JPH06239998A - Thermoplastic polyimide and polyamic acid - Google Patents

Abstract

PURPOSE:To obtain the subject polyimide comprising a specific structure, excellent in low temperature adhesivity, radiation resistance and low water absorbability, and useful for insulating coating materials, etc. CONSTITUTION:A thermoplastic polyimide represented by formula I (Ar1, Ar2, Ar4, Ar6 are divalent organic groupl Ar3, Ar5 are tetravalent organic groupl (l), (m), (n) are 0, a positive integer of >=1; l+m=>=1; (t) is a positive integer of >=1. This polyimide is produced e.g. by addition-reacting an esterdiamine of formula II (Ar10 is divalent organic group; alone or its mixture with one kind or more of diamines of formula III (Ar7 is divalent organic group) to produce an ester acid dianhydride of formula IV (Ar8 is divalent organic group) alone or its mixture with one kind or more of organic tetracarboxylic acid dianhydride of formula V (Ar9 is tetravalent organic group) in an organic solvent and subsequently subjecting the produced polyimide precursor of formula VI to a ring-closing reaction.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a thermoplastic polyimide and its precursor polyamic acid.
The present invention relates to a thermoplastic polyimide composition having excellent low-temperature adhesiveness and radiation resistance, and a polyamic acid which is a precursor thereof.

[0002]

2. Description of the Related Art Recently, with the progress of particle physics,
Construction of accelerators that generate even higher energy is progressing. In order to generate this high energy, a magnet that can carry a large current and generate a strong magnetic field is required.Recently, the number of cases where a superconducting magnet using a superconducting wire is used as the wire of the magnet is increasing. ing. An oxide containing copper as a main component is often used as a material for this superconducting wire, but if a thermosetting adhesive is used to coat this superconducting wire with an insulating coating material, heat can be applied by applying heat. The rate of oxidation of the superconducting wire changes, and the characteristics of the superconducting magnet may deteriorate. Therefore, the use of an adhesive that cures and adheres at low temperatures is essential for such applications.

An accelerator is a device for accelerating elementary particles such as protons and protons, electrons and electrons, colliding and collapsing them, and investigating the particles generated from them. However, a large amount of radiation is generated by its nature. Therefore, excellent radiation resistance is required for the insulating coating material and the adhesive used for the superconducting magnet.

[0004]

At present, a polyimide film is used as an insulating coating material for a superconducting magnet and an epoxy adhesive is used as an adhesive. However,
Polyimide film has good radiation resistance and low-temperature characteristics satisfy the requirement, but epoxy adhesive does not show sufficient radiation resistance. It is expected that the amount of radiation generated will increase as the size of the accelerator increases in the future, so adhesives that bond at low temperatures and have excellent radiation resistance are required. Polyimide compositions are said to be suitable for this.

Therefore, the present inventors have solved the above-mentioned conventional problems and provided a suitable polyimide adhesive which can be used as a polyimide adhesive and an adhesive film which are bonded at a low temperature and have excellent radiation resistance. As a result of intensive studies for the purpose, the present invention has been achieved.

[0006]

To achieve this object, the gist of the thermoplastic polyimide according to the present invention is that it is represented by the general formula (1).

[Chemical 11] (In the formula, Ar ₁ , Ar ₂ , Ar ₄ and Ar ₆ are divalent organic groups, A
r ₃ and Ar ₅ represent a tetravalent organic group. Further, l, m, and n are 0 or a positive integer of 1 or more, and the sum of l and m is 1.
It is above, and t represents a positive integer of 1 or more. ) Is a skeleton of the thermoplastic polyimide represented by.

Further, Ar ₁ in the general formula (1) is

[Chemical 12] Is at least one selected from the group of divalent organic groups shown in.

Further, Ar ₂ in the general formula (1) is

[Chemical 13] At least 1 selected from the group of divalent aromatic groups shown in
It is to be a seed.

Further, Ar ₃ in the general formula (1) is

[Chemical 14] Is at least one selected from the group of tetravalent organic groups shown in.

Further, Ar ₄ in the general formula (1) is

[Chemical 15] Is at least one selected from the group of divalent organic groups shown in.

Further, Ar ₅ in the general formula (1) is

[Chemical 16] Is at least one selected from the group of tetravalent organic groups shown in.

