JPH073019A - New aromatic polyimide polymer and polyamic acid polymer - Google Patents

Abstract

PURPOSE:To provide a new aromatic polyimide polymer which is useful as an electric or electronic material comprising specific recurring units and having low moisture absorption, high heat resistance, processability and adhesion. CONSTITUTION:The polyimide and the polyamic acid are composed of the recurring units of formula I [Ar<1> is difunctional organic group; Ar<2>, Ar<3> are tetrafunctional organic group; l and n are 1 or more; m is 0, 1 or more) and formula II (Ar<4> is difunctional organic group; Ar<5>, Ar<6> are tetrafunctional organic group; s, u are 1 or more; T is 0 or 1 or more) respectively. These polyimide and polyamic acid are obtained, for example, by reaction of an ester- diamine of formula III (Ar<7> is difunctional organic group) with at least one of organic tetracarboxylic acid dianhydrides of formula IV (Ar<8> is tetrafunctional organic group).

Description

Detailed Description of the Invention

[0001]

FIELD OF THE INVENTION The present invention relates to a polyimide resin known as a heat resistant resin. More specifically, processability,
The present invention relates to a novel aromatic polyimide polymer having excellent adhesiveness and a novel polyamic acid polymer which is a precursor thereof.

[0002]

2. Description of the Related Art In recent years, aromatic polyimides have been widely used in electric and electronic materials because of their excellent heat resistance, mechanical strength and electrical characteristics. However, since aromatic polyimide is generally insoluble and infusible,
Processed in the state of its precursor aromatic polyamic acid,
There is a need for a method of thermally and / or chemically cyclizing (imidizing) it to obtain a polyimide. For this reason, the processability is poor, and further processing beyond the processing in the polyamic acid state is difficult.

When polyimide is used for a flexible printed circuit board or the like, a method has been adopted in which an adhesive is applied to a film-shaped polyimide or copper foil and the polyimide film and the copper foil are bonded together. Therefore, an adhesive layer having heat resistance equal to or superior to that of polyimide is required. However, since there is only an adhesive having poor heat resistance, the characteristics such as heat resistance of the flexible printed circuit board are determined by the characteristics of the adhesive, and there is a problem that the high performance of polyimide cannot be exhibited.

Therefore, the present inventors have conducted diligent research with the object of solving the above-mentioned conventional problems and providing a novel aromatic polyimide polymer having excellent heat resistance, processability and adhesiveness. As a result of the repetition, the present invention has been achieved.

[0005]

To achieve this object, the gist of the novel aromatic polyimide polymer according to the present invention is that the compound represented by the general formula (1):

[Chemical 9] (In the formula, Ar ₁ represents a divalent organic group, Ar ₂ and Ar ₃ both represent a tetravalent organic group, l and n are positive integers of 1 or more, and m is 0 or a positive integer of 1 or more. Represents the integer.).

In the novel aromatic polyimide polymer, Ar ₁ in the general formula (1) is

[Chemical 10] Is a divalent organic group shown in.

In the novel aromatic polyimide polymer, Ar ₂ in the general formula (1) is

[Chemical 11] At least 1 selected from the group of tetravalent aromatic groups shown in
It is to be a seed.

Further, in the novel aromatic polyimide polymer, Ar ₃ in the general formula (1) is

[Chemical 12] At least 1 selected from the group of tetravalent aromatic groups shown in
It is to be a seed.

Next, the gist of the novel aromatic polyamic acid polymer according to the present invention is represented by the general formula (2):

[Chemical 13] (In the formula, Ar ₄ is a divalent organic group, Ar ₅ and Ar ₆ are all tetravalent organic groups, s and u are positive integers of 1 or more, and t is 0 or a positive integer of 1 or more. Represents the integer.).

In such a novel aromatic polyamic acid polymer, Ar ₄ in the general formula (2) is

[Chemical 14] Is a divalent organic group shown in.

In the novel aromatic polyamic acid polymer, Ar ₅ in the general formula (2) is

[Chemical 15] At least 1 selected from the group of tetravalent aromatic groups shown in
It is to be a seed.

