JP2999116B2 - Branched polyimide and method for producing the same - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a process for producing a polyimide having good processability.

[0002]

2. Description of the Related Art Conventionally, polyimides obtained by the reaction of a tetracarboxylic acid and a diamine have various excellent physical properties and good heat resistance, so that they will be used in the fields of electronics, the aerospace industry, etc. Is expected.

Conventionally developed polyimides often have excellent properties, but have excellent heat resistance but poor workability, and resins developed for the purpose of improving workability have poor heat resistance. There were advantages and disadvantages in performance. For example, equation (7)

[0004]

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A polyimide having a basic skeleton represented by the following formula (manufactured by DuPont, trade name: Kapton, Vespel) is a polyimide having no clear glass transition temperature and excellent heat resistance, but is used as a molding material. In such cases, processing is difficult, and processing must be performed using a special method such as powder sintering. In addition, when used as a material for electrical and electronic components, it has a property of having a high water absorption that adversely affects dimensional stability, insulation properties, and solder heat resistance. Equation (8)

[0006]

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A polyetherimide having a basic skeleton represented by the following formula (trade name, manufactured by General Electric Co., Ltd.)
Ultem) is a resin with excellent processability, but has a low glass transition temperature of 217 ° C, is soluble in halogenated hydrocarbons such as methylene chloride, and is satisfactory in terms of heat resistance and solvent resistance. is not. As a result of intensive studies to solve these disadvantages, we found that the general formula (9)

[0008]

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(Wherein, X, Y _{1 to} Y ₄ and R are the same as those described above), and have already filed an application (Japanese Patent Application Laid-Open No. 110530/1991).

The polyimide resin has a temperature of 170 ° C. to 270 ° C.
Shows a clear glass transition temperature in the range, almost no reduction in weight even at around 400 ° C., and good workability. In addition, it has excellent chemical resistance and compensates for the disadvantages of conventional polyimides.

There are various methods for synthesizing the polyimide resin.
A method is known in which a raw material, tetracarboxylic dianhydride, is reacted with a diamine to obtain a polyamic acid, and then subjected to dehydration cyclization by heat or a method of obtaining a polyimide by dehydration cyclization with acetic anhydride.

However, this polyimide resin also has problems such that the processability becomes poorer as the molecular weight increases, the resin gels during processing, and the viscosity of the resin increases.

In order to solve the above problem, the present inventors have heretofore carried out the general formula (10) wherein dicarboxylic acid anhydride is added to both ends of a diamine and further dehydration cyclization is carried out.

[0014]

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Wherein X, Y _{1 to} Y ₄ and R are the same as described above, and that the processability is improved by adding the bisimide compound to the polyimide resin. Application already filed (Japanese Patent Application No. 03
-004963, Japanese Patent Application No. 03-086558). Also,
The inventors of the present invention synthesize the polyimide by synthesizing the above diamine and tetracarboxylic dianhydride in a specific molar ratio to obtain a compound represented by the general formula (9).

[0016]

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(Wherein X, Y _{1 to} Y ₄ and R are the same as those described above), and a processability is obtained by adding the polyimide oligomer to the polyimide resin. And have already filed applications (Japanese Patent Application Nos. 04-340138 and 04-342548).

Further, the present inventors have found that by synthesizing a polyimide under a specific reaction condition, a polyimide resin having good processability containing a low molecular weight polyimide oligomer can be obtained in one pot, and has already filed an application ( Japanese Patent Application No. 05-276387). As described above, the workability is improved by the presence of a low molecular weight component such as a bisimide compound or a polyimide oligomer in the polyimide resin, but there is a problem even in such a case.

[0019]

Generally, a polyimide resin containing a large amount of low molecular weight components such as a bisimide compound or a polyimide oligomer has good workability in extrusion molding or the like, but it is difficult to stretch an extruded film. Uniform stretching cannot be performed, resulting in unevenness in the stretched film. In order to obtain a film which can be stretched uniformly, a film may be made of a polyimide having a high molecular weight. However, if the molecular weight is high, the processability is deteriorated and a raw film to be used for essential stretching cannot be obtained.

Polyimides containing a large amount of low molecular weight components have advantages and disadvantages, such as the occurrence of such problems in secondary processing such as stretching, and exhibit good workability even in extrusion molding methods. There has been a demand for a polyimide resin and a method for producing the same, which enable uniform stretching.

[0021]

The present inventors have conducted intensive studies to solve the above-mentioned problems, and as a result, introduced a specific third component into the polyimide resin at a specific ratio, and branched the polyimide resin. By making the shape, not only the moldability such as extrusion molding is better than the polyimide resin synthesized by the conventional method, but it is also found that a polyimide resin having good stretchability can be obtained, and to complete the present invention. Reached. That is, the present invention provides the following formula (1)

[0022]

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(Wherein, X is a group consisting of a direct bond, a divalent hydrocarbon group having 1 to 10 carbon atoms, a hexafluorinated isopropylidene group, a carbonyl group, a thio group, a sulfinyl group, a sulfonyl group or an oxide. Represents a selected group, Y ₁ ,
Y ₂ , Y ₃ and Y ₄ each independently represent a group selected from the group consisting of hydrogen, lower alkyl group, lower alkoxy group, chlorine and bromine, and may be the same or different. R is an aliphatic group having 2 or more carbon atoms, a cycloaliphatic group, a monocyclic aromatic group, a condensed polycyclic aromatic group, a non-condensed cyclic group in which aromatic groups are connected to each other directly or by a bridge member. Represents a tetravalent group selected from the group consisting of aromatic groups, W represents a trivalent group having at least three carbon atoms, and three amino groups are bonded to different carbon atoms; (Not bonded to adjacent carbon atoms), and W is the following formula (2)

[0024]

Embedded image 2. The branched polyimide resin according to claim 1, wherein the diamine is one or a mixture of two or more selected from the group consisting of:

[0025]

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(Wherein X is a group consisting of a direct bond, a divalent hydrocarbon group having 1 to 10 carbon atoms, a hexafluorinated isopropylidene group, a carbonyl group, a thio group, a sulfinyl group, a sulfonyl group or an oxide. Represents a selected group, Y ₁ ,
Y ₂ , Y ₃ and Y ₄ each independently represent a group selected from the group consisting of hydrogen, lower alkyl group, lower alkoxy group, chlorine and bromine. ) Is a diamine compound represented by the following formula (4):

[0027]

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(Wherein R represents an aliphatic group having 2 or more carbon atoms, a cycloaliphatic group, a monocyclic aromatic group, a condensed polycyclic aromatic group, or an aromatic group, either directly or by a bridge member. A tetravalent dianhydride selected from the group consisting of linked non-condensed cyclic aromatic groups.) And further represented by the following formula (5)

[0029]

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Wherein W is a trivalent group having at least three carbon atoms, and the three amino groups are bonded to different carbon atoms and are not bonded to adjacent carbon atoms. The reaction is carried out in the presence of a triamine represented by the following formula.