Further, Ar ₆ in the general formula (1) is

[Chemical 17] At least 1 selected from the group of divalent aromatic groups shown in
It is to be a seed.

Further, the thermoplastic polyimide is particularly represented by the general formula (2):

[Chemical 18] (In the formula, Ar ₁ , Ar ₂ and Ar ₆ represent a divalent organic group, Ar ₅ represents a tetravalent organic group, l and t are positive integers of 1 or more, and n is 0 or 1 It represents the above positive integer.).

Next, the gist of the polyamic acid, which is the precursor of the thermoplastic polyimide according to the present invention, is as follows.

[Chemical 19] (In the formula, Ar ₁ , Ar ₂ , Ar ₄ and Ar ₆ are divalent organic groups, A
r ₃ and Ar ₅ represent a tetravalent organic group. In addition, l, m, and n are 0 or a positive integer of 1 or more, the sum of l and m is 1 or more, and t represents a positive integer of 1 or more. ).

Further, the polyamic acid is particularly preferably represented by the general formula (4):

[Chemical 20] (In the formula, Ar ₁ , Ar ₂ and Ar ₆ represent a divalent organic group, Ar ₅ represents a tetravalent organic group, l and t are positive integers of 1 or more, and n is 0 or 1 It represents the above positive integer.).

[0016]

EXAMPLES Next, the thermoplastic polyimide according to the present invention and its precursor polyamic acid will be described together with the method for producing the same.

The method for producing the polyamic acid solution which is the precursor of the thermoplastic polyimide used in the present invention is carried out by using the general formula (5) H ₂ N—Ar ₇ —NH ₂ in an atmosphere of an inert gas such as argon or nitrogen. (5) A diamine represented by the formula (wherein Ar ₇ represents a divalent organic group) is dissolved or diffused in an organic solvent. In this solution, the compound of general formula (6) 21

[Chemical 21] (In the formula, Ar ₈ represents a divalent organic group.) Or only the ester dianhydride represented by the formula (7)

[Chemical formula 22] (In the formula, Ar ₉ represents a tetravalent organic group.) A mixture with at least one kind of organic tetracarboxylic dianhydride represented by the following is added in the form of a solid or a solution prepared by dissolving it in an organic solvent, General formula (4) which is a precursor of polyimide 23

[Chemical formula 23] (In the formula, Ar ₁ , Ar ₂ , Ar ₄ and Ar ₆ are divalent organic groups, A
r ₃ and Ar ₅ represent a tetravalent organic group. In addition, l, m, and n are 0 or a positive integer of 1 or more, the sum of l and m is 1 or more, and t represents a positive integer of 1 or more. The polyamic acid solution represented by this can be obtained.

Further, the method for producing a polyamic acid solution which is a precursor of another thermoplastic polyimide used in the present invention is as follows:
General formula (8)

[Chemical formula 24] (In the formula, Ar ₁₀ represents a divalent organic group.) Only an ester diamine represented by the formula or a mixture of the ester diamine and at least one diamine represented by the general formula (5) is used as an organic solvent. Dissolve or diffuse in. In this solution, only the ester acid dianhydride represented by the general formula (6), or at least one organic tetracarboxylic dianhydride represented by the general formula (7), or the ester acid dianhydride and the organic compound A mixture of tetracarboxylic acid dianhydrides is added in the form of a solution of a solid or an organic solvent to give a compound of the general formula (3) which is a precursor of polyimide.

[Chemical 25] (In the formula, Ar ₁ , Ar ₂ , Ar ₄ and Ar ₆ are divalent organic groups, A
r ₃ and Ar ₅ represent a tetravalent organic group. In addition, l, m, and n are 0 or a positive integer of 1 or more, the sum of l and m is 1 or more, and t represents a positive integer of 1 or more. The polyamic acid solution represented by this can be obtained.

In this reaction, contrary to the above, first, only the ester dianhydride represented by the general formula (7) or at least one organic tetracarboxylic acid dianhydride represented by the general formula (8) is used. A solution of an anhydride or a mixture of these ester acid dianhydrides and organic tetracarboxylic acid dianhydrides is prepared, and a diamine represented by the general formula (6) or the general formula (5) is prepared in the solution. The ester diamine may be added alone, or a solution or slurry of a solid or organic solvent of a mixture of the ester diamine and at least one diamine represented by the general formula (6) may be added.

