JP2003213130A - Polyimide resin composition and fire-resistant adhesive - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To obtain a polyimide resin composition that is excellent in heat- resistance and adhesion to a metal such as copper or stainless steel, and good in electrical characteristics and mechanical characteristics. <P>SOLUTION: The polyimide resin composition comprises an aromatic polyimide A and a polyimide B having phenylethynyl group at the end in a weight ratio of the former to the latter (A/B) of 95/5-80/20. Polyimide B is shown by formula (2) (wherein Ar<SP>2</SP>shows a bivalent organic group a main component of which is a bivalent aromatic group having at least one aromatic ring, Y shows a phenylethynyl phthalic acid imide-containing group same as a left terminal or hydrogen, an amino-terminus, an acid-terminus, or a terminal group obtained by modifying these terminals, and (m) is an integer of 1-10). <P>COPYRIGHT: (C)2003,JPO

Description

Detailed Description of the Invention

[0001]

TECHNICAL FIELD The present invention relates to a polyimide resin composition composed of a linear polyimide and a polyimide having a phenylethynyl group at the end, and a cured product thereof having excellent heat resistance. The present invention also relates to a heat resistant adhesive and a varnish containing the same.

[0002]

2. Description of the Related Art Conventionally, various polyimide resins have been developed, and in addition to their excellent heat resistance characteristics, they are also excellent in mechanical characteristics, electrical characteristics, and flame retardancy. Widely used as materials, heat resistant films, insulating varnishes, heat resistant adhesives, and molding materials. Copper clad laminate for flexible printed circuit board, adhesive film for multilayer printed circuit board, cover film for printed circuit board, semiconductor coating agent, underfill agent, TAB
It is used as a sealing material for automobiles and as a member in the aerospace field. In particular, recently, thermoplastic and moldable polyimide resins and polyimide resins soluble in organic solvents have been developed, and their application fields are expanding. In particular, in the field of semiconductors and printed circuit boards, high reliability as well as heat resistance is required, and therefore polyimide materials having excellent mechanical properties and electrical properties have come to be used. Further, recently, from the viewpoint of environmental problems, lead-free solder materials are being used, and development of materials having a high solder heat resistance temperature has been desired.

For these purposes, in recent years, melt-moldable polyimides (US Pat. Nos. 3,847,867 and 3,847,869)
Has been developed, but it had drawbacks such as a low glass transition temperature of about 215 ° C. and poor chemical resistance. Further, a melt-moldable resin having a relatively high glass transition temperature and excellent chemical resistance has also been developed (US Pat. No. 4,847,
No. 349, No. 5,087,689). However, these require a temperature of 250 ° C. or higher for molding. A thermosetting polyimide having a maleimide structure at the molecular chain end has also been reported (FDDarmory, Int'l. SAMPE.
Symp., 693, No. 19 (1974)). However, these are unsatisfactory because they have low mechanical properties after curing, particularly low tensile elongation, low impact strength, and low thermal decomposition temperature.

In recent years, a thermoplastic polyimide having a flexible molecular chain has also been developed and used as a varnish-shaped or film-shaped heat-resistant adhesive (JP-A-3-177472). In addition, a polyimide obtained by copolymerizing a soft segment such as diaminosiloxane has also been reported (Japanese Patent Laid-Open No. Hei 10 (1999) -242242).
4-36321, JP-A-5-112760). However, these are all linear thermoplastic polyimides,
Since the strength at the glass transition temperature or higher is extremely lowered, the adhesive strength at a high temperature is significantly lowered. Further, generally, when these polyimide resins are used alone as an adhesive or an adhesive film, sufficient adhesive strength cannot be obtained, and they have a problem in that they are resistant to organic solvents. Further, a thermosetting polyimide having a cross-linking reactivity at the end of the polyimide chain has also been developed (JP-A-3-259980). However, since these are low molecular weight oligomers, they are difficult to form into a film and are limited to use as a varnish. Further, it has a drawback that a high curing temperature is required.

