JP3487128B2 - Polyimide resin - Google Patents

Description

Detailed Description of the Invention

[0001]

TECHNICAL FIELD The present invention relates to a polyimide resin, and more specifically, it has a particularly high glass transition temperature, excellent heat resistance, and is soluble in various organic solvents and mineral acids or alkaline solutions. A novel polyimide resin having

[0002]

2. Description of the Related Art Polyimide resin is known as an engineering plastic excellent in heat resistance, electrical characteristics and mechanical characteristics, and has been widely put into practical use as a protective material, an insulating material or a structural material in the field of electronic equipment. There is. However, many of these polyimide resins are insoluble in both various organic solvents and mineral acids,
Further, since it is also thermally infusible, it was extremely difficult to perform its molding.

[0003]

The above-mentioned conventional aromatic polyimide resins have a high glass transition temperature and excellent heat resistance, and at the same time have good solubility in organic solvents and mineral acids. Almost nothing,
The fact that there are few aromatic polyimide resins having both heat resistance and processability has been a serious problem in the commercial use of this resin. In order to solve such a problem, a soluble polyimide resin having a triphenylamine structure (Japanese Patent Application Laid-Open No. 4-11631) has been proposed in recent years. However, it is lower than the conventional polyimide resin, and there is a problem that the heat resistance is not sufficient.

The object of the present invention is to provide a novel polyimide resin which is excellent in heat resistance and is soluble in various organic solvents and mineral acids or alkaline solutions without impairing the inherent high glass transition temperature of the polyimide resin. To provide.

[0005]

The inventors of the present invention have conducted extensive studies to solve the problems of the prior art, and as a result, the specific structural units represented by the general formula (1) and the general formula (2) are shown. The polyimide resin composed of the above general formula (1)
Containing the structural unit represented by
It was found that a polyimide resin composed of a constitutional unit derived from 4'-diaminotriphenylamine has a high glass transition temperature, is excellent in heat resistance, and is soluble in various organic solvents, mineral acids or alkaline solutions. The present invention has been accomplished.

That is, the invention of claim 1 of the present invention is
A polyimide resin comprising a structural unit represented by the following general formula (1) obtained by reacting a diamine compound and tetracarboxylic dianhydride or a diamine compound and tetracarboxylic acid dithioanhydride in an organic solvent , The Tet
Lacarboxylic acid dianhydride is pyromellitic dianhydride, 3,
4,3 ', 4'-biphenyltetracarboxylic dianhydride
, 3,4,3 ', 4'-diphenyl ether tetraca
Rubonic acid dianhydride, 3,4,3 ', 4'-benzopheno
Tetracarboxylic dianhydride, 3,4,3 ', 4'-di
Phenylsulfone tetracarboxylic dianhydride, 2,2-
Bis (3,4-dicarboxyphenyl) -1,1,1,
3,3,3-hexafluoropropane dianhydride, 3,
4,3 ", 4" -Terphenyl tetracarboxylic dianhydride
At least one tetracarboxylic acid selected from
Water, and the tetracarboxylic acid dithioanhydride is
Lomelitic acid dithioanhydride, 3,4,3 ', 4'-biphe
Nyltetracarboxylic acid dithio anhydride, 3,4,3 ′,
4'-diphenyl ether tetracarboxylic acid dithio anhydride
, 3,4,3 ', 4'-benzophenone tetracarbo
Acid dithio anhydride, 3,4,3 ', 4'-diphenyls
Rufone tetracarboxylic acid dithio anhydride, 2,2-bis
(3,4-dicarboxylphenyl) -1,1,1,
3,3,3-hexafluoropropanedithioanhydride,
3,4,3 ", 4" -Terphenyl tetracarboxylic acid diester
At least one tetracarbo selected from thioanhydride
Acid dithioanhydride, in 98% concentrated sulfuric acid at 30 ° C.,
The inherent viscosity measured at a concentration of 0.5 g / dl
It is a polyimide resin characterized by being 0.1 to 3 dl / g .

[0007]

[Chemical 3]

The invention of claim 2 of the present invention is characterized in that the polyimide resin according to claim 1 comprises a constitutional unit represented by the following formula (2).

[0009]

[Chemical 4]

[0010]

The invention according to claim 3 of the present invention comprises 30% or more of the structural unit represented by the general formula (1) according to claim 1, and the rest is derived from 4,4′-diaminotriphenylamine. It is a polyimide resin characterized by comprising a structural unit.