The reaction temperature at this time is preferably -10 to 50 ° C, more preferably -5 ° C to 20 ° C. The reaction time is 30 minutes to 3 hours. By such a reaction, the polyamic acid polymer represented by the general formula (3) or the general formula (4), which is a precursor of the thermoplastic polyimide, is produced.

Examples of the organic solvent used in the reaction for producing the polyamic acid polymer solution include sulfoxide solvents such as dimethyl sulfoxide and diethyl sulfoxide, N, N-dimethylformamide, N, N-diethylformamide. Formamide solvent such as N, N-
Acetamide-based solvents such as dimethylacetamide and N, N-diethylacetamide may be mentioned. These may be used alone or as a mixed solvent of two or three or more. Furthermore, with these polar solvents,
It can also be used as a mixed solvent with a non-solvent of a polyamic acid such as acetone, methanol, ethanol, isopropanol, or benzenemethylcellosolve.

Next, in order to obtain a polyimide from a polyamic acid polymer solution which is a precursor of a thermoplastic polyimide, a method of thermally and / or chemically performing dehydration ring closure (imidization) may be used.

The method for dehydration and ring closure of the polyamic acid polymer solution will be described in detail. In the method for thermally dehydration and ring closure, the solution of the polyamic acid polymer is used as a support plate, an organic film such as PET, a drum or an endless belt. Etc. is cast or coated on a support such as to form a film, and dried to obtain a film having a self-supporting property. This drying is preferably performed at a temperature of 100 ° C. or lower for about 5 to 90 minutes. Next, this is further heated to be dried and imidized to obtain a polyimide film made of the thermoplastic polyimide of the present invention. The temperature during heating is preferably in the range of 100 to 350 ° C, and particularly 15
0-300 degreeC is preferable. There is no limitation on the rate of temperature increase during heating, but it is preferable that the maximum temperature reaches the above temperature by gradually heating. The heating time varies depending on the film thickness and the maximum temperature, but is generally preferably in the range of 10 seconds to 30 minutes after the maximum temperature is reached. When the film having the self-supporting property is heated, it is preferable to peel the film from the support, fix the end portion in this state and heat the film to obtain a polymer having a small linear expansion coefficient.

In the method of chemically dehydrating and ring-closing, the same method as in the case of thermally dehydrating by adding a stoichiometric or more stoichiometric dehydrating agent and a catalytic amount of a tertiary amine to the solution of the polyamic acid polymer is used. And the desired polyimide film is obtained.

Comparing the thermal imidization method and the chemical imidization method, the chemical method has an advantage that the obtained polyimide has a higher mechanical strength and a smaller linear expansion coefficient. The chemical method and the thermal method can be used in combination. By imidizing the polyamic acid polymer represented by the above general formula (3) by such a method,

[Chemical formula 26] (In the formula, Ar ₁ , Ar ₂ , Ar ₄ and Ar ₆ are divalent organic groups, A
r ₃ and Ar ₅ represent a tetravalent organic group. In addition, l, m, and n are 0 or a positive integer of 1 or more, the sum of l and m is 1 or more, and t represents a positive integer of 1 or more. The polyimide composition represented by these can be obtained.

Incidentally, as the ester dianhydride represented by the above general formula (6) used in the present invention, in general, ester dianhydrides having any structure of glycols or phenols can be used. is there. Specific examples of the Ar ₈ group in the general formula (6) are shown below.

[Chemical 27] Can be mentioned. More specifically, from the viewpoint of the balance of various characteristics,

[Chemical 28] It is preferable to have as a main component.

As the organic tetracarboxylic dianhydride, organic tetracarboxylic dianhydrides having any structure can be used, but the Ar ₉ group in the above general formula (7) is a tetravalent organic group. Yes, and a specific example of this Ar ₉ group is
9

[Chemical 29] Can be mentioned. You may use these organic tetracarboxylic dianhydride individually or in combination of 2 or more types. More specifically, from the viewpoint of the balance of various characteristics,

[Chemical 30] It is preferable to use at least one of the above as the main component.

As the ester diamine represented by the above general formula (8) used in the present invention, ester diamine having any structure of general glycols or phenols can be used. A specific example of this Ar ₁₀ group is:

[Chemical 31] Can be mentioned. More specifically, from the viewpoint of the balance of various characteristics,

[Chemical 32] It is preferable to have as a main component.

