12.81 g (32 mmol) of DADE, and 118 g of NMP were added and stirred at room temperature (starting with 68 g of NMP, added in three portions with the powder, and finally 50 g of NMP). The reaction was carried out at 180 ° C. and 195 rpm for 3 hours and 20 minutes to obtain a polyimide solution having a concentration of 13% by weight.

(Thermal analysis)
Tm 506 ° C
Tg 327-339 ° C
[Example 5]
(2 PMDA+3DAT) and (4BTDA + 3DADE) having the following molar ratios were used.

  The same operation as in Example 1 was performed.

  4.67 g (16 mmol) of PMDA, 5.86 g (24 mmol) of DAT, 0.9 g of oxalic anhydride, 1.9 g of pyridine, 100 g of NMP, and 30 g of toluene are charged. After the reaction at 180 ° C. for 180 rpm, the mixture was cooled, BTDA 20.62 g (32 mmol), DADE 9.61 g (24 mmol) and NMP 165 g were added, and 180 ° C., 180 rpm for 4 hours 20 minutes. The reaction yielded a 13 wt% polyimide solution.

(Molecular weight measurement)
M 94.600
Mn 48.600 Mw / Mn 4.56
Mw 221.800
Mz 704.000 Mz / Mn 14.5
(Thermal analysis)
Tm 498 ° C
341 to 3351 to 361 ° C. showing melting point in the first measurement by DSC
Tg33 ~ 347 ℃ in the second scan
[Example 6]
(2 PMDA+3DAT) and (3BTDA + 2DADE) having the following molar ratios were used.

  The same operation as in Example 1 was performed.

  PMDA 8.73 g (20 mmol), DAT 7.33 g (30 mmol), oxalic anhydride 0.9 g, pyridine 1.9 g, NMP 150 g, and toluene 30 g are charged. The mixture was reacted at 180 ° C. and 200 rpm for 1 hour and cooled. Then, 19.33 g (30 mmol) of BTDA, 8.01 g (20 mmol) of DADE and 116 g of NMP were added, and the reaction was carried out at 180 ° C. and 185 rpm for 6 hours.

(Thermal analysis)
M 50.000
Mn 22.600 Mw / Mn 3.77
Mw 85.200
Mz 241.000 Mz / Mn 10.68
(Thermal analysis)
Tm 493 ° C
Tg 374-379 ° C
[Example 7]
Compositions with the following molar ratios (2 PMDA+3DAT) and (2BTDA + DADE) were used.

  In the same manner as in Example 1, a 13% by weight polyimide solution was produced.

  PMDA 13.00 g (60 mmol), DAT 11.00 g (90 mmol), oxalic anhydride 0.9 g, NMP 150 g, and toluene 30 g are charged. After reaction for 1 hour at 180 ° C. and 180 rpm in a nitrogen stream, air-cool.

(Molecular measurement)
M 50.800
Mn 19.300 Mw / Mn 3.80
Mw 73.400
Mz 223.900 Mz / Mn 11.58
(Thermal analysis)
Tm 505 ° C
Tg 380-383 ° C
[Example 8]
Compositions with the following molar ratios (2 PMDA+3DAT) and (1.6BTDA + 0.6DADE) were used.

  The same operation as in Example 1 was performed.

  PMDA 15.27 g (70 mmol), DAT 12.83 g (105 mmol), oxalic anhydride 0.9 g, pyridine 1.9 g, NMP 200 g, and toluene 30 g were added and reacted at 180 ° C., 175 rpm for 1 hour. Then, the reaction was carried out at 180 ° C. and 165 rpm for 4 hours and 20 minutes. Next, 18.05 g (56 mmol) of BTDA, 107 g of DADE (4.20 g) and 107 g of NMP were added and reacted at 180 ° C. and 165 rpm for 4 hours and 20 minutes to obtain a 13 wt% polyimide solution. It was.

(Molecular weight measurement)
M 87.100
Mn 51.100 Mw / Mn 5.00
Mw 255.100
Mz 918.000 Mz / Mn 18.00
(Thermal analysis)
Tm 492 ° C
Tg unknown [Example 9]
Compositions with the following molar ratios (3 PMDA+4DAT) and (6BTDA + 5DADE) were used.

  The same operation as in Example 1 was performed.