[0005]

DISCLOSURE OF THE INVENTION The present invention overcomes the above-mentioned drawbacks of the prior art, has excellent heat resistance and organic solvent resistance, and has excellent adhesiveness to metals such as copper and stainless steel. It is intended to provide a composition. Another object is to provide a polyimide resin composition which comprises a linear polyimide and a thermosetting polyimide having an acetylene group at the terminal and is capable of forming a film. Another object is to provide a varnish and heat resistant adhesive containing the same.

[0006]

That is, the present invention provides the following general formula (1):

[Chemical 5] (In the formula, Ar ¹ is a tetravalent organic group having at least one aromatic ring, R ¹ and R ² are independently an organic group having 1 to 6 carbon atoms, and X is —O—, —S— , -SO ₂ -or a divalent organic group, i, j
Represents an integer of 0 to 4 and k represents an integer of 1 or more) and a polyimide A comprising a repeating unit represented by the following general formula (2)

[Chemical 6] (Ar ² is a divalent organic group containing a divalent aromatic group having at least one aromatic ring as a main component, Y is a phenylethynyl group or hydrogen, an amine terminal, an acid terminal or a terminal that seals these terminals. Is a group, m is an integer of 1 to 10) represented by a polyimide resin composition having a phenylethynyl terminal structure represented by polyimide B as an essential component, the weight ratio A / B
Is in the range of 99/1 to 1/99, which is a polyimide resin composition.

Here, 10 of Ar ² in the general formula (2) is used.
Mol% or more is represented by the following general formula (3) or the following general formula (4)
A divalent organic group represented by is preferable.

[Chemical 7] (In the formula (3), Y is _{-O -, - C (CH 3} ) 2 -. A group represented by in formula (4), or Z is absent, -O-, -C (CH ₃ ) _2-
Or -C (CF _{3) 2} - indicates either not A is _{present, -C (CH 3) 2 -} ,
Indicates -CO-, -O-, -S-, -SO _2- , -CH ₂ -or -C (CF ₃ ) _2- )

Further, the Ar ² in the general formula (2) is 10 to 50.
It is also preferable that mol% is a divalent organic group represented by the following general formula (5).

[Chemical 8] (In the formula, R ³ represents a hydrocarbon group having 1 to 7 carbon atoms, R ⁴ represents a methyl group, an isopropyl group, a phenyl group or a vinyl group,
l represents an integer of 1 to 20)

The present invention also provides a polyimide A obtained by reacting an aromatic tetracarboxylic dianhydride with a diamine having two or more aromatic rings, an aromatic tetracarboxylic dianhydride and phenylethynyl anhydride. A polyimide obtained by reacting phthalic acid with a diamine containing 50 mol% or more of an aromatic diamine having at least one aromatic ring, the polyimide B having a terminal of 50 mol% or more a phenylethynyl group. , 1/99 to 99/1 in weight ratio. Further, the present invention is a heat resistant adhesive comprising the above polyimide resin composition or a varnish obtained by dissolving the above polyimide resin composition in an organic solvent. The present invention is also a cured product obtained by curing the above polyimide resin composition.

The polyimide resin composition of the present invention must have a polyimide (referred to as polyimide A) consisting of a repeating unit represented by the general formula (1) and a polyimide represented by general formula (2) (referred to as the polyimide B). As an ingredient. Polyimide A may consist only of the repeating unit represented by the general formula (1), or may contain other repeating units,
The repeating unit represented by the general formula (1) may be contained in an amount of 50 mol% or more, preferably 80 mol% or more. Also,
Polyimide B is a polyimide represented by the general formula (2). In the general formula (2), Y may be a group having the same phenylethynylphthalimide group as the terminal group on the left side of the formula (sometimes abbreviated as phenylacetylenyl group), hydrogen, other It can also be a terminal group. When it is another terminal group, it may have an acid terminal, an amine terminal, or the like, but it may be one that has reacted with the terminal blocking agent or the like. Polyimide B in which Y is a phenylacetylenyl group can be represented by the following formula.