Further, as Ar ₇ in the diamine compound represented by the general formula (5), essentially any divalent organic group can be used.
Four

[Chemical 33]

[Chemical 34] And the like, more specifically,

[Chemical 35] It is preferable that at least one of the above is a main component.

Next, the number of repeating block units l in the thermoplastic polyimide represented by the general formula (1),
m and n are positive integers of 0 or more, and the sum of l and m may be 1 or more, but the number of repetitions l, m, and n is preferably 15 or less. This is because the copolymerization ratio becomes unbalanced when the number of repetitions n exceeds 15 times the sum of the numbers of repetitions l and m, and the effect of polymerization becomes small. Is difficult to recognize. Further, there may be units having different values of l, m and n in one molecule of the polymer, but it is particularly preferable that the values of l, m and n are constant.

The block repeat number t may be a positive integer of 1 or more, and the molecular weight of the thermoplastic polyimide is not particularly limited, but in order to maintain the strength of the polyimide produced. The number average molecular weight is preferably 10,000 or more.

By the way, it is often difficult to directly measure the molecular weight of the polyimide polymer. In such a case, an indirect method is used to make a speculative measurement. For example, when the polyimide polymer is synthesized from polyamic acid,
The value corresponding to the molecular weight of polyamic acid is the molecular weight of polyimide.

Also in the polyamic acid polymer represented by the above general formula (3), the number of repeating block units l, m, n is a positive integer of 0 or more, and the sum of l and m is It may be 1 or more, but especially the number of repetitions 1, m, n
Is preferably 15 or less. Further, units having different values of l, m and n may be present in one molecule of the polymer, but it is particularly preferable that they are constant. Further, the block repetition number t may be a positive integer of 1 or more.

The obtained polyimide of the present invention has excellent thermoplasticity, adhesiveness (low temperature adhesiveness), low water absorption and radiation resistance. That is, such a polyimide has a clear glass transition point between 100 ° C. and 250 ° C. depending on its composition, and can be directly adhered to a polyimide film or the like by laminating at a temperature close to the glass transition point. The obtained polyimide of the present invention has a temperature of 20 ° C.
It has been confirmed that the water absorption rate when soaked in pure water for 24 hours shows a low water absorption rate of about 1%, and further exhibits excellent characteristics in radiation resistance.

Therefore, the thermoplastic polyimide according to the present invention can be formed into a film shape, and a copper foil or the like can be adhered to the flexible printed wiring board produced thereby without using an adhesive. At that time, copper foil or the like may be provided on both sides of the obtained polyimide film to be bonded, but copper foil or the like may be provided on one side of the film, and release paper or the like may be provided on the other side of the film to provide one side Only copper foil or the like may be adhered. Further, such a polyimide film is particularly effective as a substrate such as a multilayer printed wiring board.

Further, the film made of the thermoplastic polyimide according to the present invention can be used as an adhesive for other films having no adhesive property. In such an application, it can be supplied in the form of a polyimide film, which is convenient to handle. It is also possible to directly apply the polyamic acid according to the present invention to an existing base film or the like and then imidize it to provide a film having an adhesive layer. Other uses are not particularly limited.

Although the thermoplastic polyimide and the polyamic acid according to the present invention have been described above, the present invention is not limited to these examples, and the present invention is within the scope of those skilled in the art without departing from the spirit thereof. It can be implemented in a mode in which various improvements, changes and modifications are made based on the knowledge.

Next, examples of the present invention will be described more specifically, but the present invention is not limited to these examples.

Example 1 1.0 g of ethylene glycol bistrimellitic dianhydride (hereinafter referred to as TMEG) was placed in a 50 ml volumetric flask.
And dimethylformamide (hereinafter referred to as DMF) 1
0.0 g was taken, and it was sufficiently dissolved by stirring using a stirrer. On the other hand, 22.7 g of 2,2-bis (4-aminobenzyloxyphenyl) propane (hereinafter referred to as BABPP) and 68.1 g of DMF were placed in a 500 ml three-necked flask equipped with a stirrer, while replacing the atmosphere in the flask with nitrogen. Stir to dissolve well. Next, 19.0 g of TMEG was sampled in a 100 ml round-bottomed flask and added to the BABPP solution as a solid. Further, TMEG remaining on the wall surface of this 100 ml round-bottomed flask was poured into a three-necked flask with 21.5 g of DMF. After standing for about 1 hour with stirring, TM in a 50 ml volumetric flask
The EG solution was gradually charged into the three-neck flask while paying attention to the viscosity of the solution in the three-neck flask. After reaching the maximum viscosity, the addition of the TMEG solution was completed, and the mixture was allowed to stand with stirring for 1 hour to obtain a polyamic acid solution.

