JPH09165448A - Block copolymer and its production - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain a block copolymer which has excellent adhesive properties because the m.p. or glass transition point of a crystalline or amorphous polymaide segment is lower than that of a crystalline or amorphous polyimide segment in the copolymer. SOLUTION: A polyajmide-polyimide block copolymer wherein the m.p. or glass transition point of a crystalline or amorphous polyamide segment is lower than that of a crystalline or amorphous polyimide segment is obtd. by dissolving a polyamide (e.g. nylon 11) in a phenolic solvent, thermally dissolving a tetracarboxylic dianhydride (e.g. pyromellitic dianhydride or 3,3',4,4'- benzophenonetetracarboxylic dianhydride) in the resultant soln., adding a diamine (e.g. 4.4'-diaminodiphenyl ether or 4,4'-diaminodiphenylmethane) in a molar ratio to the dianhydride of (1:2)-(2:1) to the soln., and thermally reacting the soln. at about 80-150 deg.C to thereby form polyimide segments and simultaneously to conduct addition polycondensation.

Description

Detailed Description of the Invention

[0001]

TECHNICAL FIELD The present invention relates to heat resistance, adhesiveness,
The present invention relates to a polyamide-polyimide block copolymer having excellent processability, particularly a polyamide-polyimide block copolymer suitable as an adhesive component and a method for producing the same.

[0002]

2. Description of the Related Art In recent years, electronic devices have become more sophisticated, have higher performance,
As the degree of integration increases, demands for adhesives for joining electronic materials used in electronic devices have become stricter. Conventionally, epoxy adhesives have been widely used as adhesives for electronic materials. However, the adhesive has a problem that the heat resistance is insufficient because the curing time is long and the productivity is poor and the glass transition temperature is as low as about 130 ° C.

On the other hand, thermosetting polyimide adhesives and thermoplastic polyimide adhesives have been developed as adhesives having high heat resistance, but thermosetting polyimide adhesives have a long curing time. At the same time, there was a problem that the curing temperature was high, and further, outgas was generated during curing.

On the other hand, the thermoplastic polyimide adhesive has a limited chemical structure having an adhesive function as compared with the thermosetting polyimide adhesive, and its kind is relatively small. As the thermoplastic polyimide adhesive, for example, JP-A-62-6
Although the adhesive described in Japanese Patent No. 8817 is known, since the glass transition temperature is high, the adhesion temperature is as high as 320 to 350 ° C., and the field of use is limited.

Further, as the polyamide-polyimide block copolymer, one for the purpose of improving the moldability of the resin has already been known (see JP-A-58-154729). These are aromatic polyamide-aromatic polyimide block copolymers and have a problem that the adhesion temperature is too high for use as an adhesive.
Furthermore, since these polyamide-polyimide block copolymers are prepared from a polymerization solution of polyamide using carboxylic acid dihalide as a raw material, hydrogen halide accompanying dehydrohalogenation reaction, ionic impurities such as acid acceptors, etc. It is unsuitable as an adhesive for electronic materials.

[0006]

An object of the present invention is to provide a polyamide-polyimide block copolymer useful as an adhesive component having excellent heat resistance and processability, and particularly a polyamide-polyimide block copolymer suitable as an adhesive component. The object is to provide a coalesce and a manufacturing method thereof.

[0007]

The present invention is a block copolymer consisting of a polyamide segment and a polyimide segment, which is soluble in a phenolic solvent, and has a thermal transition temperature relationship between the polyamide segment and the polyimide segment. I. When the polyamide segment is crystalline and the polyimide segment is crystalline, the melting point of the polyamide segment is lower than the melting point of the crystalline polyimide segment, and when the polyimide segment is amorphous, the melting point of the polyamide segment. Is a temperature lower than the glass transition temperature of the amorphous polyimide segment, and b. When the polyamide segment is amorphous and the polyimide segment is crystalline, the glass transition temperature of the polyamide segment is lower than the melting point of the crystalline polyimide segment, and when the polyimide segment is amorphous, the polyamide segment is The glass transition temperature of the segment is lower than the glass transition temperature of the amorphous polyimide segment, wherein the block copolymer, and a polyamide soluble in a phenolic solvent, and in a phenolic solvent To a phenolic solvent obtained by subjecting a tetracarboxylic dianhydride component and a diamine component to a heating polyaddition condensation reaction at a tetracarboxylic dianhydride / diamine molar ratio of 2/1 to 1/2 Each molecular end of the soluble polyimide is ligated in the phenolic solvent. Characterized in that, there is provided a process for producing the block copolymer of the description.