PMDA 9.80 g (45 mmol), DAT 7.33 g (60 mmol), oxalic anhydride 0.9 g, pyridine 1.1 g, NMP 200 g, and toluene 30 g are charged. After 1 hour of reaction at 180 ° C. and 185 rpm, the mixture was air-cooled, and 29.00 g (90 mmol) of BTDA, 15.00 g (75 mmol) of DADE and 177 g of NMP were added. Then, when the reaction was carried out at 180 ° C. and 180 rpm, a gel was generated, so the reaction was stopped.
[Example 10]
Compositions with the following molar ratios (3 PMDA+4DAT) and (5BTDA + 4DADE) were used.

  The same operation as in Example 1 was performed.

PMDA 9.8 g (45 mmol), DAT 7.33 g (60 mmol), oxalic anhydride 0.9 g, pyridine 1.9 g, NMP 200 g, and toluene 30 g are charged. After reacting at 180 ° C. and 200 rpm for 1 hour, the mixture was air-cooled, 24.17 g (75 mmol) of BTDA, 12.01 g (60 mmol) of DADE, and 129 g of NMP were added, stirred, and then heated. The mixture was reacted at 180 ° C. and 185 rpm for 3 hours and 45 minutes to obtain a 13 wt% polyimide solution. During the reaction, 113 g of NMP was further added, but a gel was generated.
[Example 11]
Compositions with the following molar ratios (3 PMDA+4DAT) and (4BTDA + 3DADE) were used.

  The same operation as in Example 1 was performed to obtain a 13% by weight polyimide solution.

  11.12 g (51 mmol) of PMDA, 8.31 g (68 mmol) of DAT, 0.9 g of oxalic anhydride, 1.9 g of pyridine, 150 g of NMP, and 30 g of toluene are added. After the reaction at 180 ° C. and 185 rpm, air-cooled, 21.91 g (68 mmol) of BTDA, 10.21 g (51 mmol) of DADE, and 166 g of NMP were added and stirred, and then 180 ° C. and 185 rpm. For 4 hours and 10 minutes.

(Thermal analysis)
Tm 496 ° C
Tg 315-363 ° C
[Example 12]
Compositions with the following molar ratios (3 PMDA+4DAT) and (3BTDA + 2DADE) were used.

  The same operation as in Example 1 was performed to obtain a 13% by weight polyimide solution.

  PMDA 13.09 g (60 mmol), DAT 9.77 g (80 mmol), oxalic anhydride 0.9 g, pyridine 1.9 g, NMP 200 g and toluene 30 g were added and stirred, after reaction at 180 ° C., 200 rpm for 1 hour. After cooling with air, 19.33 g (60 mmol) of BTDA, 8.01 g (40 mmol) of DADE and 111 g of NMP were added and stirred, and then reacted at 180 ° C. and 185 rpm for 3 hours and 50 minutes.

(Molecular weight measurement)
M 78.700
Mn 54.800 Mw / Mn 4.33
Mw 237.200
Mz 876.800 Mz / Mn 15.95
(Thermal analysis)
Tm 496 ° C
Tg 367-380 ° C
[Example 13]
Compositions with the following molar ratios (3 PMDA+4DAT) and (2BTDA + DADE) were used.

  The same operation as in Example 1 was performed to obtain a 13% by weight polyimide solution.

  PMDA 16.36 g (75 mmol), DAT 12.22 g (100 mmol), oxalic anhydride 0.9 g, pyridine 1.9 g, NMP 200 g, and toluene 30 g are charged. After reacting at 180 ° C. and 190 rpm for 1 hour, air-cooled, BTDA 16.11 g (50 mmol), DADE 5.01 g (25 mmol) and NMP 103 g were added and stirred. Subsequently, it was reacted at 180 ° C. and 180 rpm for 3 hours 30 minutes to obtain a polyimide solution.

(Thermal analysis)
Tm 503 ° C
Tg unknown [Example 14]
Compositions (3 PMDA+4DAT) and (1.5BTDA + 0.5DADE) were used.

  The same operation as in Example 1 was performed to obtain a polyimide solution having a concentration of 13% by weight.

  PMDA 19.63 g (90 mmol), DAT 14.66 g (120 mmol), oxalic anhydride 0.9 g, pyridine 1.9 g, NMP 250 g and toluene 30 g were added and stirred. Then, after reacting at 180 ° C. and 175 rpm for 1 hour, air cooling is performed. 14.5 g (45 mmol) of BTDA, 3.0 g (15 mmol) of DADE, and 64 g of NMP were added and stirred, and then reacted at 180 ° C. and 165 rpm for 4 hours and 50 minutes to obtain a polyimide solution.