This polyamic acid solution was formed into a film by the following method and then imidized to obtain a laminated film, and its characteristics were examined. First, 2.0 g of isoquinoline and 20.0 g of acetic anhydride were placed in a 100 ml volumetric flask and stirred well. Next, this solution was added to the prepared polyamic acid solution and well stirred for 2 minutes. After degassing, apply on a PET film, heat at 80 ° C. for 25 minutes, peel off the PET film, continuously raise the temperature from 150 ° C. to 200 ° C., then heat for 10 minutes and imidize Then, a film-shaped thermoplastic polyimide was obtained. When the glass transition point of the obtained thermoplastic polyimide was measured by TMA, the glass transition point was 122 ° C. Also, regarding the obtained thermoplastic polyimide, ASTM D-570
According to the measurement of water absorption rate, the water absorption rate was 0.95%. The results of these measurements are shown in Table 1.

[0041]

[Table 1]

Further, a polyimide film Apical (registered trademark, manufactured by Kanegafuchi Chemical Industry Co., Ltd.), the obtained film-like thermoplastic polyimide, and release paper are laminated and arranged at 150 ° C. and 2.2 cm / cm 2. It was laminated at a speed of min to obtain an insulating coating material. Further, the release paper is peeled off from this insulating coating material, and a copper foil is placed in place of the release paper.
A copper clad laminated film was obtained by laminating at a speed of 2.2 cm / min.

The peel strength of the obtained laminated film was examined. Measurement of peel strength is JIS K6481
The peel strength was 1.4 when the test was performed at room temperature.
(kg / cm). The results are shown in Table 1. further,
When a radiation resistance test was performed by irradiation with 5 MGy using an electron beam of 2 MeV, the laminated film was not discolored and no deterioration of the material was observed.

Example 2 In the same manner as in Example 1 except that 13.3 g of 1,3-bis (4-aminophenoxy) -2,2-dimethylpropane was used instead of BABPP, a film-like heat treatment was conducted. A plastic polyimide was obtained. After that, an insulating coating material was prepared in the same manner as in Example 1, and then a copper clad laminated film was obtained.

The glass transition point and the water absorption rate of the obtained thermoplastic polyimide were measured in the same manner as in Example 1. The glass transition point was 130 ° C., and the water absorption rate was 1.1.
It was 3%. Further, regarding the obtained laminated film,
When the peel strength was examined in the same manner as in Example 1, the peel strength was 2.0 (kg / cm). The results are shown in Table 1. Furthermore, when a radiation resistance test was performed by irradiation with 5 MGy using an electron beam of 2 MeV, the laminated film was not discolored and no deterioration of the material was observed.

Example 3 In a 50 ml volumetric flask (1), 2,2-bis [4- (4-
Aminophenoxy) phenyl] propane (hereinafter, BAP
It is called P. ) 16.9 g and dimethylformamide (hereinafter, referred to as DMF) 25.4 g were taken, stirred with a stirrer and sufficiently dissolved. In another 50 ml volumetric flask (2), 1.0 g of BAPP and 10.0 g of DMF.
Was taken, and similarly melted sufficiently. On the other hand, in a 500 ml three-necked flask equipped with a stirrer, 2,2-bis (4-hydroxyphenyl) propanedibenzoate-2,2 ′, 3
3'-tetracarboxylic acid dianhydride (hereinafter referred to as ESDA) 11.9 g, pyromellitic dianhydride (PMDA) 4.5 g, and DMF25.
0 g was added, and while cooling with ice water, and replacing the atmosphere in the flask with nitrogen, the mixture was stirred and sufficiently dissolved.

First, 500 ml of the BAPP solution obtained in advance in the 50 ml volumetric flask (1) was stirred.
Immediately charged into a three-necked flask. After standing for about 30 minutes with stirring, BA in a 50 ml volumetric flask (2)
The PP solution was gradually charged into the three-necked flask while paying attention to the viscosity of the solution in the three-necked flask. After reaching the maximum viscosity, the addition of the BAPP solution in the 50 ml volumetric flask (2) was completed, and the mixture was left for 1 hour with stirring. Then DM
78.2 g of F was added and stirred to obtain a polyamic acid solution.