[0008]

BEST MODE FOR CARRYING OUT THE INVENTION Polyamide A polyamide soluble in a phenolic solvent used in the present invention is a raw material in view of a thermal transition temperature (melting point or glass transition temperature; hereinafter the same) with a polyimide segment. A polyamide using an aliphatic or alicyclic group as at least one of the components of dicarboxylic acid and diamine is preferable. So-called aramid (polyamide having 85% or more of amide groups directly bonded to an aromatic ring) has poor solubility in a phenolic solvent and tends to have a higher heat transition temperature than polyimide, which is not preferable. Specifically, nylon 6,6, nylon 6,10, nylon 6,12, nylon 11, nylon 12, nylon MX
D6 (crystalline polyamide obtained from metaxylylenediamine and adipic acid), nylon 4,6, nylon 6
Crystalline nylon and amorphous nylon such as T (polyamide obtained from hexamethylenediamine and terephthalic acid chloride) and nylon RIM (copolymer of ε-caprolactam and diol or diamine component) can be used.

These can be produced by a known method, or commercially available products can be used alone or in combination of two or more kinds. Nylon RI
Examples of the diol or diamine component used for producing M include polyether diol, polyether diamine, polydiene diol and hydrogenated product thereof, and polydiene diamine and hydrogenated product thereof.

The amorphous nylon is produced by polycondensation of dicarboxylic acid and diamine and / or diisocyanate or ring-opening polymerization of lactam. Among these production raw materials, dicarboxylic acid is, for example, adipic acid, Azelaic acid, terephthalic acid, isophthalic acid,
Examples thereof include cyclohexane-1,4-dicarboxylic acid, and examples of the diamine or diisocyanate include:
For example, hexamethylenediamine, trimethyl-1,6-
Diamines such as hexamethylene diamine, 4,4'-diaminodicyclohexylene methane, 4,4'-diamino-3,3'-dimethyldicyclohexylene methane, 4,4'-diaminodicyclohexylene propane and isophorone diamine; Examples of the diisocyanate include 4,4'-diphenylmethane diisocyanate and tolylene diisocyanate, and examples of the lactam include ε-
Examples thereof include caprolactam and ω-laurotactic. The dicarboxylic acids, diamines, diisocyanates and lactams can be used alone or in combination of two or more, and the dicarboxylic acids and diamines and / or the diisocyanates and lactams can also be reacted.

If necessary, the concentration of amino groups, isocyanate groups or carboxyl groups at the molecular ends of these polyamides may be adjusted to facilitate the preparation of block copolymers. It is also preferable to unify both ends of the molecule with the same functional group in order to increase the degree of blocking. In order to unify both ends of the molecule into the same functional group, in the case of a polyamide produced by polycondensation, the reaction equivalence ratio of one monomer may be increased to perform polycondensation.
In the case of polyamide produced by ring-opening polymerization, dicarboxylic acid or diamine may be added after the ring-opening polymerization to cause a condensation reaction.

Polyamides in which the functional groups at both ends of the molecule are unified to be amino groups or isocyanate groups react with a polyimide whose functional groups at the molecular ends are acid anhydride groups to form an imide ring and form a block copolymer. . In addition, polyamide that unifies the functional groups at both ends of the molecule into carboxyl groups,
The functional group at the terminal of the molecule reacts with the polyimide having an amino group to form an amide bond, forming a block copolymer.

The polyamide used in the present invention may have a number average molecular weight in the range of 500 to 200,000.

Polyimide The polyimide soluble in the phenol solvent used for the polyimide of the present invention is produced by subjecting tetracarboxylic dianhydride and diamine to polyaddition condensation reaction.