[0031]

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(Wherein Z is a group consisting of a monocyclic aromatic group, a condensed polycyclic aromatic group, and a non-condensed polycyclic aromatic group in which the aromatic groups are connected to each other directly or by a bridging member. The reaction is carried out in the presence of a dicarboxylic anhydride represented by the following formula: wherein the amount of tetracarboxylic dianhydride is 0.90 to 0.99 mole ratio per mole of diamine. And the amount of triamine is 0.0
And the ratio of the total number of equivalents of tetracarboxylic dianhydride and dicarboxylic anhydride to the total number of equivalents of diamine and triamine is 1.0 to 2.0.
Equation (1) that is

[0033]

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(Wherein X, Y _{1 to} Y ₄ , W and R are the same as described above). This is a method for producing a branched polyimide resin having a repeating unit represented by the following formula: 3,5-triaminobenzene,
1,3,5-triaminocyclohexane, 1,4,5-
A method for producing the branched polyimide resin, which is one or a mixture of two or more selected from triaminonaphthalenes, and a film obtained from the branched polyimide resin.

Hereinafter, the present invention will be described in detail. When the polyimide resin obtained in the present invention is obtained by reacting a diamine compound with a tetracarboxylic dianhydride to obtain a polyimide resin, a triamine having three amino groups is added and reacted to form a branch in the polyimide skeleton. It has a characteristic that it has a shape like structure.

The polyimide resin obtained in the present invention has a branched structure, so that when compared with a conventional linear polyimide resin having the same molecular weight, it exhibits the same melt viscosity during melt molding such as extrusion molding, and has the same melt viscosity. And a more uniform stretching is possible because the intermolecular entanglement is increased.

The diamine used in the present invention includes bis [4- (3-aminophenoxy) phenyl] methane,
1,1-bis [4- (3-aminophenoxy) phenyl] ethane, 1,2- [4- (3-aminophenoxy)
Phenyl] ethane, 2,2-bis [4- (3-aminophenoxy) phenyl] propane, 2,2-bis [4-
(3-aminophenoxy) phenyl] butane, 2,2-
Bis [4- (3-aminophenoxy) phenyl] -1,
1,1,3,3,3-hexafluoropropane, 4,
4'-bis (3-aminophenoxy) biphenyl, bis [4- (3-aminophenoxy) phenyl] ketone, bis [4- (3-aminophenoxy) phenyl] sulfide, bis [4- (3-aminophenoxy) Phenyl] sulfoxide, bis [4- (3-aminophenoxy) phenyl] sulfone, bis [4- (3-aminophenoxy)
Phenyl] ether and the like, and these are used alone or in combination of two or more.

As the tetracarboxylic dianhydride, ethylene tetracarboxylic dianhydride, cyclopentanecarboxylic dianhydride, pyromellitic dianhydride, 3.3 ', 4
4'-benzophenonetetracarboxylic dianhydride, 2,
2 ', 3,3'-benzophenonetetracarboxylic dianhydride, 3,3', 4,4'-biphenyltetracarboxylic dianhydride, 2,2 ', 3,3'-biphenyltetracarboxylic dianhydride 2,2′-bis (3,4-dicarboxyphenyl) propane dianhydride, 2,2′-bis (2,3-dicarboxyphenyl) propane dianhydride,
Bis (3,4-dicarboxyphenyl) ether dianhydride, bis (3,4-dicarboxyphenyl) sulfone dianhydride, 1,1-bis (2,3-dicarboxyphenyl) ethane dianhydride, bis (2,3-dicarboxyphenyl) methane dianhydride, 1,1-bis (2,3-dicarboxyphenyl) ethane dianhydride, bis (3,4-dicarboxyphenyl) methane dianhydride, 2, 3,6,7-
Naphthalenetetracarboxylic dianhydride, 1,4,5,8
-Naphthalenetetracarboxylic dianhydride, 1,2,5
6-naphthalenetetracarboxylic dianhydride, 1,2,2
3,4-benzenetetracarboxylic dianhydride, 3,4
9,10-berylenetetracarboxylic dianhydride, 2,
3,6,7-anthracenecarboxylic dianhydride, 1,
Examples thereof include 2,7,8-phenanthrene carboxylic dianhydride and the like, which are used alone or in combination of two or more.

As the triamine, melamine, 1,3,
Examples thereof include 5-triaminobenzene, 1,3,5-triaminocyclohexane, and 1,4,5-triaminonaphthalene, which may be used alone or as a mixture of two or more. Examples of the dicarboxylic anhydride represented by the general formula (4) used as a terminal blocking agent in the present invention include phthalic anhydride, 2,3-benzophenone dicarboxylic anhydride,
3,4-benzophenone dicarboxylic anhydride, 2,3-
Dicarboxyphenyl-phenyl-ether anhydride,
3,4-dicarboxyphenyl-phenyl-ether anhydride, 3,4-biphenyldicarboxylic anhydride, 2,3
-Dicarboxyphenyl-phenyl-sulfone anhydride,
2,3-dicarboxyphenyl-phenyl-sulfide anhydride, 1,2-naphthalenedicarboxylic anhydride, 2,
3-naphthalenedicarboxylic acid anhydride, 1,8-naphthalenedicarboxylic acid anhydride, 2,3-anthracenedicarboxylic acid anhydride, 1,9-anthracenedicarboxylic acid anhydride, etc., and these may be used alone or in combination of two or more. Used as

According to the method of the present invention, a starting material diamine, tetracarboxylic dianhydride, triamine, dicarboxylic anhydride is added to an organic solvent and reacted.
(A) A method in which a diamine, a triamine, and a tetracarboxylic dianhydride are reacted, and then a dicarboxylic anhydride is added to continue the reaction. (B) A diamine, a triamine, and a dicarboxylic anhydride are added and reacted. (D) adding diamine, triamine, tetracarboxylic dianhydride and dicarboxylic anhydride at the same time and reacting them.
After reacting diamine, tetracarboxylic dianhydride,
Any addition or reaction may be used, such as a method of adding triamine, continuing the reaction, further adding a dicarboxylic anhydride, and continuing the reaction.