[Chemical 9] Here, Ar ² , Ar ³ and n have the same meanings as Ar ² , Ar ³ and m in the general formula (2). Then, at least a part of Y may be a phenylacetylenyl group. Polyimide
The ratio (weight ratio) of A to polyimide B needs to be in the above range, but is preferably in the range of 10/90 to 50/50. The polyimide resin composition of the present invention forms a cured product by the crosslinking reaction of the terminal phenylethynyl groups by heat treatment.

In the general formulas (1) and (2), Ar ¹ and Ar ³ are independently a tetravalent organic group having at least one aromatic ring and correspond to the residue of an aromatic tetracarboxylic acid. . Such a tetravalent organic group, polyimide A and
It is easily understood from the aromatic tetracarboxylic dianhydride as the raw material of B.

In the general formula (1), the divalent organic group consisting of two benzene rings linked by X corresponds to an aromatic diamine residue. Such a divalent organic group can be easily understood from the aromatic diamine as a raw material of the polyimide A described later. The benzene ring has an alkyl group, a phenyl group,
It may have an organic group having 1 to 6 carbon atoms such as an ester group and an amide group, and up to four substituents such as halogen. Preferred substituents have 3 carbon atoms such as methyl group and ethyl group.
The following are lower alkyl groups. Also, X is alkylene,
Divalent organic groups such as alkylidene and arylene, O, S, SO ₂
, Etc., but a divalent organic group has a carbon number of 1
~ 3 alkylene or alkylidene are preferred.

In the general formula (1), k represents the number of repetitions and is an integer of 1 or more. The weight average molecular weight of Polyimide A is preferably in the range of 2000 to 20000. In the general formula (2), m represents the number of repetitions and is in the range of 1-10. The weight average molecular weight of Polyimide B is preferably in the range of 500 to 5000.

In the general formula (2), Ar ² is a divalent organic group having at least one aromatic ring and corresponds to the residue of the aromatic diamine. Such a divalent organic group can be easily understood from the aromatic diamine as a raw material of the polyimide B described later. Or part thereof is entirely Ar ² is a group represented by the general formula (3) or (4) is preferably a group in which some of the Ar ² is represented by the general formula (5). In order to improve flexibility and adhesion / adhesion to the polyimide chain, 10 mol% or more of Ar ² in the general formula (2), preferably 5
It is preferable that 0 mol% or more, more preferably 80 mol% or more, is a group represented by the general formula (3) or (4). Also, in order to improve the flexibility of the polyimide chain,
10 to 50 mol%, preferably 10 to 30 mol% of Ar ² in the general formula (2) is preferably the group represented by the general formula (5). In this case, the total of the group represented by the general formula (3) and the group represented by the general formula (4) is Ar.
60 mol% of ² , preferably 90 mol% or more. Further, as for the diamine residue in the general formula (1), 10 mol% or more, preferably 50 mol% or more, more preferably 80 mol% or more is a group represented by the general formula (3) or (4). Be good. Also, 10 to 5
It is also advantageous that 0 mol%, preferably 10 to 30 mol%, is a group represented by the above general formula (5).

[0015]

BEST MODE FOR CARRYING OUT THE INVENTION Polyimide A can be synthesized by reacting an aromatic tetracarboxylic dianhydride with an aromatic diamine. The molar ratio of aromatic tetracarboxylic dianhydride and aromatic diamine is 1: 0.95 to 1.05,
The ratio is preferably in the range of 1: 0.97 to 1.03.