(Thermal analysis)
Tm 500 ℃
Tg unknown [Example 15]
(4 PMDA+5DAT) and (5BTDA + 4DADE) having the following molar ratios were used.

  The same operation as in Example 1 was performed to obtain a 13% by weight polyimide solution.

  PMDA 11.34 g (52 mmol), DAT 7.94 g (65 mmol), oxalic anhydride 0.9 g, pyridine 1.9 g, NMP 200 g, and toluene 30 g are charged. After reacting at 180 ° C. and 200 rpm for 1 hour, air-cooled, BTDA 20.95 g (65 mmol), DADE 10.41 g (52 mmol) and NMP 111 g were added and stirred. Subsequently, it reacted at 180 ° C. and 185 rpm for 3 hours and 50 minutes to obtain a polyimide solution having a concentration of 13% by weight.

(Molecular weight measurement)
M 78.700
Mn 40.400 Mw / Mn 3.70
Mw 149.400
Mz 405.100 Mz / Mn 10.00
(Thermal analysis)
Tm 512 ° C
Tg 340-360 ° C
[Example 16]
(4 PMDA+5DAT) and (3BTDA + 2DADE) having the following molar ratios were used.

  The same operation as in Example 1 was performed to obtain a 13% by weight polyimide solution.

PMDA 11.34 g (52 mmol), DAT 7.94 g (65 mmol), oxalic anhydride 0.9 g, pyridine 1.9 g, NMP 200 g, and toluene 30 g are charged. Subsequently, after reacting at 180 ° C. and 180 rpm for 1 hour, the mixture was air-cooled, BTDA 12.58 g (39 mmol), DADE 5.2 g (26 mmol), and NMP 26 g were added and stirred. The reaction was carried out at 180 ° C. and 180 rpm, but a precipitate was formed during the reaction, and the reaction was stopped.
[Example 17 (reference example)]
(BTDA + DAT + DADE) and (PMDA) having the following molar ratios were used.

  The same operation as in Example 1 was performed to obtain a 13% concentration polyimide solution.

BTDA 8.06 g (25 mmol), DADE 10.01 g (50 mmol), oxalic anhydride 1.0 g, pyridine 1.8 g, NMP 150 g, and toluene 40 g are charged. The reaction is carried out at 180 ° C. and 165 rpm for 20 minutes and air-cooled. The powder which mixed BTDA 8.06g (25 mmol) and DAT6.11g (50 mmol) was added slowly, and also NMP50g was added and stirred. Next, this solution heated and stirred at 180 ° C. and 150 rpm for 30 minutes is air-cooled and 10.91 g (50 mmol) of PMDA is added little by little. Next, 11 g of NMP is added and the mixture is stirred at room temperature. The mixture was reacted at 180 ° C. and 125 rpm for 2 hours and 10 minutes, and then reacted at 180 ° C. and 150 rpm for 50 minutes to obtain a uniform polyimide solution.
[Example 18 (reference example)]
(BTDA + PMDA + 2DAT) having the following molar ratio was used.

  Add 19.33 g (60 mmol) of BTDA, 13.09 g (60 mmol) of PMDA, 14.66 g (120 mmol) of DAT, 0.9 g of oxalic anhydride, 1.9 g of pyridine, 286 g of NMP and 30 g of toluene, and stir at room temperature for 30 minutes. It is a liquid. This was placed in a silicon bath and reacted at 180 ° C. and 175 rpm for 3 hours and 50 minutes to obtain a 13% uniform polyimide solution. It is a random copolymer polyimide containing no DADE.

(Molecular weight measurement)
M 81.100
Mn 45.800 Mw / Mn 8.89
Mw 407.300
Mz 2236.000 Mz / Mn 48.8
(Thermal analysis)
Tm 503 ° C
Tg 381-394 ° C
[Example 19 (reference example)]
(2BTDA + 3PMDA + 5DAT) having the following molar ratio was used.

  The same operation as in Example 18 was performed to obtain a 13% random copolymer polyimide solution. 16.11 g (50 mmol) of BTDA, 16.36 g (75 mmol) of PMDA, 15.27 g (125 mmol) of DAT, 0.9 g of oxalic anhydride, 1.9 g of pyridine, 286 g of NMP and 30 g of toluene are added and stirred at room temperature for 30 minutes. Then, a random copolymer polyimide solution containing no DADE heated and stirred at 180 ° C. and 175 rpm for 3 hours and 50 minutes was obtained.

(Thermal analysis)
Tm 508 ° C
Tg (not confirmed)
[Example 20 (reference example)]
(2 PMDA+BTDA+3DAT) having the following molar ratio was used.