The triamine used in the present invention must have three amino groups bonded to different carbon atoms and not bonded to carbon atoms adjacent to each other. If they are bonded to the same carbon atom or bonded to adjacent carbon atoms, they will not react completely due to steric hindrance, leaving unreacted amino groups, or amide as an intermediate This is because the state of the acid group may remain. In the case where the compound is bonded to an adjacent carbon atom, the formula (11)

[0042]

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Since a ladder structure of (where R and W are the same as above) is adopted, the polyimide resin does not become a branched polyimide, and the effect of the polyimide resin of the present invention cannot be obtained.

The amount of tetracarboxylic dianhydride is 0.90 to 0.99 mole ratio, preferably 0.91 to 0.988 mole ratio, more preferably 0.1 to 0.9 mole ratio per mole of diamine.
915 to 0.985 molar ratio, most preferably 0.92 to 0.92
It is in the range of 0.98 mole ratio. If the molar ratio is less than 0.90, sufficient strength alone cannot be obtained. If the molar ratio exceeds 0.99, the viscosity at the time of melting becomes extremely high, and molding becomes difficult.

The amount of the triamine is 0.001 to 0.1 mole ratio per mole of diamine, preferably 0.001 to 0.1.
2 to 0.08 mole ratio, more preferably 0.005 to 0.
07 molar ratio, more preferably 0.008 to 0.06 molar ratio, most preferably 0.01 to 0.05 molar ratio. If the molar ratio is less than 0.001 mole, the effect of branching does not appear. If the molar ratio exceeds 0.1 mole ratio, gelation occurs during synthesis or the viscosity at the time of melting is extremely high, and molding becomes difficult.

Further, the amount of dicarboxylic anhydride used for terminal capping is such that the total amount of tetracarboxylic dianhydride and dicarboxylic anhydride is equivalent to 1.0 to 2 with respect to 1 mol of total of diamine and triamine. It is necessary to adjust so as to be 0.0. More preferably, it is in the range of 1.0 to 1.5.
If the ratio is less than 1.0 mole ratio, no sufficient effect of terminating the terminal appears, and if it exceeds 2.0 mole ratio, the effect does not change much and it is economically disadvantageous.

As the solvent used for the polymerization, for example, N, N
-Dimethylformamide, N, N-dimethylacetamide, N, N-diethylacetamide, N, N-dimethylmethoxyacetamide, N-methyl-2-pyrrolidone,
1,3-dimethyl-2-imidazolidinone, N-methylcaprolactam, 1,2-dimethoxyethane, bis (2
-Methoxyethyl) ether, 1,2-bis (2-methoxyethoxy) ethane, bis [2- (2-methoxyethoxy) ethyl] ether, tetrahydrofuran, 1,3
-Dioxane, 1,4-dioxane, pyridine, picoline, dimethyl sulfoxide, dimethyl sulfone, tetramethyl urea, hexamethyl phosphoramide, phenol, m-cresol, p-cresol, p-chlorophenol, anisole and the like. These may be used as a mixture. Among these, m-cresol, p-
Cresol is particularly preferred.

The reaction temperature is usually in the range of 0 ° C. to 250 ° C. Preferably 60 ° C to 240 ° C, more preferably 1 ° C to 240 ° C.
00 ° C to 220 ° C, more preferably 140 ° C to 210
The reaction may be carried out at a temperature in the range of 180C to 200C. The reaction pressure is not particularly limited,
It does not matter at all whether it is carried out under normal pressure or under pressure.

The reaction time varies depending on the reaction temperature, but is generally at least 1 hour, particularly preferably in the range of 2 to 6 hours. If the reaction time is shorter than 1 hour, the molecular weight of the produced polymer will not be sufficiently increased. Even if the reaction time is longer than 6 hours, there is no great difference in the physical properties of the produced polymer.

When the polyimide of the present invention is subjected to melt molding, other thermoplastic resins such as polyethylene, polypropylene, polycarbonate, polyarylate, polyamide, polysulfone, polyethersulfone, and polyether may be used as long as the object of the present invention is not impaired. Ketone, polyetheretherketone, polyphenylene sulfide,
An appropriate amount of polyamide imide, polyether imide, modified polyphenylene oxide or the like can be blended according to the purpose.

Further, the following fillers and the like used in ordinary resin compositions may be used to such an extent that the object of the invention is not impaired. That is, reinforcement of abrasion resistance materials such as graphite, carborundum, silica stone powder, molybdenum disulfide, fluororesin, glass fiber, carbon fiber, boron fiber, silicon carbide fiber, carbon whisker, asbestos, metal fiber, ceramic fiber, etc. Materials, flame retardant materials such as antimony trioxide, magnesium carbonate, calcium carbonate, etc., electric property improving materials such as clay and mica,
Tracking resistance improving materials such as asbestos, silica and graphite, acid resistance improving materials such as barium sulfate, silica and calcium metasilicate, heat conductivity improving materials such as iron powder, zinc powder, aluminum powder and copper powder, and other glass beads,
Glass sphere talc, diatomaceous earth, alumina, Silasbarn,
Hydrated alumina, metal oxides, coloring agents and the like.