Specific examples of the tetracarboxylic dianhydride include pyromellitic dianhydride, 3,3 ', 4,4'.
-Benzophenone tetracarboxylic dianhydride, 2,
2 ', 3,3'-benzophenone tetracarboxylic dianhydride, 3,3', 4,4'-biphenyltetracarboxylic dianhydride, 2,2 ', 3,3'-biphenyltetracarboxylic dianhydride 2,2-bis (3,4-dicarboxyphenyl) propane dianhydride, 2,2-bis (2,3
-Dicarboxyphenyl) propane dianhydride, bis (3,4-dicarboxyphenyl) ether dianhydride,
Bis (3,4-dicarboxyphenyl) sulfone dianhydride, 1,1-bis (2,3-dicarboxyphenyl) ethane dianhydride, bis (2,3-dicarboxyphenyl)
Methane dianhydride, bis (3,4-dicarboxyphenyl) methane dianhydride, 2,2-bis (3,4-dicarboxyphenyl) hexafluoropropane dianhydride, 2,
3,6,7-naphthalenetetracarboxylic dianhydride,
1,4,5,8-naphthalenetetracarboxylic dianhydride, 1,2,5,6-naphthalenetetracarboxylic dianhydride, 1,2,3,4-benzenetetracarboxylic dianhydride, 3, 4,9,10-Perylene tetracarboxylic dianhydride, 2,3,6,7-anthracene tetracarboxylic dianhydride, 1,2,7,8-phenanthrene tetracarboxylic dianhydride, 2,2- Bis (4-hydroxyphenyl) propane bis trimellitate dianhydride, 4,4 '
-Dihydroxybenzophenone bis trimetate dianhydride, 4,4'-dihydroxy diphenyl ether bis trimellitate dianhydride, 4,4'-dihydroxy diphenyl sulfone bis trimellitate dianhydride, 1,4-dihydroxyphenyl bis trimellitate dianhydride Thing 2,
Aromatic tetracarboxylic acid dianhydrides such as 2-bis (4-hydroxyphenyl) hexafluoropropane bis trimellitate dianhydride; 2,3,5-tricarboxycyclopentyl acetic acid dianhydride, ethylene tetracarboxylic acid dianhydride , 1,2,3,4-cyclobutanetetracarboxylic acid dianhydride, 1,2,4,5-cyclopentanetetracarboxylic acid dianhydride, and the like. These can be used alone or in combination of two or more, and it is preferable to use at least one aromatic tetracarboxylic dianhydride. Among them, pyrrolimet dianhydride, 3,3 ', 4,4'-benzophenone tetracarboxylic dianhydride, 3,3',
4,4′-biphenyltetracarboxylic dianhydride, bis (3,4-dicarboxyphenyl) ether dianhydride,
Bis (3,4-dicarboxyphenyl) sulfone dianhydride is mentioned as a particularly preferred one.