  In the same manner as in Example 18, a 13% by weight random copolymer solution was obtained. PMDA 17.45 g (80 mmol), BTDA 12.89 g (40 mmol), DAT 14.61 g (120 mmol), oxalic anhydride 0.9 g, pyridine 1.9 g, NMP 272 g and toluene 30 g were added and stirred at room temperature to obtain a homogeneous solution. Got. Then it was heated and stirred. Heating at 180 ° C. and 175 rpm for 3 hours and 45 minutes gave a uniform polyimide solution.

(Thermal analysis)
Tm 499 ° C
Tg (not confirmed)

The results of Examples 1 to 20 are shown in Table 3 and Table 4.

[Example 21]
The four films produced in Examples 1, 6, 12, and 17 were subjected to a tensile test using a sample having a width of 20.0 mm, a thickness of 0.057 mm, and a length of 50 mm. The results are shown in Table 5.

Claims (8)

(A) An imide oligomer formed by the reaction of pyromellitic dianhydride and 2,4-diaminotoluene (1.2 to 2 mol) in the presence of an acid catalyst, benzophenone tetracarboxylic dianhydride and 4, 4'-diaminodiphenyl ether is added and reacted to form a quaternary block copolymer polyimide solution, wherein the molar ratio of total acid dianhydride to total aromatic diamine is 1: 1 to 0.95; The weight average molecular weight is 50,000 to 600,000 in terms of styrene, and the quaternary block copolymer polyimide has a glass transition temperature of 300 ° C. or higher and (b) a polar solvent containing an aromatic hydrocarbon,
A four-component block copolymerized polyimide composition used as a film, insulating varnish, sealant, adhesive, and ink for a jet printer. In the method for producing a quaternary block copolymer polyimide,
(A) Pyromellitic dianhydride (1 mol) and diaminotoluene (1.2 to 2 mol) are reacted in a polar solvent containing hydrocarbon at 160 to 200 ° C. in the presence of an acid catalyst to give an imide oligomer. The first stage,
(B) A second stage in which benzophenone tetracarboxylic dianhydride and 4,4′-diaminodiphenyl ether are added to an imide oligomer and heated to 160 to 200 ° C. to obtain a quaternary block copolymer polyimide, The manufacturing method of the said block copolymerization polyimide solution whose glass transition temperature is 300 degreeC or more including the process which the molar ratio of a total acid dianhydride and a total aromatic diamine is 1: 1-0.95 here . In the block copolymer polyimide, the molar ratio of pyromellitic dianhydride / benzophenone tetracarboxylic dianhydride is 0.5 to 1.5, and the molar ratio of 4,4′-diaminodiphenyl ether / diaminotoluene is 0.00. The manufacturing method according to claim 2 , wherein a polyimide film having a thermal decomposition start temperature of 490 ° C. or higher and a glass transition temperature of 300 ° C. or higher is formed. In the block copolymerized polyimide, the molar ratio of 4,4′-diaminodiphenyl ether / diaminotoluene is 1 ± 0.1, and is a block copolymerized polyimide exhibiting a melting point, comprising an adhesive, a resin for a metal laminate, The method for producing a block copolymerized polyimide solution according to claim 2 , wherein the block copolymerized polyimide solution can be used as a sealant or an ink for a jet printer. The molar ratio of pyromellitic dianhydride / benzophenonetetracarboxylic dianhydride is 0.6 to 1.3, and the molar ratio of 4,4'-diaminodiphenyl ether / diaminotoluene is 0.2 to 0.8. The method for producing a block copolymerized polyimide solution according to claim 2, which is a polyimide composition having a thermal decomposition starting temperature of 490 ° C or higher and a glass transition temperature of 350 ° C or higher. The hydrocarbon is selected from the group consisting of toluene, xylene and mixtures thereof, and the polar solvent comprises N-methylpyrrolidone, N, N'-dimethylacetamide, N, N'-dimethylformamide, sulfolane and mixtures thereof. is selected from the group a process according to claim 2 content of the polyimide block copolymer is 10 wt% or more soluble in the polar solvent. Acid catalyst is oxalic acid and pyridine, oxalic acid and N- methylmorpholine, malonic acid and pyridine, and The composition of claim 1, wherein a two-component catalyst selected from the group consisting of malonic acid and N- methylmorpholine . The composition of claim 1 wherein the acid catalyst is a two-component system catalyst consisting of γ- valerolactone and pyridine or N- methylmorpholine.

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