[0052]

EXAMPLES Hereinafter, the present invention will be described specifically with reference to Examples and Comparative Examples, but the present invention is not limited to these Examples. Example 1 368.4 g (1.0 mol) of 4,4′-bis (3-aminophenoxy) biphenyl and phthalic anhydride 2 were placed in a reaction vessel equipped with a stirrer, a reflux condenser, and a nitrogen inlet tube.
6.64 g (0.18 mol), pyromellitic anhydride 20
6.1 g (0.945 mol), 3.15 g of melamine
(0.025 mol) and 2,200 g of m-cresol
And heated to 200 ° C. with stirring, at 200 ° C. for 6 hours.
Incubated for hours. Next, toluene was charged to the reaction solution, and the precipitate was separated by filtration, washed several times with toluene, and dried at 250 ° C. for 6 hours under a nitrogen atmosphere to obtain 51
2 g of polyimide powder was obtained. The obtained polyimide powder was dried at 200 ° C. for 20 hours under a nitrogen stream, and after sufficiently removing water, it was supplied to a 25 mm vent type extruder, and 400 ° C.
The mixture was melt-extruded from a die having a diameter of 3 mm, cooled and solidified, and cut by a pelletizer to obtain a polyimide pellet having a diameter of about 2 mm and a length of about 3 mm. The polyimide pellet was dried at 200 ° C. for 20 hours under a nitrogen stream to sufficiently remove water, then supplied to a 25 mm extruder, heated and melted at 410 ° C., and slit 150 mm in width using a slit die (having a gap of 0.6 m).
m), and a polyimide film having a thickness of about 200 μm was obtained on a roll at 220 ° C. The logarithmic viscosity of this polyimide film was 0.55 dl / g.
Here, the logarithmic viscosity was determined using a mixed solvent of parachlorophenol and phenol (weight ratio 90:10) at a concentration of 0.5 g.
/ 100 ml solvent, measured at 35 ° C. Using the polyimide film obtained in this example, the change with time of the melt viscosity was measured with an orifice having a diameter of 0.1 cm and a length of 1 cm using a Koka type flow tester (CFT-500, manufactured by Shimadzu Corporation). After keeping the temperature at 420 ° C. for 5 minutes, it was partially extruded at a pressure of 100 kg / cm ² and the viscosity was measured. 100 kg / cm ^{2 for the} rest
And the viscosity was measured. 420 ° C
The relationship between the holding time and the melt viscosity is shown in Table 1 (Table 1). Even if the holding time is prolonged, there is almost no change in the melt viscosity, indicating that the thermal stability is good. It can be seen that the melting characteristics are the same as in Comparative Example 1 to be described later, despite the fact that they contain a branched structure. This film is 90m on each side
m and cut into a batch-type stretching machine (Iwamoto Seisakusho's batch-type stretching machine BIX-703 type).
The film was stretched 2.5 times in a uniaxial direction at 0 ° C., then stretched 2.5 times in a direction perpendicular thereto, and further heat-treated at 300 ° C. for 30 minutes to obtain a biaxially stretched film. Evaluation of the stretching ratio is as follows. Eighteen grid lines at 5 mm intervals are written in the film plane in each of the vertical and horizontal directions, and the distance between the grid lines after stretching at 100 points of intersection at each of the 10 central portions is measured to determine the stretching ratio. , The rate of change from the average and standard deviation (standard deviation ÷ average x 100%)
I asked. As a result, the average value of the stretching ratio in the second axis was 2.
495, the fluctuation rate was 2.90%. The fluctuation rate was extremely small as compared with Comparative Examples 1 and 4 described later, and it was recognized that excellent uniform stretching was performed.

Example 2 Example 1 was repeated except that 3.13 g (0.025 mol) of 1,3,5-triaminobenzene was used as the starting triamine.
An experiment was performed in the same manner as described above to obtain 511 g of polyimide powder,
Further, pelletization and film formation were performed in the same manner as in Example 1. The logarithmic viscosity of the obtained film is 0.55 dl /
g. Table 1 (Table 1) shows the change over time in the melt viscosity. Even if the holding time is prolonged, there is almost no change in the melt viscosity, indicating that the thermal stability is good. The obtained film was biaxially stretched in the same manner as in Example 1. As a result, the average value of the stretching ratio in the second axis was 2.490, and the fluctuation rate was 2.92%.
It was confirmed that the variation rate was extremely small as compared with Comparative Examples 1 and 4 described later, and that excellent uniform stretching was performed.

Example 3 An experiment was conducted in the same manner as in Example 1 except that 3.23 g (0.025 mol) of 1,3,5-triaminocyclohexane was used as a starting triamine to obtain 512 g of a polyimide powder. Further, pelletization and film formation were performed in the same manner as in Example 1. The logarithmic viscosity of the obtained film is 0.55 d
1 / g. Table 1 (Table 1) shows the change over time in the melt viscosity. Even if the holding time is prolonged, there is almost no change in the melt viscosity, indicating that the thermal stability is good. The obtained film was biaxially stretched in the same manner as in Example 1. As a result, the average value of the stretching ratio in the second axis was 2.492, and the fluctuation rate was 2.9.
It was 4%, which was much smaller than that of Comparative Examples 1 and 4 described later, and it was confirmed that excellent uniform stretching was performed.

Example 4 Example 1 was repeated except that 4.38 g (0.025 mol) of 1,4,5-triaminonaphthalene was used as the starting triamine.
The same experiment was performed to obtain 513 g of polyimide powder,
Further, pelletization and film formation were performed in the same manner as in Example 1. The logarithmic viscosity of the obtained film is 0.55 dl /
g. Table 1 (Table 1) shows the change over time in the melt viscosity. Even if the holding time is prolonged, there is almost no change in the melt viscosity, indicating that the thermal stability is good. The obtained film was biaxially stretched in the same manner as in Example 1. As a result, the average value of the stretching ratio in the second axis was 2.490, and the variation was 3.04%.
It was confirmed that the variation rate was extremely small as compared with Comparative Examples 1 and 4 described later, and that excellent uniform stretching was performed.

Example 5 1.89 g (0.015 mol) of melamine and 1.23 g of 1,3,5-tetraaminobenzene were added to the starting triamine.
An experiment was performed in the same manner as in Example 1 except that (0.010 mol) was used, to obtain 513 g of a polyimide powder. Further, pelletization and film formation were performed as in Example 1. The logarithmic viscosity of the obtained film was 0.55 dl / g. Table 1 (Table 1) shows the change over time in the melt viscosity. Even if the holding time is prolonged, there is almost no change in the melt viscosity, indicating that the thermal stability is good. The obtained film was biaxially stretched in the same manner as in Example 1. As a result, the average value of the stretching ratio in the second axis was 2.495, and the variation was 3.03%.
It was recognized that the variation rate was extremely small as compared with Comparative Examples 1 and 4 described later, and that excellent uniform stretching was performed.