Specific examples of the diamine include o-phenylenediamine, m-phenylenediamine, p-phenylenediamine, m-aminobenzylamine, p-aminobenzylamine, 2-chloro-1,4-phenylenediamine, 4 -Chloro-1,2-phenylenediamine, 2,
3-diaminotoluene, 2,4-diaminotoluene,
2,5-diaminotoluene, 2,6-diaminotoluene, 3,4-diaminotoluene, 2-methoxy-1,4
-Phenylenediamine, 4-methoxy-1,2-phenylenediamine, 4-methoxy-1,3-phenylenediamine, benzidine, 3,3'-dichlorobenzidine,
3,3'-dimethylbenzidine, 3,3'-dimethoxybenzidine, 3,3'-diaminodiphenyl ether,
3,4'-diaminodiphenyl ether, 4,4'-diaminodiphenyl ether, 3,3'-diaminodiphenyl sulfide, 3,4'-diaminodiphenyl sulfide, 4,4'-diaminodiphenyl sulfide, 3,
3'-diaminodiphenyl sulfoxide, 3,4'-diaminodiphenyl sulfoxide, 4,4'-diaminodiphenyl sulfoxide, 3,3'-diaminodiphenyl sulfone, 3,4'-diaminodiphenyl sulfone,
4,4'-diaminodiphenyl sulfone, 3,3'-diaminobenzophenone, 3,4'-diaminobenzophenone, 4,4'-diaminobenzophenone, 3,3'-
Diaminodiphenylmethane, 3,4'-diaminodiphenylmethane, 4,4'-diaminodiphenylmethane, bis [4- (3-aminophenoxy) phenyl] methane,
Bis [4- (4-aminophenoxy) phenyl] methane, 1,1-bis [4- (3-aminophenoxy) phenyl] ethane, 1,1-bis [4- (4-aminophenoxy) phenyl] ethane, 1,2-bis [4- (3-aminophenoxy) phenyl] ethane, 1,2-bis [4
-(4-Aminophenoxy) phenyl] ethane, 2,2
-Bis [4- (4-aminophenoxy) phenyl] propane, 2,2-bis [4- (3-aminophenoxy) phenyl] butane, 2,2-bis [4- (4-aminophenoxy) phenyl] butane , 2,2-bis [4- (4-
Aminophenoxy) phenyl] 1,1,1,3,3,3
-Hexafluoropropane, 1,4-bis (4-aminophenoxy) benzene, 1,4-bis (3-aminophenoxy) benzene, 1,3-bis (4-aminophenoxy) benzene, 1,3-bis ( 3-aminophenoxy)
Benzene, 4,4'-bis (4-aminophenoxy) biphenyl, bis [4- (4-aminophenoxy) phenyl] ketone, bis [4- (4-aminophenoxy) phenyl] sulfide, bis [4- (3 -Aminophenoxy) phenyl] sulfoxide, bis [4- (4-aminophenoxy) phenyl] sulfoxide, bis [4- (4
-Aminophenoxy) phenyl] sulfone, bis [4-
(4-Aminophenoxy) phenyl] ether, 1,4
-Bis [4- (3-aminophenoxy) benzoyl] benzene, 1,3-bis [4- (3-aminophenoxy)
Benzoyl] benzene, 4,4'-bis [3- (4-aminophenoxy) benzoyl] diphenyl ether,
4,4'-bis [3- (3-aminophenoxy) benzoyl] diphenyl ether, 4,4'-bis [4- (4
-Amino-α, α-dimethylbenzyl) phenoxy] benzophenone, 4,4'-bis [4- (4-amino-
α, α-Dimethylbenzyl) phenoxy] diphenyl sulfone, bis [4- {4- (4-aminophenoxy) phenoxy} phenyl] ketone, bis [4- {4-aminophenoxy) phenoxy} phenyl] sulfone, 1,4
An aromatic diamine such as -bis [4- (4-aminophenoxy) -α, α-dimethylbenzyl] benzene and 1,3-bis [4- (4-aminophenoxy) -α, α-dimethylbenzyl] benzene; 1,2-diaminoethane, 1,
3-diaminopropane, 1,4-diaminobutane, 1,
5-diaminopentane, 1,6-diaminohexane,
Aliphatic diamines such as 1,7-diaminoheptane, 1,8-diaminooctane, 1,9-diaminononane, 1,10-diaminodecane, 1,11-diaminoundecane and 1,12-diaminododecane can be mentioned. These can be used alone or in combination of two or more, and it is preferable to use at least one aromatic diamine. Among them, 4,4'-diaminodiphenyl ether, 4,4'-diaminodiphenyl sulfide, 4,
4'-diaminobenzophenone, 4,4'-diaminodiphenyl sulfoxide, 4,4'-diaminodiphenylmethane, 2,2'-bis (4-aminophenyl) propane, 2,2-bis (4-aminophenyl) hexafluoro Particularly preferred are propane, 2,4-diaminotoluene and 2,6-diaminotoluene.

As the method for synthesizing the polyimide used in the present invention, at least one kind of aromatic tetracarboxylic dianhydride and at least one kind of aromatic diamine as described above are used, for example, dimethylformamide, dimethylacetamide, N.
A two-step method in which polyamic acid is synthesized by polycondensation in an amide solvent such as methylpyrrolidone, and then the polyamic acid is dehydrated and ring-closed by a thermal imidization method or a chemical imidization method, or At least one aromatic tetracarboxylic dianhydride and at least one aromatic diamine;
-Cresol, m-cresol, p-cresol, p-
A one-step method of producing a polyimide by heating and reacting in a phenol solvent such as chlorophenol can be mentioned, but the one-step method is preferable.