[0012]

BEST MODE FOR CARRYING OUT THE INVENTION The present invention will be described in detail below.
The polyimide resin of the present invention is produced using a hydroxytriphenyldiamine compound represented by the following formula (3) and a tetracarboxylic dianhydride represented by the following general formula (4) as raw materials, or the following formula ( It is produced by using a hydroxytriphenyldiamine compound represented by 3) and a tetracarboxylic acid dithio anhydride represented by the following general formula (5) as raw materials.

[0013]

[Chemical 5]

[0014]

[Chemical 6]

[0015]

[Chemical 7]

The hydroxytriphenyldiamine compound represented by the above formula (3) is 4,4'-diamino-
This refers to 4 "-hydroxytriphenylamine, and this diamine can be easily produced by using, for example, p-halonitrobenzene and 4-benzyloxyaniline as starting materials. To give a specific example, 4-benzyloxyaniline and p-benzyloxyaniline are used.
-Chloronitrobenzene in dimethyl sulfoxide, 1
After reacting at 00 ° C. and recrystallizing the obtained compound,
It can be obtained by reducing with zinc and hydrochloric acid and further neutralizing with a weak alkali.

Specific examples of the tetracarboxylic dianhydride represented by the above general formula (4) include pyromellitic dianhydride and 3,4,3 ′, 4′-biphenyltetracarboxylic acid. Dianhydride, 3,4,3 ', 4'-diphenyl ether tetracarboxylic acid dianhydride, 3,4,3',
4'-benzophenone tetracarboxylic dianhydride, 3,
4,3 ', 4'-Diphenylsulfone tetracarboxylic dianhydride, 2,2-bis (3,4-dicarboxyphenyl) -1,1,1,3,3,3-hexafluoropropanedi An anhydride, 3,4,3 ", 4" -terphenyl tetracarboxylic dianhydride, etc. can be illustrated. These tetracarboxylic acids may be used alone or in combination of two or more.

Specific examples of the tetracarboxylic acid dithio anhydride represented by the above general formula (5) include, for example, pyromellitic acid dithio anhydride, 3,4,3 ', 4'-.
Biphenyl tetracarboxylic acid dithio anhydride, 3,4
3 ', 4'-diphenyl ether tetracarboxylic acid dithio anhydride, 3,4,3', 4'-benzophenone tetracarboxylic acid dithio anhydride, 3,4,3 ', 4'-diphenyl sulfone tetra Carboxylic acid dithio anhydride, 2,2-
Bis (3,4-dicarboxylphenyl) -1,1,
Examples include 1,3,3,3-hexafluoropropanedithioanhydride and 3,4,3 ″, 4 ″ -terphenyltetracarboxylic acid dithioanhydride. These tetrathiocarboxylic acids may be used alone or in combination of two or more.

An example of the first method for producing the polyimide resin of the present invention will be described. The diamine compound and the tetracarboxylic dianhydride are reacted in an organic solvent at -20 to 50 ° C for several minutes to several days. Thus, a polyamic acid is obtained, and then a polyimide resin is obtained by heating or treatment with a dehydration ring-closing agent. Examples of the organic solvent that can be used in the polyamic acid synthesis reaction include amide solvents such as N, N-dimethylacetamide and N-methyl-2-pyrrolidone, benzene, anisole, diphenyl ether,
Aromatic solvents such as nitrobenzene, benzonitrile, pyridine, chloroform, dichloromethane, 1,2-
Examples thereof include halogen-based solvents such as dichloroethane and 1,1,2,2-tetrachloroethane, ether-based solvents such as tetrahydrofuran, dioxane, and diglyme. Especially N, N-dimethylacetamide,
When an amide-based solvent such as N-methyl-2-pyrrolidone is used, a highly polymerized polyamic acid can be obtained.

Then, the obtained polyamic acid is added to 200-
Heat at 350 ° C. to obtain a polyimide resin. Further, the polyimide resin can be obtained by treating the polyamic acid with a dehydrating ring-closing agent such as a mixed solution of acetic anhydride and pyridine.

In this method, the molecular weight of the polyimide resin of the present invention is limited by the amount of the diamine compound charged, and a high molecular weight polyimide resin can be produced when used in equimolar amounts.

As an example of the second method for producing the polyimide resin of the present invention, the diamine compound and the tetracarboxylic acid dithio anhydride are reacted in an organic solvent at 20 to 200 ° C. for several minutes to several days. To obtain a polyimide resin. Examples of the organic solvent that can be used in the synthesis reaction of this polyimide include amide solvents such as N, N-dimethylacetamide and N-methyl-2-pyrrolidone,
Aromatic solvents such as benzene, anisole, diphenyl ether, nitrobenzene, benzonitrile, pyridine, halogen solvents such as chloroform, dichloromethane, 1,2-dichloroethane, 1,1,2,2-tetrachloroethane, tetrahydrofuran Examples thereof include ether solvents such as dioxane, dioxane, and diglyme. Especially when an amide-based solvent such as N, N-dimethylacetamide or N-methyl-2-pyrrolidone is used,
A high polymer polyimide can be obtained.