Example 6 Bis [4- (3-aminophenoxy) was used as the starting diamine.
The experiment was carried out in the same manner as in Example 1 except that 396.0 g (1.0 mol) of [phenyl] ketone was used, and 524 g of a polyimide powder was obtained. Further, pelletization and film formation were carried out as in Example 1. The logarithmic viscosity of the obtained film is
It was 0.58 dl / g. Table 1 (Table 1) shows the change over time in the melt viscosity. Even if the holding time is prolonged, there is almost no change in the melt viscosity, indicating that the thermal stability is good. The obtained film was biaxially stretched in the same manner as in Example 1. As a result, the average value of the stretching ratio of the second axis was 2.492, the variation was 3.05%, the variation was extremely small, and the uniformity was excellent. It was recognized that stretching was performed.

Example 7 3,3 ', 4,4' was added to the starting material tetracarboxylic dianhydride.
-Benzophenonetetracarboxylic dianhydride 304.5
An experiment was conducted in the same manner as in Example 1 except that g (0.945 mol) was used, to obtain 591.3 g of a polyimide powder. Further, pelletization and film formation were performed in the same manner as in Example 1.
The logarithmic viscosity of the obtained film was 0.59 dl / g. Table 1 (Table 1) shows the change over time in the melt viscosity. Even if the holding time is prolonged, there is almost no change in the melt viscosity, indicating that the thermal stability is good. As a result of biaxially stretching the obtained film in the same manner as in Example 1, the average value of the stretching ratio of the second axis was 2.492, and the variation was 3.03%.
It was recognized that the fluctuation rate was extremely small, and favorable uniform stretching was performed.

Example 8 12.6 g (0.1 mol) of melamine was used as the starting triamine and 53.28 g of phthalic anhydride was used as the dicarboxylic anhydride.
An experiment was performed in the same manner as in Example 1 except that (0.36 mol) was used, to obtain 561.5 g of a polyimide powder. Further, pelletization and film formation were performed in the same manner as in Example 1. The logarithmic viscosity of the obtained film was 0.86 dl / g. Table 1 (Table 1) shows the change over time in the melt viscosity. As the holding time increased, the melt viscosity increased and the thermal stability was somewhat poor, but a film could be produced. The obtained film was biaxially stretched in the same manner as in Example 1. As a result, the average value of the stretching ratio in the second axis was 2.495, and the fluctuation rate was 2.98%.
It was confirmed that the variation rate was extremely small and good uniform stretching was performed.

Example 9 0.126 g (0.001 g) of melamine was added to triamine as a raw material.
Mol), 17.76 phthalic anhydride to dicarboxylic anhydride.
An experiment was conducted in the same manner as in Example 1 except that g (0.12 mol) was used, and 509.5 g of a polyimide powder was obtained. Further, pelletization and film formation were performed as in Example 1. The logarithmic viscosity of the obtained film was 0.54 dl / g. Table 1 (Table 1) shows the change over time in the melt viscosity. Even if the holding time is prolonged, there is almost no change in the melt viscosity, indicating that the thermal stability is good. The obtained film was biaxially stretched in the same manner as in Example 1. As a result, the average value of the stretching ratio of the second axis was 2.495, and the variation was 5.05%.
It was recognized that the fluctuation rate was extremely small, and favorable uniform stretching was performed.

Example 10 Except that 200.56 g (0.92 mol) of pyromellitic anhydride was used as the starting tetracarboxylic dianhydride and 34.04 g (0.23 mol) of phthalic anhydride were used as the dicarboxylic anhydride. Conducted an experiment in the same manner as in Example 1 to obtain 510.3 g of a polyimide powder, and further, pelletized as in Example 1,
The film was formed. The logarithmic viscosity of the obtained film was 0.52 dl / g. Table 1 (Table 1) shows the change over time in the melt viscosity. Even if the holding time is prolonged, there is almost no change in the melt viscosity, indicating that the thermal stability is good. The obtained film was biaxially stretched in the same manner as in Example 1. As a result, the average value of the stretching ratio of the second axis was 2.497, the fluctuation rate was 4.55%, the fluctuation rate was extremely small, and the uniformity was excellent. It was recognized that stretching was performed.

Example 11 368.2 g of phthalic anhydride as a dicarboxylic anhydride
An experiment was conducted in the same manner as in Example 1 except that (2.26 mol) was used, and 514.0 g of a polyimide powder was obtained. Further, pelletization and film formation were performed as in Example 1. The logarithmic viscosity of the obtained film was 0.50 dl / g. Table 1 (Table 1) shows the change over time in the melt viscosity. Even if the holding time is prolonged, there is almost no change in the melt viscosity, indicating that the thermal stability is good. As a result of biaxially stretching the obtained film in the same manner as in Example 1, the average value of the stretching ratio of the second axis was 2.497, and the variation was 4.54%.
It was recognized that the fluctuation rate was extremely small, and favorable uniform stretching was performed.

Example 12 0.126 g (0.001 g) of melamine was added to the starting triamine.
Mol), and 196.2 g (0.90 mol) of pyromellitic anhydride as the tetracarboxylic anhydride and 29.60 g (0.20 mol) of phthalic anhydride as the dicarboxylic anhydride. An experiment was performed to obtain 499.5 g of a polyimide powder, and pelletization and film formation were performed in the same manner as in Example 1. The logarithmic viscosity of the obtained film is
It was 0.46 dl / g. Table 1 (Table 1) shows the change over time in the melt viscosity. Even if the holding time is prolonged, there is almost no change in the melt viscosity, indicating that the thermal stability is good. The obtained film was biaxially stretched in the same manner as in Example 1. As a result, the average value of the stretching ratio of the second axis was 2.495, the fluctuation rate was 6.15%, the fluctuation rate was extremely small, and the uniformity was excellent. It was recognized that stretching was performed.