Further, in such a novel aromatic polyamic acid polymer, Ar ₆ in the general formula (2) is

[Chemical 16] At least 1 selected from the group of tetravalent aromatic groups shown in
It is to be a seed.

[0013]

EXAMPLES Next, a method for producing the novel aromatic polyimide polymer according to the present invention and the novel aromatic polyamic acid polymer which is a precursor thereof will be explained.

First, in the atmosphere of an inert gas such as argon or nitrogen, the compound represented by the general formula (3) is used.

[Chemical 17] (In the formula, Ar ₇ represents a divalent organic group.) The ester diamine represented by the formula is dissolved or diffused in an organic solvent. In this solution, the compound of the general formula (4) 18

[Chemical 18] (In the formula, Ar ₈ represents a tetravalent organic group.) By adding at least one organic tetracarboxylic dianhydride represented by the solid form or a solution with an organic solvent,
General formula (2), which is a precursor of a novel aromatic polyimide polymer,

[Chemical 19] (In the formula, Ar ₄ is a divalent organic group, Ar ₅ and Ar ₆ are all tetravalent organic groups, s and u are positive integers of 1 or more, and t is 0 or a positive integer of 1 or more. A new aromatic polyamic acid polymer solution represented by the formula (1) is produced. The reaction temperature at this time is -10 to 50 ° C, more preferably -5 to 20 ° C. The reaction time is 30 minutes to 6 hours.

In the reaction for producing this novel aromatic polyamic acid polymer solution, contrary to the above, first, at least one organic tetracarboxylic acid represented by the above general formula (4) is dissolved or diffused in an organic solvent. It is also possible to prepare the above solution and add a solution or slurry of the ester diamine represented by the above general formula (3) in the solid or organic solvent to the solution.

The organic solvent used in the reaction for producing the novel aromatic polyamic acid polymer solution is, for example,
Sulfoxide solvents such as dimethyl sulfoxide and diethyl sulfoxide, N, N′-dimethylformamide,
Examples thereof include formamide solvents such as N, N′-diethylformamide, acetamide solvents such as N, N′-dimethylacetamide and N, N′-diethylacetamide. These may be used alone or as a mixed solvent of two or three or more. Further, it can be used as a mixed solvent with a non-solvent of polyamic acid such as acetone, methanol, ethanol, isopropanol, and benzenemethylcellosolve together with these polar solvents.

Next, in order to obtain a polyimide polymer from a polyamic acid polymer solution which is a precursor of a novel aromatic polyimide polymer, the polyamic acid polymer is thermally and / or chemically dehydrated and cyclized (imidized). ) Method may be used.

A method for dehydrating and ring-closing the polyamic acid polymer will be specifically described. First, in the method of thermally dehydrating and ring-closing, the solution of the polyamic acid polymer is cast or applied on a support plate, an organic film such as PET, or a support such as a drum or an endless belt to form a film, and dried. To obtain a self-supporting film. This drying is preferably performed at a temperature of 150 ° C. or lower for about 5 to 90 minutes. Then, this is further heated to be dried and imidized to obtain a polyimide film made of the polyimide polymer of the present invention. The temperature during heating is preferably in the range of 150 to 350 ° 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 is
Although it varies depending on the thickness of the film and the maximum temperature, it is generally preferably in the range of 10 seconds to 5 minutes after the maximum temperature is reached.
When the film having self-supporting properties is heated, it is preferable to peel it off from the support and fix the ends in the state of the film and heat it, because a polyimide polymer film having a small linear thermal expansion coefficient can be obtained.

Further, 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. To obtain the desired polyimide polymer film.

Comparing the thermal imidization method and the chemical imidization method, the chemical method has the advantage that the polyimide obtained has a higher mechanical strength and a smaller coefficient of linear thermal expansion. is there. In addition, it is also possible to use the method of thermally imidizing and the method of chemically imidizing together.

By imidizing the novel aromatic polyamic acid polymer represented by the general formula (2) by such a thermal and / or chemical method, the compound represented by the general formula (1)
0

[Chemical 20] (In the formula, Ar ₁ represents a divalent organic group, Ar ₂ and Ar ₃ both represent a tetravalent organic group, l and n are positive integers of 1 or more, and m is 0 or a positive integer of 1 or more. , Which represents an integer of 1.), is produced.