The proportion of tetracarboxylic dianhydride and diamine used in the synthesis of polyimide is usually 2/1 to
It is in the range of 1/2 (molar ratio). When one of the monomers is used in an excessive amount, it is possible to prepare a monomer having a relatively low molecular weight and a uniform type of functional groups at the molecular ends.

Examples of the phenolic solvent used in the above-mentioned synthesis include phenol, o-cresol, m-cresol, p-cresol, p-chlorophenol, etc., which have been mentioned above. From the economical viewpoint, m-cresol is particularly preferable.

The logarithmic viscosity [ηinh] of the polyimide thus obtained (measured with an Ubbelohde viscometer in m-cresol at 30 ° C. and a concentration of 0.5 g / dl) is:
Usually, 0.1 to 10.0 dl / g, preferably 0.3 to
3.0 dl / g, and glass transition temperature (measured by a dynamic viscoelasticity test at a heating rate of 4 ° C./min at 1 Hz).
Is usually 100 to 400 ° C., preferably 200 to 35
0 ° C.

Block Copolymer The method for producing a block copolymer of the present invention is characterized in that the molecular ends of the polyamide and the polyimide are subjected to a coupling reaction in a phenol solvent which is a common solvent for both. There is. As the production method, for example, a polyamide in which the types of functional groups at the molecular ends are unified beforehand and a polyimide in which the functional groups at the molecular ends are adjusted in advance so as to react with the molecular ends of the polyamide are heated in a phenolic solvent. Then, a method for producing a block copolymer by polycondensing the molecular ends, or a polyamide in which the types of functional groups at the molecular ends are standardized in advance and the proportion used to react with the molecular ends of the polyamide are adjusted. The method in which the tetracarboxylic dianhydride and the diamine are heated in a phenolic solvent to synthesize a polyimide segment and at the same time a block copolymer is produced. The above-mentioned solvents can be used as the phenolic solvent.

In the method for producing the block copolymer of the present invention, the reaction temperature is usually 80 to 180 ° C., and the polymerization time is
Usually, it is 15 minutes to 5 hours. The formation of the block copolymer can be confirmed by measuring the terminal functional group concentration and comparing the solution viscosity (logarithmic viscosity) of each segment with the viscosity of the obtained copolymer.

The thermal transition temperature relationship between the polyamide segment and the polyimide segment in the block copolymer of the present invention is as follows. When the polyamide segment is crystalline and the polyimide segment is crystalline, the melting point of the polyamide segment is lower than the melting point of the crystalline polyimide segment, and when the polyimide segment is amorphous, the melting point of the polyamide segment. Is a temperature lower than the glass transition temperature of the amorphous polyimide segment, and b. When the polyamide segment is amorphous and the polyimide segment is crystalline, the glass transition temperature of the polyamide segment is lower than the melting point of the crystalline polyimide segment, and when the polyimide segment is amorphous, the polyamide segment is The glass transition temperature of the segment is characterized by being lower than the glass transition temperature of the amorphous polyimide segment, and such a molecular design is preferable for exhibiting adhesive function when used as an adhesive. .

Among them, those having a crystalline polyamide segment and an amorphous polyimide segment structure are particularly preferable because they have a good balance between heat resistance and processability when used as an adhesive.

The block copolymer of the present invention does not require high-temperature heat treatment for thermal imidization of a polyamide / polyamic acid block copolymer, unlike the polyamide / polyimide block copolymers known so far. Yes, only heat treatment to evaporate the solvent is required. Further, since the imidization reaction is completed, there is an advantage that the processing problem that the amic acid component remains in the block copolymer and outgas is generated by the subsequent heat treatment can be solved. Furthermore, by adopting a polyamide soluble in phenolic solvents, dehalogenation, as is found in the solution of a polyamide / polyamic acid block copolymer, which is prepared from a conventionally known polyamide polymerization solution from carboxylic acid dihalide. It does not include ionic compounds consisting of hydrogen halides and acid acceptors associated with hydrogen reactions. Therefore, the obtained polymer thin film does not contain ionic impurities or compounds that cause corrosive properties, which are unfavorable for electronic material applications, and is extremely advantageous for preparing high-purity polymers.