This polyamic acid solution was coated on a PET film, then heated at 80 ° C. for 25 minutes and dried to the extent that it had self-supporting properties. Thereafter, the polyamic acid film was peeled off from the PET film, fixed on a metal support, and then heated at 150 ° C., 200 ° C., 250 ° C., and 300 ° C. for 5 minutes in order to imidize the thermoplastic polyimide polymer. I got a film. Furthermore, a polyimide film (Kanefuchi Chemical Industry Co., Ltd., Apical (registered trademark)), a film of the thermoplastic polyimide polymer obtained above, and a copper foil (35 μm thick) are overlaid, and the temperature is 300 ° C.
Lamination was performed at a speed of 2.2 cm / min to obtain a copper clad laminated film.

The glass transition point and water absorption rate of the obtained thermoplastic polyimide were measured in the same manner as in Example 1. The glass transition point was 222 ° C., and the water absorption rate was 1.1.
It was 3%. Further, regarding the obtained laminated film,
When the peel strength was examined in the same manner as in Example 1, the peel strength was 2.0 (kg / cm). The results are shown in Table 1. Furthermore, when a radiation resistance test was performed by irradiation with 5 MGy using an electron beam of 2 MeV, the laminated film was not discolored and no deterioration of the material was observed.

Example 4 Copolymerization was carried out by adding 30 ml of DMF, 22.7 g of BABPP and 10.6 g of PMDA to the polyamic acid polymer solution obtained in Example 1 for copolymerization. A combined solution was obtained. Using this polyamic acid polymer solution, imidization was carried out in the same manner as in Example 1 to obtain a film-shaped thermoplastic polyimide. After that, an insulating coating agent was prepared in the same manner as in Example 1, and then a copper clad laminated film was obtained.

The glass transition point and the water absorption rate of the obtained thermoplastic polyimide were measured in the same manner as in Example 1. The glass transition point was 185 ° C. and the water absorption rate was 1.4.
It was 5%. Further, regarding the obtained laminated film,
When the peel strength was examined in the same manner as in Example 1, the peel strength was 1.6 kg / cm 2. The results are shown in Table 1.
Furthermore, when a radiation resistance test was performed by irradiation with 5 MGy using an electron beam of 2 MeV, the laminated film was not discolored and no deterioration of the material was observed.

Comparative Example 1 (Thermoplastic Polyimide Using BTDA and BAPP) First, in a 50 ml volumetric flask, 1.94 g of 3,3 ', 4,4'-benzophenone tetracarboxylic dianhydride (BTDA) and 30.0 g of DMF were prepared. It was taken and melted sufficiently. Also, in a 500 ml three-necked flask equipped with a stirrer, 51.8 g of BAPP and 310.0 g of DMF are placed,
While cooling with ice water, the atmosphere in the three-necked flask was replaced with nitrogen while stirring to sufficiently dissolve it. Next, 38.8 g of BTDA was collected in a 100 ml eggplant-shaped flask and added to the BAPP solution as a solid. Furthermore, 10.0 g of BTDA remaining on the wall surface of this 100 ml eggplant flask was added.
Pour into a three neck flask by MF. After standing for about 30 minutes with stirring, B in a 50 ml volumetric flask
The TDA solution was gradually charged into the three-necked flask while paying attention to the viscosity of the solution in the three-necked flask. After reaching the maximum viscosity, the addition of the BTDA solution was completed, and the mixture was left for 1 hour with stirring to obtain a polyamic acid solution.

This polyamic acid solution was imidized in the same manner as in Example 1 to obtain a thermoplastic polyimide polymer film. Furthermore, polyimide film (Kanefuchi Chemical Industry Co., Ltd.)
Manufactured by Apical (registered trademark)), the thermoplastic polyimide polymer film obtained above, and a copper foil (thickness of 35 μm)
And were laminated at 300 ° C. and a speed of 2.2 cm / min to obtain a copper clad laminated film.