Here, as the ester diamine represented by the above general formula (3) used in the present invention, ester diamines having any structure can be used, but the Ar ₇ group in the general formula (3) is It is a divalent organic group. A concrete example of this Ar ₇ group is:

[Chemical 21] Can be mentioned. More specifically, from the viewpoint of the balance of various characteristics,

[Chemical formula 22] It is preferable to have as a main component.

As the organic tetracarboxylic dianhydride represented by the general formula (4), it is possible to use organic tetracarboxylic dianhydrides having any structure, but the general formula (4) The Ar ₈ group therein is a tetravalent organic group, and particularly preferably an aromatic group. Specific examples of this Ar ₈ group include Chemical formula 23 and Chemical formula 24

[Chemical formula 23]

[Chemical formula 24] Can be mentioned. You may use these organic tetracarboxylic dianhydride individually or in combination of 2 or more types. More specifically, in terms of the balance of various characteristics,

[Chemical 25] It is preferable that at least one of the above is a main component.

Next, regarding the number of repeating block units in the novel aromatic polyimide polymer represented by the general formula (1), l (ell) is a positive integer of 1 or more, and m is 0 or It may be a positive integer of 1 or more, but in the case of copolymerization, l and m are preferably in the range of 1 to 15, respectively. This is because when the ratio of the number of repetitions l and m exceeds 15, the copolymerization ratio becomes too biased and the effect of copolymerization becomes small. Further, units having different values of l and m may be present in one molecule of the polymer, but it is preferable that the values of l and m are the same.

The number n of repeating blocks in the above general formula (1) may be a positive integer of 1 or more, and the molecular weight of this novel aromatic polyimide copolymer is not particularly limited, but it is generated. In order to maintain the strength of the prepared polyimide resin, the number average molecular weight is 50,000 or more, and further 8
It is preferably 10,000 or more, particularly 100,000 or more, and more preferably 120,000 or more. By the way, it is often difficult to directly measure the molecular weight of a 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.

In the novel aromatic polyimide polymer represented by the above-mentioned general formula (1), in order that the repeating numbers l, m and n of the block unit are within a predetermined range, the above-mentioned general formula (2) In the novel aromatic polyamic acid polymer represented by (4), it is preferable that the block repeating numbers s, t, and u are within a predetermined range. That is, the repeating number s is a positive integer of 1 or more, and t may be 0 or a positive integer of 1 or more, but in the case of copolymerization, s and t are each in the range of 1 to 15. Is desirable. Further, the block repetition number u may be a positive integer of 1 or more.

The obtained novel aromatic polyimide polymer of the present invention has excellent thermoplasticity, adhesiveness and low water absorption. That is, the novel aromatic polyimide polymer has a clear glass transition point between 100 ° C. and 350 ° 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, a copper-clad laminate in which the polyimide film and the copper foil are adhered can be relatively easily manufactured. Further, it has been confirmed that the obtained novel aromatic polyimide polymer of the present invention has a low water absorption rate of about 1% when immersed in pure water at 20 ° C. for 24 hours.

Therefore, even when a flexible printed wiring board is formed by arranging and adhering copper foil or the like on one or both surfaces of the film produced from the obtained novel aromatic polyimide polymer without using an adhesive. Alternatively, a copper foil or the like may be provided on one side of the film, and a release paper or the like may be provided on the other side, and the copper foil or the like may be adhered to only one side. Further, such a polyimide film is particularly effective as a substrate such as a multilayer printed wiring board.

Further, the film comprising the novel aromatic polyimide polymer according to the present invention can be used as an adhesive layer 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. Other uses are not particularly limited.

Although the examples of the novel aromatic polyimide polymer and the novel aromatic polyamic acid polymer according to the present invention have been described above, the present invention is not limited to these examples, and the present invention is not limited to these examples. The present invention can be implemented with various improvements, changes and modifications based on the knowledge of those skilled in the art without departing from the spirit of the invention.