Example 13 0.126 g (0.001 g) of melamine was added to triamine as a raw material.
Mol), 215.8 g (0.99 mol) of pyromellitic anhydride as the tetracarboxylic anhydride and 34.04 g (0.23 mol) of phthalic anhydride as the dicarboxylic anhydride. An experiment was conducted to obtain 502.2 g of a polyimide powder, which was further formed into a pellet and a film in the same manner as in Example 1. The logarithmic viscosity of the obtained film is
0.88 dl / g. Table 1 (Table 1) shows the change over time in the melt viscosity. As the holding time increased, the melt viscosity increased and the thermal stability was somewhat poor, but a film could be produced. As a result of biaxially stretching the obtained film in the same manner as in Example 1, the average value of the stretching ratio in the second axis was 2.49.
5. The fluctuation rate was 2.99%, the fluctuation rate was extremely small, and it was recognized that good uniform stretching was performed.

Example 14 12.6 g (0.1 mol) of melamine was used as the starting triamine and pyromellitic anhydride 1 was used as the tetracarboxylic anhydride.
An experiment was conducted in the same manner as in Example 1 except that 96.2 g (0.90 mol) and 65.12 g (0.44 mol) of phthalic anhydride were used as the dicarboxylic anhydride to obtain 517.1 g of a polyimide powder. Further, pelletization and film formation were performed in the same manner as in Example 1. The logarithmic viscosity of the obtained film is
0.74 dl / g. Table 1 (Table 1) shows the change over time in the melt viscosity. As the holding time increased, the melt viscosity increased and the thermal stability was somewhat poor, but a film could be produced. As a result of biaxially stretching the obtained film in the same manner as in Example 1, the average value of the stretching ratio in the second axis was 2.49.
7. The fluctuation rate was 3.05%, and the fluctuation rate was extremely small, and it was confirmed that excellent uniform stretching was performed.

Example 15 12.6 g (0.1 mol) of melamine was used as the starting triamine, and pyromellitic anhydride 2 was used as the tetracarboxylic anhydride.
The experiment was carried out in the same manner as in Example 1 except that 15.8 g (0.99 mol) and 41.44 g (0.28 mol) of phthalic anhydride were used as the dicarboxylic anhydride to obtain 534.6 g of a polyimide powder. Further, pelletization and film formation were performed in the same manner as in Example 1. The logarithmic viscosity of the obtained film is
0.95 dl / g. Table 1 (Table 1) shows the change over time in the melt viscosity. As the holding time increased, the melt viscosity increased and the thermal stability was somewhat poor, but a film could be produced. As a result of biaxially stretching the obtained film in the same manner as in Example 1, the average value of the stretching ratio in the second axis was 2.49.
7. The fluctuation rate was 2.89%, the fluctuation rate was extremely small, and it was recognized that good uniform stretching was performed.

[0067]

[Table 1] Note: The melt viscosity is a value measured at 420 ° C., and the unit is centipoise. The thickening ratio is a value obtained by dividing a value at 420 ° C./30 minutes by a value at 420 ° C./5 minutes.

Comparative Example 1 An experiment was conducted in the same manner as in Example 1 except that melamine was not used as a triamine, to obtain 507.2 g of a polyimide powder.
Further, pelletization and film formation were performed in the same manner as in Example 1. The logarithmic viscosity of the obtained film is 0.54 dl /
g. Table 2 (Table 2) shows the change over time in the melt viscosity. Even if the holding time is prolonged, there is almost no change in the melt viscosity, indicating that the thermal stability is good. However, the obtained film was biaxially stretched in the same manner as in Example 1. As a result, the average value of the stretching ratio of the second axis reached 2.497, and the variation rate reached 14.57%. It was recognized that uniform stretching was not performed.

Comparative Example 2 An experiment was conducted in the same manner as in Example 1 except that 0.1 g (0.0008 mol) of melamine was used as a triamine.
6.9 g of polyimide powder was obtained, and pelletized and formed into a film in the same manner as in Example 1. The logarithmic viscosity of the obtained film was 0.54 dl / g. Table 2 (Table 2) shows the change over time in the melt viscosity. Even if the holding time is prolonged, there is almost no change in the melt viscosity, indicating that the thermal stability is good. However, the obtained film was biaxially stretched in the same manner as in Example 1, and as a result, the average value of the stretching ratio of the second axis reached 2.496, and the variation rate reached 9.65%. It was recognized that uniform stretching was not performed. It can be seen that the amount of triamine is small and the effect of the invention is not sufficiently exhibited.

Comparative Example 3 13.86 g (0.11 mol) of melamine as a triamine and 56.24 g of phthalic anhydride in dicarboxylic anhydride.
An experiment was conducted in the same manner as in Example 1 except for using 0.38 mol, to obtain 544.6 g of a polyimide powder. Further, pelletization and film formation were attempted in the same manner as in Example 1. Was so high that no film could be obtained. This is probably because the amount of the triamine was too large, and the polymer was crosslinked to lose the thermoplastic property.

Comparative Example 4 Melamine was not used as a triamine, and pyromellitic anhydride was 208.19 g as a tetracarboxylic dianhydride.
(0.955 mol), and an experiment was conducted in the same manner as in Example 1 except for using 13.32 g (0.09 mol) of phthalic anhydride as a dicarboxylic anhydride, to obtain 508.2 g of a polyimide powder. As in the case of No. 1, pelletization and film formation were performed. The logarithmic viscosity of the obtained film is 0.5
It was 7 dl / g. In addition, the change with time of the melt viscosity
It is shown in the table (Table 2). Even if the holding time is prolonged, there is almost no change in the melt viscosity, indicating that the thermal stability is good. However, as a result of biaxially stretching the obtained film in the same manner as in Example 1, the average value of the stretching ratio of the second axis was 2.493,
The variation rate reached 8.44%, indicating that the variation rate was large and good uniform stretching was not performed. Comparative Example 4
The film obtained in Example 1 had a logarithmic viscosity and a melt viscosity of Example 1.
Although the film was higher than the film obtained in Example 1, good uniform stretching was not performed, indicating that the effect of the branched structure by the triamine of Example 1 was large.