Specific examples of the aromatic tetracarboxylic dianhydride used as a raw material for the polyimide A include pyromellitic dianhydride (PMDA) and 3,3 ′, 4,4′-diphenylsulfone tetracarboxylic dianhydride. Anhydrous (DSDA), 3,3 ', 4,4'
-Biphenyltetracarboxylic dianhydride (BPDA), 2,
3 ', 3,4'-biphenyltetracarboxylic dianhydride (a-BPD
A), 3,3 ', 4,4'-benzophenone tetracarboxylic dianhydride (BTDA), 2,2'-bis (3,4-dicarboxyphenyl) hexafluoropropane dianhydride (BDCF), 2 2,2'-bis (2,3-dicarboxyphenyl) ether dianhydride (a-
ODPA), 2,2'-bis (3,4-dicarboxyphenyl) propane dianhydride (BDCP), 2,2'-bis (3,4-dicarboxyphenyl) hexafluoropropane dianhydride (BDCF) , 1,
4,5,8-naphthalenetetracarboxylic dianhydride (NTCA),
Cyclopentane-1,2,3,4-tetracarboxylic dianhydride
(CPTA), pyrrolidine-2,3,4,5-tetracarboxylic dianhydride (PTCA), 1,2,3,4-butanetetracarboxylic dianhydride (BTCA) and the like, Without being limited to these, various aromatic tetracarboxylic dianhydrides can be used. Moreover, these can be used 1 type or in combination of 2 or more types. From the viewpoint of improving heat resistance and suppressing the coefficient of thermal expansion, pyromellitic dianhydride (PMDA) is preferable. From the viewpoint of imparting flexibility and solubility in organic solvents, 3,3 ', 4,4 '-Diphenylsulfone tetracarboxylic dianhydride (DSDA), 3,3', 4,4'-biphenyltetracarboxylic dianhydride (BPDA), 2,2'-bis (3,4-dicarboxyphenyl) Hexafluoropropane dianhydride (BDCF) is preferably used.

Polyimide B is phenylethynyl phthalic anhydride (PEPA), aromatic tetracarboxylic dianhydride,
It can be synthesized by reacting a diamine containing 50 mol% or more of an aromatic diamine. The molar ratio of PEPA, aromatic tetracarboxylic dianhydride and diamine is (PEPA
Number of moles x 2 + number of moles of aromatic tetracarboxylic dianhydride): number of moles of diamine = 1: 0.95 to 1.05, preferably
It is preferable to set the range of 1: 0.97 to 1.03. Also, the number of moles of PEPA: the number of moles of aromatic tetracarboxylic dianhydride,
The range is from 2: 1 to 19, preferably about 1: 2 to 8.

Specific examples of the aromatic tetracarboxylic dianhydride used as a raw material for the polyimide B include pyromellitic dianhydride (PMDA) and 3,3 ′, 4,4′-diphenylsulfone tetracarboxylic dianhydride. Anhydrous (DSDA), 3,3 ', 4,4'
-Biphenyltetracarboxylic dianhydride (BPDA), 2,
3 ', 3,4'-biphenyltetracarboxylic dianhydride (a-BPD
A), 3,3 ', 4,4'-benzophenone tetracarboxylic dianhydride (BTDA), 2,2'-bis (3,4-dicarboxyphenyl) hexafluoropropane dianhydride (BDCF), 2 2,2'-bis (2,3-dicarboxyphenyl) ether dianhydride (a-
ODPA), 2,2'-bis (3,4-dicarboxyphenyl) propane dianhydride (BDCP), 2,2'-bis (3,4-dicarboxyphenyl) hexafluoropropane dianhydride (BDCF) , 1,
4,5,8-naphthalenetetracarboxylic dianhydride (NTCA),
Cyclopentane-1,2,3,4-tetracarboxylic dianhydride
(CPTA), pyrrolidine-2,3,4,5-tetracarboxylic dianhydride (PTCA), 1,2,3,4-butanetetracarboxylic dianhydride (BTCA) and the like, Without being limited to these, various aromatic tetracarboxylic dianhydrides can be used. Moreover, these can be used 1 type or in combination of 2 or more types. From the viewpoint of improving heat resistance and suppressing the coefficient of thermal expansion, pyromellitic dianhydride (PMDA) is preferable. From the viewpoint of imparting flexibility and solubility in organic solvents, 3,3 ', 4,4 '-Diphenylsulfone tetracarboxylic dianhydride (DSDA), 3,3', 4,4'-biphenyltetracarboxylic dianhydride (BPDA), 2,2'-bis (3,4-dicarboxyphenyl) Hexafluoropropane dianhydride (BDCF) is preferably used.