In this method, the molecular weight of the polyimide resin of the present invention is limited by the charged amount with the diamine compound, and a high molecular weight polyimide resin can be produced when used in an equimolar amount.

In the polyimide resin of the present invention, 98%
The inherent viscosity measured in concentrated sulfuric acid at 30 ° C. and a concentration of 0.5 g / dl is not particularly limited, but is 0.1 to 3 dl.
/ G is preferable, and more preferably 0.2 to 2 dl / g. The reason is that the inherent viscosity is 0.1 dl / g.
If it is less than the above range, the molded product formed into a film or the like will not have sufficient properties such as mechanical properties and heat resistance, and if the inherent viscosity exceeds 3 dl / g, the solubility in an organic solvent will be poor.

The polyimide resin of the present invention thus produced becomes soluble in mineral acids such as sulfuric acid. Further, depending on the manufacturing method used, the tetracarboxylic acid dianhydride derivative represented by the general formula (4) and the tetracarboxylic acid dithioanhydride derivative represented by the general formula (5), the solubility thereof is particularly high. However, in some resins, it is soluble in all or part of the solvent such as N-methyl-2-pyrrolidone, dimethylimidazolidinone, dimethyl sulfoxide, metacresol, orthochlorophenol, pyridine. Become.

The polyimide represented by the general formula (2) includes, for example, organic amines such as tetraammonium hydroxide and triethanolamine, alkaline aqueous solutions such as sodium hydroxide and potassium hydroxide, sodium phosphate, potassium phosphate and the like. It becomes completely or partially soluble in the alkali metal phosphates and the like.

The polyimide resin of the present invention is 320
Since it has a high glass transition point of ℃ or more, it is thermally stable and has excellent heat resistance.

The polyimide resin of the present invention contains 30% or more, preferably 4% or more of the structural unit represented by the general formula (1).
0% or more, more preferably 50% or more, and the remaining 4
It includes a polyimide resin composed of a constitutional unit derived from 4'-diaminotriphenylamine. When the content of the structural unit represented by the general formula (1) is less than 30%, heat resistance is poor, which is not preferable.

The polyimide resin of the present invention may be blended with other resins such as polyamide resin and conventional polyimide resin, and various additives as long as the characteristics are not impaired.

[0030]

EXAMPLES The present invention will now be specifically described with reference to examples and comparative examples, but the present invention is not limited to these examples without departing from the gist of the present invention.

(Example 1) 4,4'-diamino-4 "-
Hydroxytriphenylamine 0.595 g (0.02
0 mol) was dissolved in 10 ml of N, N-dimethylacetamide, and 0.601 g (0.020 mol) of 3,4,3 ′, 4′-biphenyltetracarboxylic dianhydride was dissolved as a solid at once. added. After stirring at 25 ° C. for 12 hours, the viscous polymerization solution was cast on a glass plate and dried at room temperature under reduced pressure of about 30 torr for 1 day. On the other hand, the reaction solution was poured into 350 ml of methanol to obtain a polyamic acid solid. The film of polyamic acid prepared on the former glass plate is heated at 100 ° C. for 1 hour and 2
Heat treatment was performed at 00 ° C. for 1 hour and at 300 ° C. for 1 hour under a nitrogen stream to obtain a polyimide resin film. The polyimide resin (film) has an infrared absorption spectrum of 17
Absorption of the carbonyl group of the imide bond were observed respectively in 80 cm ^-1 and 1725 cm ^-1. The inherent viscosity of the obtained polyimide resin was 0.32 dl / g (9
Measured in 8% concentrated sulfuric acid at 30 ° C. and a concentration of 0.5 g / dl.
The same applies below). The inherent viscosity of the polyamic acid was 0.30 dl / g (in dimethylacetamide,
It was measured at 30 ° C. and a concentration of 0.5 g / dl. The same applies below). The glass transition temperature of the obtained polyimide resin was 388 ° C. as shown in Table 1 when measured by a differential scanning calorimeter, and the 10% weight loss temperature by a thermogravimetric measuring device was 511 ° C. in air and nitrogen. It was 536 ° C.
Table 2 shows the solubility of the obtained polyimide resin in a solvent.