Comparative Example 5 1,2,4-Triaminobenzene as triamine
An experiment was performed in the same manner as in Example 1 except that 05 g (0.025 mol) was used, to obtain 511 g of a polyimide powder. Further, pelletization and film formation were performed in the same manner as in Example 1.
The logarithmic viscosity of the obtained film was 0.54 dl / g. Table 2 (Table 2) shows the change over time in the melt viscosity. Even if the holding time is prolonged, there is almost no change in the melt viscosity, indicating that the thermal stability is good. However, as a result of biaxially stretching the obtained film in the same manner as in Example 1, the average value of the stretching ratio of the second axis was 2.490, and the variation was 10.
As a result, the variation rate was as large as 49%, and it was recognized that good uniform stretching was not performed. Among the three amino groups of the triamine, some of them are bonded to adjacent carbon atoms, so they have a ladder structure and do not have a branched structure, so it is considered that the effects of the invention are not sufficiently exhibited.

Comparative Example 6 25.16 g of phthalic anhydride as a dicarboxylic anhydride
An experiment was performed in the same manner as in Example 1 except that (0.17 mol) was used, and 521.0 g of a polyimide powder was obtained. Further, pelletization and film formation were performed as in Example 1. The logarithmic viscosity of the obtained film was 0.56 dl / g. Table 2 (Table 2) shows the change over time in the melt viscosity. When the holding time is prolonged, the melt viscosity increases, and although the film is obtained, it can be seen that the film is inferior in heat stability to Example 1. This is probably because unreacted terminals remained because the amount of phthalic anhydride did not reach the equivalent.
However, the obtained film was biaxially stretched in the same manner as in Example 1, and as a result, the average value of the stretching ratio of the second axis was 2.496, and the variation was 3.00%. It was recognized that uniform stretching was performed.

Comparative Example 7 0.113 g (0.000 g) of melamine was added to triamine as a raw material.
9 mol), and 196.2 g (0.90 mol) of pyromellitic anhydride as the tetracarboxylic anhydride and 31.08 g (0.21 mol) of phthalic anhydride as the dicarboxylic anhydride. In the same way, 489.5 g
And a pellet was formed into a film in the same manner as in Example 1. The logarithmic viscosity of the obtained film was 0.46 dl / g. Table 2 (Table 2) shows the change over time in the melt viscosity. Even if the retention time is extended,
There was almost no change in the melt viscosity, indicating that the thermal stability was good. However, the obtained film was biaxially stretched in the same manner as in Example 1. As a result, the average value of the stretching ratio of the second axis reached 2.496, and the variation rate reached 11.63%. It was recognized that uniform stretching was not performed. It can be seen that the amount of triamine is small and the effect of the invention is not sufficiently exhibited.

Comparative Example 8 0.126 g (0.001 g) of melamine was added to triamine as a raw material.
Mol), and 194.0 g (0.89 mol) of pyromellitic anhydride as the tetracarboxylic anhydride and 34.04 g (0.23 mol) of phthalic anhydride as the dicarboxylic anhydride. An experiment was performed to obtain 479.5 g of a polyimide powder, and further, pelletization and film formation were performed in the same manner as in Example 1. The logarithmic viscosity of the obtained film was 0.44 dl / g. Table 2 (Table 2) shows the change over time in the melt viscosity. Even if the retention time is extended,
There was almost no change in the melt viscosity, indicating that the thermal stability was good. However, as a result of biaxially stretching the obtained film in the same manner as in Example 1, the average value of the stretching ratio of the second axis reached 2.496, and the variation rate reached 9.93%. It was recognized that uniform stretching was not performed. It can be seen that the effect of the invention is not sufficiently exhibited because the amount of tetracarboxylic dianhydride is small and the molecular weight is low.

Comparative Example 9 0.113 g (0.000 g) of melamine was added to triamine as a raw material.
9 mol), 215.8 g (0.99 mol) of pyromellitic anhydride as tetracarboxylic anhydride, and 2.66 g (0.018 mol) of phthalic anhydride as dicarboxylic anhydride. The same experiment was performed, and 499.1 g was used.
And a pellet was formed into a film in the same manner as in Example 1. The logarithmic viscosity of the obtained film was 0.82 dl / g. Table 2 (Table 2) shows the change over time in the melt viscosity. Even if the retention time is extended,
There was almost no change in the melt viscosity, indicating that the thermal stability was good. However, as a result of biaxially stretching the obtained film in the same manner as in Example 1, the average value of the stretching ratio of the second axis reached 2.496, and the variation rate reached 8.46%. It was recognized that uniform stretching was not performed. It can be seen that the amount of triamine is small and the effect of the invention is not sufficiently exhibited.

COMPARATIVE EXAMPLE 10 12.6 g (0.1 mol) of melamine was used as the starting triamine, and pyromellitic anhydride 1 was used as the tetracarboxylic anhydride.
The experiment was carried out in the same manner as in Example 1 except that 94.0 g (0.89 mol) and 68.08 g (0.46 mol) of phthalic anhydride were used as the dicarboxylic anhydride to obtain 537.9 g of a polyimide powder. And further pelletized as in Example 1,
The film was formed. The logarithmic viscosity of the obtained film was 0.49 dl / g. Table 2 (Table 2) shows the change over time in the melt viscosity. Even if the holding time is prolonged, there is almost no change in the melt viscosity, indicating that the thermal stability is good. However, as a result of biaxially stretching the obtained film in the same manner as in Example 1, the average value of the stretching ratio of the second axis reached 2.496, and the fluctuation rate reached 7.49%. It was recognized that uniform stretching was not performed. It can be seen that the effect of the invention is not sufficiently exhibited because the amount of tetracarboxylic dianhydride is small and the molecular weight is low.

Comparative Example 11 0.126 g (0.001 g) of melamine was added to triamine as a raw material.
Mol), 216.1 g (0.991 mol) of pyromellitic anhydride as the tetracarboxylic anhydride, and 3.11 g (0.021 mol) of phthalic anhydride as the dicarboxylic anhydride. Experiment with 503.4g
Polyimide powder was obtained, and pelletization and film formation were attempted in the same manner as in Example 1. However, the melt viscosity was extremely high, and a film could not be obtained. This is probably because the amount of the tetracarboxylic dianhydride was too large, the molecular weight of the polymer was increased, and the thermoplastic property was lost.