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

Example 1 Conversion into a 50 ml volumetric flask 26

[Chemical formula 26] Ethylene glycol bistrimellitic dianhydride (hereinafter, referred to as TMEG) (1.0 g) and dimethylformamide (hereinafter, referred to as DMF) (10.0 g) were taken, and they were sufficiently dissolved by stirring with a stirrer. On the other hand,
Converted to a 500 ml three-necked flask equipped with a stirrer 27

[Chemical 27] 2,2-bis (4-aminobenzyloxyphenyl) propane (hereinafter referred to as BABPP) 22.
7 g and 68.1 g of DMF were added, and the atmosphere in the flask was stirred while replacing the atmosphere in the flask with nitrogen to sufficiently dissolve it.

Next, 19.0 g of TMEG was sampled in a 100 ml round-bottomed flask and added as a solid to the BABPP solution in the three-necked flask. Furthermore, this 1
TMEG remaining on the wall surface of a 00 ml eggplant-shaped flask was dissolved with 21.5 g of DMF, poured into the three-necked flask, and left with stirring for about 1 hour. Then, the TMEG solution in the volumetric flask 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 TMEG solution was completed, and the mixture was allowed to stand with stirring for 1 hour to obtain a polyamic acid solution.

The film formation was performed as follows. First, 1
Isoquinoline 2.0 in a 00 ml volumetric flask
g and acetic anhydride 20.0 g were taken and stirred well. next,
This solution was added to the prepared polyamic acid solution and well stirred for 2 minutes. After degassing, apply on PET film and apply
After heating at 25 ° C. for 25 minutes, the PET film was peeled off from the polyamic acid film which became self-supporting. Then, the temperature was continuously raised from 150 ° C. to 200 ° C., and after the temperature was raised, it was heated for 5 minutes to imidize. Further, copper foil (thickness of 35 μm) is formed on both sides of the obtained polyimide film.
Was placed and heated to 300 ° C. and laminated at a speed of 2.2 cm / min to obtain a copper clad plate.

The glass transition point (° C.) and peel strength (kg / c) of the obtained polyimide film and copper clad plate were measured.
m) and water absorption (%) were investigated. Glass transition point is TMA
The peel strength was measured according to JIS K6481 and the water absorption was measured according to ASTM D-570. The results are shown in Table 1.

[Table 1]

Example 2 Into a 50 ml volumetric flask 28

[Chemical 28] 2,2'-bis (4-hydroxyphenyl) represented by
Propane dibenzoate-2,2 ', 3,3'-tetracarboxylic acid dianhydride (hereinafter referred to as E
Called SDA. ) 1.0 g and DMF 10.0 g were taken and fully dissolved by stirring using a stirrer. On the other hand, BA in a 500 ml three-necked flask equipped with a stirrer.
BPP (12.9 g) and DMF (38.7 g) were added, and the atmosphere in the flask was agitated while substituting with nitrogen to sufficiently dissolve the atmosphere.

Next, 14.9 g of ESDA was sampled in a 100 ml eggplant-shaped flask and added in solid form to the BABPP solution in the three-necked flask. Furthermore, this 1
The ESDA remaining on the wall surface of the 00 ml eggplant flask was dissolved in 37.7 g of DMF and poured into the three-necked flask. After standing for about 1 hour with stirring, the ESDA solution in the volumetric flask was gradually charged into the three-necked flask while paying attention to the viscosity in the three-necked flask. After reaching the maximum viscosity, the addition of the ESDA solution was terminated, and the mixture was allowed to stand with stirring for 1 hour to obtain a polyamic acid solution.

The film formation was performed as follows. First, 1
Isoquinoline 1.1 in a 00 ml volumetric flask
g and 11.0 g of acetic anhydride were taken and stirred well. next,
This solution was added to the prepared polyamic acid solution and well stirred for 2 minutes. After degassing, apply on PET film and apply
After the PET film was peeled from the polyamic acid film that became self-supporting by heating at 25 ° C for 25 minutes, the temperature was continuously raised from 150 ° C to 250 ° C, and after heating for 5 minutes, the imide was heated. Made into Further, copper foil (35 μm thick) was placed on both sides of the obtained polyimide film, heated to 300 ° C. and laminated at a speed of 2.2 cm / min to obtain a copper clad plate.