The glass transition point and the water absorption rate of the obtained thermoplastic polyimide were measured in the same manner as in Example 1. The glass transition point was 238 ° C. and the water absorption rate was 1.9.
It was 8%. Further, regarding the obtained laminated film,
When the peel strength was examined in the same manner as in Example 1, the peel strength could not be measured because there was no adhesion.
The results are shown in Table 1. Furthermore, when a radiation resistance test was performed by irradiation with 5 MGy using an electron beam of 2 MeV, the laminated film was not discolored and no deterioration of the material was observed.

Comparative Example 2 A laminate was prepared in the same manner as in Example 1 except that an epoxy adhesive consisting of Epicoat 828 (trade name) manufactured by Yuka Shell Co., Ltd. was used as the adhesive instead of the thermoplastic polyimide according to the present invention. I got a film.

When the characteristics were examined in the same manner as in Example 1, the glass transition point of this epoxy adhesive was 178 ° C., and the water absorption was 1.98%. When the peel strength of the obtained laminated film was examined in the same manner as in Example 1, the peel strength could not be measured because it was not adhered. The results are shown in Table 1. further,
When a radiation resistance test was performed by irradiation with 5 MGy using an electron beam of 2 MeV, the laminated film turned black.

[0057]

As described above, the thermoplastic polyimides represented by the general formulas (1) and (2) in the present invention have excellent thermoplasticity, adhesiveness, low water absorption and radiation resistance. ing. That is, such a thermoplastic polyimide has a clear glass transition point between 100 ° C. and 220 ° C. depending on its composition, and can be directly adhered to a copper foil or the like by laminating at a temperature close to the glass transition point. Therefore, it can be used after being processed into a film in the form of polyimide. Further, the polyamic acid represented by the general formulas (3) and (4), which is the precursor thereof, can be directly applied to the base film to be imidized to easily form a film having an adhesive layer. Further, since the thermoplastic polyimide of the present invention exhibits a low water absorption rate of about 1%, it is possible to prevent deterioration of various performances such as heat resistance deterioration. From the above points, the thermoplastic polyimide and the polyamic acid according to the present invention can realize excellent low-temperature adhesiveness and radiation resistance as an adhesive alternative to an epoxy adhesive, and are suitable as an adhesive film. A thermoplastic polyimide composition can be obtained.

[Procedure amendment]

[Submission date] January 14, 1994

[Procedure Amendment 1]

[Document name to be amended] Statement

[Name of item to be corrected] Claim 8

[Correction method] Change

[Correction content]

[Chemical 8] (In the formula, Ar ₁ , Ar ₂ and Ar ₆ represent a divalent organic group, Ar ₅ represents a tetravalent organic group, and l and t are positive integers of 1 or more, n
Represents a positive integer of 0 or 1 or more. ) Is represented by the thermoplastic polyimide.

[Procedure Amendment 2]

[Document name to be amended] Statement

[Correction target item name] 0013

[Correction method] Change

[Correction content]

Further, the thermoplastic polyimide is particularly preferably
General formula (2)

[Chemical 18] (In the formula, Ar ₁ , Ar ₂ and Ar ₆ represent a divalent organic group, Ar ₅ represents a tetravalent organic group, l and t are positive integers of 1 or more, and n is 0 or 1 It represents the above positive integer.).

[Procedure 3]

[Document name to be amended] Statement

[Name of item to be corrected] 0023

[Correction method] Change

[Correction content]

A method for dehydrating and ring-closing the polyamic acid polymer solution will be specifically described. In the method for thermally dehydrating and ring-closing, the solution of the polyamic acid polymer is used as a support plate, an organic film such as PET, a drum or an endless belt. Etc. is cast or coated on a support such as to form a film, and dried to obtain a film having a self-supporting property. This drying is preferably performed at a temperature of 100 ° C. or lower for about 5 to 90 minutes. Next, this is further heated and dried to imidize to obtain a polyimide film made of the thermoplastic polyimide of the present invention. The temperature during heating is preferably in the range of 100 to 350 ° C, particularly preferably 150 to 300 ° C. There is no limitation on the rate of temperature increase during heating, but it is preferable that the maximum temperature reaches the above temperature by gradually heating. The heating time varies depending on the film thickness and the maximum temperature, but is generally preferably in the range of 10 seconds to 30 minutes after the maximum temperature is reached. When the film having the self-supporting property is heated, it is preferable to peel the film from the support, fix the end portion in this state and heat the film to obtain a polymer having a small linear expansion coefficient.