COMPARATIVE EXAMPLE 12 13.9 g (0.11 mol) of melamine was used as the starting triamine, and pyromellitic anhydride 1 was used as the tetracarboxylic anhydride.
An experiment was conducted in the same manner as in Example 1 except that 96.2 g (0.90 mol) and 68.08 g (0.46 mol) of phthalic anhydride were used as a dicarboxylic anhydride, to obtain 527.1 g of a polyimide powder. And further pelletized as in Example 1,
An attempt was made to form a film, but the melt viscosity was extremely high, and a film could not be obtained. This is probably because the amount of the triamine was too large, and the polymer was crosslinked to lose the thermoplastic property.

COMPARATIVE EXAMPLE 13 12.6 g (0.1 mol) of melamine was used as the starting triamine, and pyromellitic anhydride 2 was used as the tetracarboxylic anhydride.
An experiment was conducted in the same manner as in Example 1 except for using 16.1 g (0.991 mol) and 41.44 g (0.28 mol) of phthalic anhydride as a dicarboxylic anhydride, to obtain 522.6 g of a polyimide powder. Further, pelletization and film formation were attempted in the same manner as in Example 1, but the melt viscosity was extremely high, and a film could not be obtained. This is probably because the amount of the tetracarboxylic dianhydride was too large, the molecular weight of the polymer was increased, and the thermoplastic property was lost.

Comparative Example 14 13.9 g (0.11 mol) of melamine was used as the starting triamine, and pyromellitic anhydride 2 was used as the tetracarboxylic anhydride.
An experiment was conducted in the same manner as in Example 1 except that 15.8 g (0.99 mol) and 45.88 g (0.31 mol) of phthalic anhydride were used as dicarboxylic anhydride to obtain 537.1 g of a polyimide powder. And further pelletized as in Example 1,
An attempt was made to form a film, but the melt viscosity was extremely high, and a film could not be obtained. This is probably because the amount of the triamine was too large, and the polymer was crosslinked to lose the thermoplastic property.

[0082]

[Table 2] Note: The melt viscosity is a value measured at 420 ° C., and the unit is centipoise. The thickening ratio is a value obtained by dividing a value at 420 ° C./30 minutes by a value at 420 ° C./5 minutes. Comparative Examples 3 and 1
1, 12, 13, and 14 did not give a film and could not be measured.

[0083]

According to the method of the present invention, it is possible to provide a polyimide resin which not only has excellent thermal stability during processing but also can be stretched uniformly in the production of a stretched film. It is an inexpensive and simple method industrially, and the present invention is significant.

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Claims (5)

(57) [Claims] [Claim 1] The following formula (1) (Wherein X is selected from the group consisting of a direct bond, a divalent hydrocarbon group having 1 to 10 carbon atoms, a hexafluorinated isopropylidene group, a carbonyl group, a thio group, a sulfinyl group, a sulfonyl group and an oxide. Y ₁ , Y ₂ , Y
₃ and Y ₄ each independently represent a group selected from the group consisting of hydrogen, lower alkyl group, lower alkoxy group, chlorine and bromine, and may be the same or different. R is an aliphatic group having 2 or more carbon atoms, a cycloaliphatic group, a monocyclic aromatic group, a condensed polycyclic aromatic group, a non-condensed cyclic group in which aromatic groups are connected to each other directly or by a bridge member. Represents a tetravalent group selected from the group consisting of aromatic groups, W represents a trivalent group having at least three carbon atoms, and three amino groups are bonded to different carbon atoms; (Not bonded to adjacent carbon atoms). 2. W is the following formula (2): The branched polyimide resin according to claim 1, which is one or a mixture of two or more selected from the group consisting of: 3. The method for producing a branched polyimide resin according to claim 1, wherein the diamine is represented by the following formula (3). (Wherein X is selected from the group consisting of a direct bond, a divalent hydrocarbon group having 1 to 10 carbon atoms, a hexafluorinated isopropylidene group, a carbonyl group, a thio group, a sulfinyl group, a sulfonyl group and an oxide. Y ₁ , Y ₂ , Y
₃ and Y ₄ each independently represent a group selected from the group consisting of hydrogen, lower alkyl group, lower alkoxy group, chlorine and bromine. Wherein the tetracarboxylic dianhydride is represented by the following formula (4): (Wherein, R represents an aliphatic group having 2 or more carbon atoms, a cycloaliphatic group,
And a tetravalent group selected from the group consisting of a monocyclic aromatic group, a condensed polycyclic aromatic group, and a non-condensed cyclic aromatic group in which the aromatic groups are connected to each other directly or by a crosslinking member. Is a tetracarboxylic dianhydride represented by the following formula (5): Wherein W is a trivalent group having at least three carbon atoms, and the three amino groups are bonded to different carbon atoms and are not bonded to adjacent carbon atoms. The reaction is carried out in the presence of triamine, and the reaction is further carried out according to the following formula (6). Wherein Z is selected from the group consisting of a monocyclic aromatic group, a fused polycyclic aromatic group, and a non-fused polycyclic aromatic group in which the aromatic groups are interconnected directly or by a bridging member. The reaction is carried out in the presence of a dicarboxylic anhydride represented by the formula: wherein the amount of tetracarboxylic dianhydride is 0.90 to 0.99 mole ratio per mole of diamine; And the amount of triamine is 0.001 to 0.1 mole ratio with respect to 1 mole of diamine, and the sum of the number of equivalents of tetracarboxylic dianhydride and dicarboxylic anhydride with respect to 1 of the total number of equivalents of diamine and triamine. Formula (1) wherein the ratio of is 1.0 to 2.0. (Wherein, X, Y _{1 to} Y ₄ , W and R are the same as described above) as a basic skeleton. 4. The triamine is one or a mixture of two or more selected from melamine, 1,3,5-triaminobenzene, 1,3,5-triaminocyclohexane and 1,4,5-triaminonaphthalene. The method for producing a branched polyimide resin according to claim 3. 5. A film obtained from the branched polyimide resin according to claim 1.