(Comparative Example 1) 4,4'-diamino-4 "-
Instead of hydroxytriphenylamine, JP
A polyimide resin was obtained in the same manner as in Example 1 except that 4,4′-diaminotriphenylamine disclosed in 11631 was used. The glass transition temperature of the obtained polyimide resin was measured in the same manner as in Example 1 and the results are shown in Table 1.
Table 2 shows the solubility in the solvent.

(Example 2) 3, 4, 3'of Example 1
A polyimide resin film was obtained in the same manner as in Example 1 except that pyromellitic dianhydride was used instead of 4′-biphenyltetracarboxylic dianhydride. Infrared absorption spectrum of the polyimide resin (film) showed absorption of carbonyl group of imide bond at 1780 cm ⁻¹ and 1725 cm ⁻¹ , respectively. The inherent viscosity of the obtained polyimide resin was 0.34 dl / g. The inherent viscosity of polyamic acid is 0.2.
It was 8 dl / g. When the glass transition temperature of the obtained polyimide resin was measured in the same manner as in Example 1,
As shown in Table 1, the temperature was 384 ° C., and the 10% weight loss temperature measured by a thermogravimetry device was 489 ° C. in air and 51% in nitrogen.
It was 1 ° C. Table 2 shows the solubility of the obtained polyimide resin in a solvent.

(Comparative Example 2) 4,4'-diamino-4 "-
Instead of hydroxytriphenylamine, JP
A polyimide resin was obtained in the same manner as in Example 2 except that 4,4'-diaminotriphenylamine disclosed in 11631 was used. When the glass transition temperature of the obtained polyimide resin was measured in the same manner as in Example 1,
It was not observed as shown in Table 1. Table 2 shows the solubility of the obtained polyimide resin in a solvent.

Example 3 Example 1 was repeated except that 3,4,3 ′, 4′-diphenyl ether tetracarboxylic acid dianhydride was used in place of the pyromellitic dianhydride of Example 2.
A polyimide resin film was obtained by the same method as described in (1). Infrared absorption spectrum of the polyimide resin (film) showed absorption of carbonyl group of imide bond at 1780 cm ⁻¹ and 1725 cm ⁻¹ , respectively. The obtained polyimide resin has an inherent viscosity of 0.31 dl /
It was g. The inherent viscosity of the polyamic acid was 0.24 dl / g. When the glass transition temperature of the obtained polyimide resin was measured in the same manner as in Example 1, it was 358 ° C. as shown in Table 1, and the 10% weight loss temperature by a thermogravimetric measuring device was 475 ° C. in air. , 544 ° C. in nitrogen. Table 2 shows the solubility of the obtained polyimide resin in a solvent.

(Comparative Example 3) 4,4'-diamino-4 "-
Instead of hydroxytriphenylamine, JP
A polyimide resin was obtained in the same manner as in Example 3 except that 4,4'-diaminotriphenylamine disclosed in 11631 was used. The glass transition temperature of the obtained polyimide resin was measured in the same manner as in Example 1 and the results are shown in Table 1.
Table 2 shows the solubility in the solvent.

(Example 4) The same as Example 1 except that 3,4,3 ', 4'-benzophenonetetracarboxylic dianhydride was used in place of the pyromellitic dianhydride of Example 2. A polyimide resin film was obtained by various methods. Infrared absorption spectrum of the polyimide resin (film) showed absorption of carbonyl group of imide bond at 1780 cm ⁻¹ and 1725 cm ⁻¹ , respectively. The obtained polyimide resin had an inherent viscosity of 0.4 dl / g. The inherent viscosity of polyamic acid is 0.46.
It was dl / g. When the glass transition temperature of the obtained polyimide resin was measured in the same manner as in Example 1, it was 322 ° C. as shown in Table 1, and the 10% weight loss temperature by the thermogravimetric measuring device was 462 ° C. in air. , In nitrogen 526
It was ℃. Table 2 shows the solubility of the obtained polyimide resin in a solvent.

(Comparative Example 4) 4,4'-diamino-4 "-
Instead of hydroxytriphenylamine, JP
A polyimide resin was obtained in the same manner as in Example 4 except that 4,4'-diaminotriphenylamine disclosed in 11631 was used. The glass transition temperature of the obtained polyimide resin was measured in the same manner as in Example 1 and the results are shown in Table 1.
Table 2 shows the solubility in the solvent.