The diamine used as a raw material for synthesizing the polyimides A and B can be commonly used as long as it has two or more aromatic rings. However, the diamine used as a raw material for synthesizing the polyimide B can be used even if it has one aromatic ring.
Furthermore, as the diamine used as a raw material for the polyimide B, 50 mol% or more, preferably 70 mol% or more, is at least one aromatic diamine having at least two aromatic rings and two amino groups in the molecule. Can be used. From the viewpoint of improving flexibility, the aromatic diamine is preferably an aromatic diamine having at least three phenylene rings. The diamine other than the aromatic diamine is preferably a diamine having a siloxane group represented by the general formula (4).

Preferred specific examples of the aromatic diamine used as a raw material for synthesizing polyimides A and B include diamino compounds having two phenylene rings, 4,4'-diaminodiphenyl ether, 4,4'-diaminodiphenyl sulfide, 4,4'-diaminodiphenyl sulfone, 4,
4'-diaminodiphenylmethane, 2,2'-bis (4-aminophenyl) propane, 2,2'-bis (4-aminophenyl) hexafluoropropane and the like can be mentioned.

Specific preferred examples of the aromatic diamine having three phenylene rings include diamino compounds represented by the following (a) to (d).

[Chemical 10]

Preferred specific examples of the aromatic diamine having four phenylene rings include aromatic diamines represented by the following (e) to (t).

[Chemical 11]

[0023]

[Chemical 12]

The siloxanediamine used as the raw material for the polyimide B is a siloxanediamine having a unit represented by the above general formula (5). General formula (5)
As the siloxane-based diamine used to form the unit represented by the following general formula (6)

[Chemical 13] And a diaminopolysiloxane represented by R ³ , R ⁴ and l in the general formula (6) have the same meaning as in the general formula (5).

Examples of the method for synthesizing the polyimide A include 1) a method of synthesizing a polyimide precursor solution by low temperature solution polymerization, and then chemically or thermally ring-closing it to imidize. By changing the molar ratio of the tetracarboxylic dianhydride and the diamine, which are polyimide raw materials, the polymerization viscosity can be adjusted, but usually 1.0: 0.9 to 1.
By preparing in the range of 1, it is possible to obtain a polyimide precursor solution or a polyimide solution capable of forming a film.

The polyimide B can be synthesized by low temperature polycondensation as in the above method.
The total number of carboxylic acid anhydride groups of phenylethynyl phthalic anhydride (a) and tetracarboxylic acid anhydride (b) is diamine.
It is preferable that the number of amino groups in (c) is the same as that of the reaction. Furthermore, the molar ratio of these raw materials is (a) /
It is preferable that (b) / (c) = 40/80/100 to 2/99/100.

The polyimide resin composition of the present invention is a resin composition comprising a linear polyimide and a polyimide having a terminal phenylethynyl group, and the terminal phenylethynyl group is crosslinked by heating at 300 ° C to 400 ° C. Can be advanced. By advancing this reaction, it is possible to improve heat resistance and chemical resistance, and further improve the adhesive strength to the metal substrate. Further, since the linear polyimide and the resin composition are formed, the material can be processed into a film and used, and is a material having excellent mechanical properties even after heating and curing. Polyimide A has a softening point or Tg of 150 ° C or higher, and polyimide B has a softening point or Tg.
The temperature is preferably 150 ° C. or higher, and the mixing of these may be a method of mixing in a solution state, a method of mixing with a precursor solution to imidize and drying. The reduced viscosity of polyimide A is preferably about 0.3 to 1.5 dl / g.