The properties of the obtained polyimide film and copper clad plate were examined in the same manner as in Example 1. The results are shown in Table 1.

Comparative Example 1 For comparison, 3,3 ', 4,4'-benzophenyltetracarboxylic dianhydride (hereinafter referred to as BTDA
Say. ) And 2,2′-bis [4- (4-aminophenoxy) phenyl] propane (hereinafter referred to as BAPP) were used to prepare a thermoplastic polyimide. First,
BTDA 1.94 in a 50 ml volumetric flask.
g and 30.0 g of DMF were taken and sufficiently dissolved. In addition, BA in a 500 ml three-necked flask equipped with a stirrer.
PP (51.8 g) and DMF (310.0 g) were taken and sufficiently dissolved while cooling with ice water and stirring while replacing the atmosphere in the flask with nitrogen.

Next, 38.8 g of BTDA was sampled in a 100 ml eggplant-shaped flask and added to the BAPP solution in a solid state. In addition, 10.0 g of BTDA remaining on the wall surface of the 100 ml eggplant flask was left.
It was melted with DMF, and poured into the three-necked flask, and left for 30 minutes while stirring. Then, the BTDA solution in the volumetric flask 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. Then, DMF was added so that the sample amount would be 500 g, and the mixture was stirred to obtain a polyamic acid solution.

This amic acid solution was applied on an aluminum foil,
After peeling the aluminum foil from the polyamic acid film that has become self-supporting by heating at 80 ° C. for 25 minutes,
The film is 150 ℃, 200 ℃, 250 ℃, 300
It was imidized by heating at 5 ° C. for 5 minutes each. Further, a copper foil (thickness of 35 μm) was placed on both sides of the obtained polyimide film, heated at 300 ° C., and laminated at a speed of 2.2 cm / min. However, the copper foil did not adhere to the polyimide film.

The glass transition point and water absorption of the obtained polyimide film were examined in the same manner as in Example 1. The results are shown in Table 1.

[0044]

As described above, the general formula (1) according to the present invention
The novel aromatic polyimide polymer represented by the formula (1) has excellent heat resistance and thermoplasticity, can realize adhesiveness, and has a low water absorption rate and excellent processability.

Claims (8)

[Claims] 1. A compound represented by the general formula (1): (In the formula, Ar ₁ represents a divalent organic group, Ar ₂ and Ar ₃ both represent a tetravalent organic group, l and n are positive integers of 1 or more, and m is 0 or a positive integer of 1 or more. Represents an integer of 1.), and a novel aromatic polyimide polymer. 2. Ar ₁ in the general formula (1) is represented by the following formula: The novel aromatic polyimide polymer according to claim 1, wherein the novel aromatic polyimide polymer is a divalent organic group. 3. Ar ₂ in the general formula (1) is represented by the following formula: At least 1 selected from the group of tetravalent aromatic groups shown in
The novel aromatic polyimide polymer according to claim 1 or 2, which is a seed. 4. Ar ₃ in the general formula (1) is represented by the following formula: At least 1 selected from the group of tetravalent aromatic groups shown in
The novel aromatic polyimide polymer according to any one of claims 1 to 3, which is a seed. 5. A compound represented by the general formula (2) 5: (In the formula, Ar ₄ is a divalent organic group, Ar ₅ and Ar ₆ are all tetravalent organic groups, s and u are positive integers of 1 or more, and t is 0 or a positive integer of 1 or more. Represents an integer of 1.), and a novel aromatic polyamic acid polymer. 6. Ar ₄ in the general formula (2) is represented by the following chemical formula: The novel aromatic polyamic acid polymer according to claim 5, wherein the novel aromatic polyamic acid polymer is a divalent organic group. 7. Ar ₅ in the general formula (2) is represented by the following formula: At least 1 selected from the group of tetravalent aromatic groups shown in
The novel aromatic polyamic acid polymer according to claim 5 or 6, which is a seed. 8. Ar ₆ in the general formula (2) is represented by the following formula: At least 1 selected from the group of tetravalent aromatic groups shown in
The novel aromatic polyamic acid polymer according to any one of claims 5 to 7, which is a species.