Example 5 Instead of the pyromellitic dianhydride of Example 2, 2,2-bis (3,4-dicarboxyphenyl) -1,1,1,3,3,3-hexa A polyimide resin film was obtained in the same manner as in Example 1 except that fluoropropane dianhydride was used. The polyimide resin (film) has an infrared absorption spectrum of 1
Absorption of imide-bonded carbonyl groups was observed at 780 cm ⁻¹ and 1725 cm ⁻¹ , respectively. The obtained polyimide resin had an inherent viscosity of 0.36 dl / g.
The inherent viscosity of polyamic acid is 0.34 dl /
It was g. When the glass transition temperature of the obtained polyimide resin was measured in the same manner as in Example 1, it was 343 ° C. as shown in Table 1, which was 10% measured by a thermogravimetric device.
The weight loss temperature was 495 ° C in air and 513 ° C in nitrogen. Table 2 shows the solubility of the obtained polyimide resin in a solvent.

(Comparative Example 5) 4,4'-diamino-4 "-
Instead of hydroxytriphenylamine, JP
A polyimide resin was obtained in the same manner as in Example 5 except that 4,4'-diaminotriphenylamine disclosed in 11631 was used. The glass transition temperature of the obtained polyimide resin was measured in the same manner as in Example 1 and the results are shown in Table 1.
Table 2 shows the solubility in the solvent.

[0041]

[Table 1]

[0042]

[Table 2]

It can be seen from Tables 1 and 2 that the polyimide resins of Examples 1 to 5 of the present invention have a high glass transition temperature inherent to polyimide resins and are soluble in various solvents. On the other hand, the polyimide resins of Comparative Examples 1 to 5 are soluble in various solvents, but have a low glass transition temperature.

[0044]

While many of the conventional polyimide resins have low solubility in solvents and mineral acids, it is difficult to mold them, whereas the polyimide resins of the present invention are difficult to mold. Or, it is soluble in an alkaline solution, and a molded product such as a film of a polyimide resin can be easily formed by this solution, and also has a high glass transition temperature and excellent heat resistance, so that it can be used as an industrial material. Great value.

─────────────────────────────────────────────────── ─── Continuation of the front page (58) Fields surveyed (Int.Cl. ⁷ , DB name) C08G 73/00-73/26 CAPLUS (STN) REGISTRY (STN)

Claims (3)

(57) [Claims] 1. A polyimide comprising a constitutional unit represented by the following general formula (1) obtained by reacting a diamine compound and a tetracarboxylic acid dianhydride or a diamine compound and a tetracarboxylic acid dithioanhydride in an organic solvent. In resin
Thus, the tetracarboxylic dianhydride is pyromellitic dianhydride.
, 3,4,3 ', 4'-biphenyltetracarboxylic acid
Dianhydride, 3,4,3 ', 4'-diphenyl ether ether
Tracarboxylic acid dianhydride, 3,4,3 ', 4'-benzo
Phenone tetracarboxylic dianhydride, 3,4,3 ',
4'-diphenylsulfone tetracarboxylic acid dianhydride,
2,2-bis (3,4-dicarboxyphenyl) -1,
1,1,3,3,3-hexafluoropropane dianhydride
, 3,4,3 ", 4" -Terphenyl tetracarboxylic
At least one tetracarbohydrate selected from dianhydrides
An acid dianhydride, wherein the tetracarboxylic acid dithioanhydride is pyromellitic acid
Thioanhydride, 3,4,3 ', 4'-biphenyltetraca
Rubonic acid dithio anhydride, 3,4,3 ', 4'-diphenyl
Ruthertetracarboxylic acid dithio anhydride, 3,4
3 ', 4'-benzophenone tetracarboxylic acid dithio nothing
Water, 3,4,3 ', 4'-diphenylsulfone tetra
Carboxylic acid dithioanhydride, 2,2-bis (3,4-dica)
Ruboxylphenyl) -1,1,1,3,3,3-hexyl
Safuropropane dithio anhydride, 3,4,3 ", 4"
-Selected from terphenyl tetracarboxylic acid dithio anhydride
At least one tetracarboxylic acid dithioanhydride
Yes, in 98% concentrated sulfuric acid at 30 ° C, concentration of 0.5 g / dl
Has an inherent viscosity of 0.1 to 3 dl / g
Polyimide resin, characterized in that that. [Chemical 1] 2. The polyimide resin according to claim 1, comprising a constitutional unit represented by the following formula (2). [Chemical 2] 3. A constitutional unit comprising 30% or more of the constitutional unit represented by the general formula (1) according to claim 1, and the rest consisting of constitutional units derived from 4,4′-diaminotriphenylamine. Polyimide resin.