The polyimide resin composition of the present invention may contain resin components other than polyimide A and polyimide B, and other components such as fillers and pigments. The polyimide A and polyimide B are 50 wt% in all resin components. % Or more, preferably 80 wt% or more.

The polyimide resin composition of the present invention comprises a linear polyimide and a polyimide having a terminal acetylene group, and the polyimide having a terminal acetylene group can form a crosslinked structure by heating. Further, since the linear polyimide and the resin composition are formed, it can be processed into a film and used. These are excellent in heat resistance and substrate adhesion, can improve organic solvent resistance, and have good electrical properties and mechanical properties.
As a peripheral member for assembling laminated boards for printed wiring boards, printed wiring boards, semiconductor encapsulating materials, semiconductor mounting modules, other various electronic parts, automobiles, aircraft parts,
It can be used as a building member, a carbon fiber, a carbon electrode, a binder such as various composite materials, a matrix resin, or an adhesive material. The heat-resistant adhesive of the present invention is
The polyimide resin composition of the present invention is used as an active ingredient. It will consist of The varnish of the present invention is obtained by dissolving the polyimide resin composition of the present invention in an organic solvent. In this case, when the polyimide is synthesized in a solvent, it can be the organic solvent. The cured product of the present invention is obtained by heating the polyimide resin composition to crosslink the ethynyl group,
Excellent heat resistance and solvent resistance.

[0030]

EXAMPLES The present invention will be described in detail below with reference to examples, but the present invention is not limited to these examples. In addition, the abbreviations of the resin raw materials in the examples mean the followings other than those described in the text. DADE: 4,4'-diaminodiphenyl ether TPEQ: 1,4'-bis (4-aminophenoxy) benzene BAPP: 2,2-bis [4- (4-aminophenoxy) phenyl] propane BAPS: bis [4- ( 4-Aminophenoxy) phenyl] sulfone BAPSM: bis [4- (3-aminophenoxy) phenyl]
Sulfone BAPB: Bis [4- (4-aminophenoxy)] biphenyl PSX800: manufactured by Toray Dow Corning (BY16-853C), diaminopolysiloxane PSX1000 having an average molecular weight of 800 represented by the general formula (6): Toray Dow Corning Manufactured by (BY16-853), a diaminopolysiloxane represented by the general formula (6) and having an average molecular weight of 1000.

Example 1 Synthesis of Polyimide A Solution In a 1 L separable flask equipped with a Dean-Stark type dehydration cooling device and a stirring blade, N-methyl-2-pyrrolidinone (NM
P) 200 ml and toluene 100 ml are put, the temperature is kept at 25 ° C or lower by ice cooling, and BTDA (32.2
g, 0.1 mol) and PSX800 (8 g, 0.01 mol) were added dropwise little by little and then reacted for 2 hours. Then the diamine BAP
S (37.1 g, 0.09 mol) was added little by little as a powder. After reacting for 2 hours to sufficiently polymerize the polyamic acid, the temperature is gradually increased until reflux of toluene occurs,
Water generated by the imidization dehydration reaction was removed outside the polymerization reaction system. 1 hour after the completion of the dehydration imidization reaction
The reaction was terminated by stirring at 150 ° C. NMP was added to the obtained polyimide resin to adjust the solid content concentration to 20% by weight. The resin raw material composition and the solution viscosity of the resin are shown in Table 1.