[Procedure amendment 4]

[Document name to be amended] Statement

[Correction target item name] 0026

[Correction method] Change

[Correction content]

By the way, as the ester acid dianhydride represented by the above general formula (6) used in the present invention, in general, ester acid dianhydrides having any structure of glycols or phenols can be used. is there. Specific examples of the Ar ₈ group in the general formula (6) are shown below.

[Chemical 27] Can be mentioned. More specifically, from the viewpoint of the balance of various characteristics,

[Chemical 28] It is preferable to have as a main component.

[Procedure Amendment 5]

[Document name to be amended] Statement

[Correction target item name] 0028

[Correction method] Change

[Correction content]

As the ester diamine represented by the above general formula (8) used in the present invention, ester diamine having any structure of general glycols or phenols can be used. A specific example of this Ar ₁₀ group is:

[Chemical 31] Can be mentioned. More specifically, from the viewpoint of the balance of various characteristics,

[Chemical 32] It is preferable to have as a main component.

[Procedure correction 6]

[Document name to be amended] Statement

[Correction target item name] 0050

[Correction method] Change

[Correction content]

Example 4 The polyamic acid polymer solution obtained in Example 1 was further
30.0 g DMF and 22.7 g BABPP.
Copolymerization was performed by adding 6 g of PMDA to obtain a polyamic acid polymer solution. Using this polyamic acid polymer solution, imidization was carried out in the same manner as in Example 1 to obtain a film-shaped thermoplastic polyimide. After that, an insulating coating agent was prepared in the same manner as in Example 1, and then a copper clad laminated film was obtained.

Claims (10)

[Claims] 1. A compound represented by the general formula (1): (In the formula, Ar ₁ , Ar ₂ , Ar ₄ and Ar ₆ are divalent organic groups, A
r ₃ and Ar ₅ represent a tetravalent organic group. In addition, l, m, and n are 0 or a positive integer of 1 or more, the sum of l and m is 1 or more, and t represents a positive integer of 1 or more. ) Is represented by the thermoplastic polyimide. 2. Ar ₁ in the general formula (1) is represented by the following formula: The thermoplastic polyimide according to claim 1, which is at least one selected from the group of divalent organic groups shown in 1. 3. Ar ₂ in the general formula (1) is represented by the following formula: At least 1 selected from the group of divalent aromatic groups shown in
The thermoplastic polyimide according to claim 1 or 2, wherein the thermoplastic polyimide is a seed. 4. Ar ₃ in the general formula (1) is represented by the following formula: It is at least 1 sort (s) selected from the group of the tetravalent organic group shown in Claim 4, The thermoplastic polyimide in any one of Claim 1 thru | or 3. 5. Ar ₄ in the general formula (1) is represented by the following formula: It is at least 1 sort (s) selected from the group of the bivalent organic group shown in Claim 5, The thermoplastic polyimide in any one of Claim 1 thru | or 4 characterized by the above-mentioned. 6. Ar ₅ in the general formula (1) is represented by the following formula: It is at least 1 sort (s) selected from the group of the tetravalent organic group shown in Claim 6, The thermoplastic polyimide in any one of Claim 1 thru | or 5 characterized by the above-mentioned. 7. Ar ₆ in the general formula (1) is represented by the following formula: At least 1 selected from the group of divalent aromatic groups shown in
The thermoplastic polyimide according to any one of claims 1 to 6, which is a seed. 8. A compound represented by the general formula (2): (In the formula, Ar ₁ , Ar ₂ and Ar ₆ represent a divalent organic group, Ar ₅ represents a tetravalent organic group, and l and t are positive integers of 1 or more, n
Represents a positive integer of 0 or 1 or more. ) Is represented by the thermoplastic polyimide. 9. A compound represented by the general formula (3) 9: (In the formula, Ar ₁ , Ar ₂ , Ar ₄ and Ar ₆ are divalent organic groups, A
r ₃ and Ar ₅ represent a tetravalent organic group. In addition, l, m, and n are 0 or a positive integer of 1 or more, the sum of l and m is 1 or more, and t represents a positive integer of 1 or more. ) The polyamic acid is represented by 10. A compound represented by the general formula (4): (In the formula, Ar ₁ , Ar ₂ and Ar ₆ represent a divalent organic group, Ar ₅ represents a tetravalent organic group, l and t are positive integers of 1 or more, n
Represents a positive integer of 0 or 1 or more. ) The polyamic acid is represented by