Synthesis of Polyimide B Solution Dean-Stark type dehydration cooling device, N-methyl-2-pyrrolidinone (NM
P) 200 ml and toluene 100 ml are put, the temperature is kept at 25 ° C or lower by ice cooling, and PEPA (4.9
g, 0.02 mol), BTDA (29.0 g, 0.09 mol) and diamine
BAPS (37.1 g, 0.1 mol) was added little by little as a powder. After reacting for 2 hours to sufficiently polymerize the polyamic acid, the temperature is gradually increased until reflux of toluene occurs,
Water generated by the imidization dehydration reaction was removed outside the polymerization reaction system. 1 hour after the completion of the dehydration imidization reaction
The reaction was terminated by stirring at 150 ° C. NMP was added to the obtained polyimide resin to adjust the solid content concentration to 20% by weight. Table 2 shows the resin composition and the solution viscosity of the obtained resin.

Preparation of Polyimide Resin Composition After thoroughly mixing 150 g of the polyimide A solution and 50 g of the polyimide B solution, the mixed solution was cast on a glass substrate and cast using a doctor blade. Furthermore,
This is placed in an inert oven under a nitrogen stream at 100 ° C for 60
After drying for 60 minutes at 150 ° C. for 60 minutes, the resin layer was isolated from the glass substrate and fixed to a metal frame made of stainless steel. This was dried at 200 ° C. for 10 minutes to obtain a film of the heat resistant resin composition.

This film was further heat-treated at 250 ° C. for 10 minutes, and then its physical properties were measured. Using this film as an adhesive film, the adhesive strength with copper and stainless steel was measured at 250 ° C. for 10 minutes at a pressure of 19.6 MPa. The results are shown in Table 3. Further, the film of the heat-resistant resin composition obtained by drying at 200 ° C. for 10 minutes was dried at 250 ° C. for 1 minute.
The adhesive strength with copper and stainless steel was measured at 0 minutes, 350 ° C. for 10 minutes, and a pressure of 19.6 MPa. After drying at 200 ℃ for 10 minutes,
The film was subjected to heat treatment at 250 ° C. for 10 minutes and 350 ° C. for 10 minutes, and then the film physical properties of the heat resistant resin composition were measured. The results are shown in Table 4.

The glass transition temperature (Tg) is the dynamic viscoelasticity measuring device (DMA), and the coefficient of thermal expansion is the thermomechanical analyzer (Tg).
MA), thermal decomposition start temperature (5% weight loss temperature) is measured by thermogravimetric analyzer (TGA)
The measurement was performed according to K 6911. For adhesive strength,
The film adhesive obtained by the above method is sandwiched between metal adherends having a thickness of 50 μm, and a predetermined press-bonding temperature (final temperature 250 ° C. and final temperature 350
C.) and crimping pressure (19.6 MPa) according to JIS K 6850. After adhesion, the 180 ° C peeling (T peeling) strength was measured using Autograph AG-500A (manufactured by Shimadzu Corporation). Solubility is measured by adding 0.5 g of resin to 100 ml of THF and NMP.
Solubility with respect to. ○ indicates complete dissolution,
X indicates insolubility.

Examples 2 to 8 Polyimide resin compositions were produced in the same manner as described in Example 1 except for the composition of the polyimide raw material and evaluated in the same manner.

Comparative Examples 1 to 3 Polyimide resin compositions were produced in the same manner as described in Example 1 except that the raw material compositions of the resins were different, and the evaluation was conducted in the same manner. The raw material composition of polyimide A is shown in Table 1, and the raw material composition of polyimide B is shown in Table 2. The physical properties of the film obtained by the 250 ° C. treatment are shown in Table 3, and the physical properties of the film obtained by the 350 ° C. treatment are shown in Table 4. The raw material composition of the polyimide resin is shown in Tables 1 and 2, the physical properties of the film obtained by drying at 250 ° C are shown in Table 3, and the physical properties of the film obtained by drying at 350 ° C are shown in Table 4.

[0038]

[Table 1]

[0039]

[Table 2]

[0040]

[Table 3]

[0041]

[Table 4]

[0042]

The polyimide resin composition of the present invention has excellent heat resistance and excellent adhesion to metals such as copper and stainless steel. Furthermore, since it has good electrical and mechanical properties, it can be used as a laminated board for printed wiring boards, a printed wiring board, a semiconductor encapsulation material, a semiconductor mounting module, an IC encapsulation material, and various electronic component peripheral members, as well as these. It is also useful as an additive for improving the functions of the materials used. In addition to automobiles, aircraft components, building components, etc., they can be used as binders and matrix resins for carbon fibers, carbon electrodes, various composite materials, etc. Furthermore, the heat resistant resin of the present invention can be used not only as a varnish but also in the form of a film, a sheet, a fiber or the like.

Continued front page    F-term (reference) 4J002 CM04W CM04X GJ01 HA05                 4J038 DJ021 DL031 NA14 NA15                       PB09                 4J040 EH031 EK031 LA08 NA19                 4J043 PA08 PB23 QB15 QB26 QB31                       RA35 SA06 TA22 UA032                       UA122 UA131 UA132 UA141                       UA151 UA262 UA332 UA762                       UB011 UB021 UB022 UB061                       UB062 UB121 UB122 UB131                       UB141 UB152 UB281 UB301                       UB302 UB321 UB401 UB402                       VA012 VA021 VA022 VA031                       VA051 VA062 VA092 VA102                       XA13 ZA02 ZA12 ZB01

Claims (7)

[Claims] 1. The following general formula (1): (In the formula, Ar ¹ is a tetravalent organic group having at least one aromatic ring, R ¹ and R ² are independently an organic group having 1 to 6 carbon atoms, and X is —O—, —S— , -SO ₂ -or a divalent organic group, i, j
Represents an integer of 0 to 4 and k represents an integer of 1 or more), and a polyimide A comprising a repeating unit represented by the following general formula (2) (Ar ² is a divalent organic group whose main component is a divalent aromatic group having at least one aromatic ring, Y is a phenylethynyl phthalimide-containing group or hydrogen, an amine terminal, an acid terminal or these terminals A modified terminal group, m represents an integer of 1 to 10) represented by the polyimide resin composition having a phenylethynyl terminal structure represented by the polyimide B as an essential component, the weight ratio A / B, 99 The polyimide resin composition is in the range of / 1/1/99. ^2. 10 mol% of Ar ² in the general formula (2)
The polyimide resin composition according to claim 1, wherein the above is a divalent organic group represented by the following general formula (3) or the following general formula (4). [Chemical 3] (In the formula (3), Y is _{-O -, - C (CH 3} ) 2 -. A group represented by in formula (4), or Z is absent, -O-, -C (CH ₃ ) _2-
Or -C (CF _{3) 2} - indicates either not A is _{present, -C (CH 3) 2 -} ,
Indicates -CO-, -O-, -S-, -SO _2- , -CH ₂ -or -C (CF ₃ ) _2- ) 3. 10 to 50 mol% of Ar ² in the general formula (2) is represented by the following general formula (5): (In the formula, R ³ represents a hydrocarbon group having 1 to 7 carbon atoms, R ⁴ represents a methyl group, an isopropyl group, a phenyl group or a vinyl group,
The polyimide resin composition according to claim 1 or 2, wherein the polyimide resin composition is a divalent organic group represented by the formula (1 is an integer of 1 to 20). 4. A polyimide A obtained by reacting an aromatic tetracarboxylic dianhydride with a diamine having two or more aromatic rings, an aromatic tetracarboxylic dianhydride, phenylethynyl phthalic anhydride and at least A polyimide obtained by reacting a diamine containing 50 mol% or more of an aromatic diamine having one aromatic ring, wherein
Polyimide B in which 0 mol% or more is a phenylethynyl group
And a polyimide resin composition prepared by mixing 1 and 99 in a weight ratio of 1/99 to 99/1. 5. A heat resistant adhesive comprising the polyimide resin composition according to claim 1. 6. A varnish obtained by dissolving the polyimide resin composition according to claim 1 in an organic solvent. 7. A cured product obtained by curing the polyimide resin composition according to claim 1.