Adhesive When the block copolymer of the present invention is used as an adhesive,
The adhesive comprises a polymer alloy containing the block copolymer of the present invention. Examples of the other polymer component include polyamide and polyimide, and the block copolymer of the present invention contains 1% by weight or more based on the total amount of the polymer component.
The content is preferably 3% by weight or more, and particularly preferably 5% by weight or more.

The adhesive may be used as a varnish (solution) or in the form of a film. When used as a varnish, apply the varnish to one adherend, remove the solvent by heating or reduced pressure to form a thin film,
It can be adhered by superposing it on the other body to be adhered and by thermocompression bonding. On the other hand, in the case of using it in the form of a film, it can be adhered by forming a film in advance, sandwiching the film between two adherends, and thermocompression bonding. As the adhesive, the film form is preferable because it does not cause shrinkage stress due to the removal of the solvent, and is suitable for adhesion of a thin material that is easily warped, and also because the processing time can be shortened.

The heating temperature under the processing conditions of the adhesive is in the temperature range from the heat transition temperature of the polyamide component to the heat transition temperature of the polyimide component, usually 50 to 3
Between 00 ° C.

When the block copolymer of the present invention is used for the adhesive, a polyimide segment excellent in heat resistance is formed in the molecule even though processing is facilitated by heating above the heat transition temperature of the polyamide segment. Since it is contained in, the adhesive layer does not flow, and it has excellent heat resistance.

Since it contains a polyamide segment having an excellent adhesive function, the adhesive force can be imparted by pressure-bonding at a relatively low pressure of 10 kg / cm ² or less, usually for 1 to 180 seconds. .

With respect to the adhesive, silica, alumina, titania,
Inorganic fillers such as glass, iron oxide, ceramics; add one or more usual additives such as antioxidants, heat stabilizers, UV absorbers, flame retardants, flame retardant aids, antistatic agents, lubricants, colorants, etc. be able to.

EXAMPLES The present invention will be described in more detail below with reference to examples. However, the present invention is not limited to these examples.

Example 1 A flask (internal volume 3 l) equipped with a stirrer and a nitrogen gas introducing tube was charged with 8% by weight of nylon 1
2 (grimamide L25 made by EMS) 750 g of m-cresol solution was added, and 653 g of m-cresol was further added, and then 10.74 g of pyromellitic dianhydride.
(49.2 mmol), 47.59 g of 3,3 ', 4,4'-benzophenone tetracarboxylic acid dianhydride (14
7.7 mmol) was added and the mixture was heated to 100 ° C. and stirred for 30 minutes to dissolve the monomer. Next, 9.77 g (48.8 mmo) of 4,4'-diaminodiphenyl ether
l), 4,4'-diaminodiphenylmethane 29.02
g (146.3 mmol) was added, the temperature was raised to 160 ° C., the mixture was stirred for 1 hour, and 12-nylon / polyimide = 4.
A 0/60 (weight ratio) block copolymer solution was obtained. The amino group of nylon-12 before the reaction was detected by neutralization titration, but the amino group was not detected after the reaction.
It was confirmed that the two components were introduced as the polyamide segment of the block copolymer. The logarithmic viscosity of the obtained block copolymer in m-cresol was 1.49.
It was dl / g (concentration; 0.5 g / dl, 30 ° C.).

The above block copolymer solution was applied onto a copper-clad laminate using a doctor blade, and m-cresol was removed by heating to obtain a copper-clad laminate having an adhesive thin film with a thickness of 10 μm. It was The adhesive thin film side of this copper-clad laminate was overlaid with a copper foil having a thickness of 35 μm and a width of 1 cm, and the temperature was 200 ° C. and the pressure was 3 kg / cm ² with a pressing machine.
And was pressure-bonded for 3 seconds to prepare an adhesion test piece. The peel strength of this adhesion test piece was measured according to JIS C6481 and found to be 2.1 kg / cm.

When the adhesive strength of this test piece was measured in an atmosphere of 150 ° C., the adhesive strength of 0.90 kg / cm was maintained. Furthermore, temperature 85 ℃, humidity 85
The peel strength after holding for 1 week under the condition of% RH was measured, and the peel strength of 0.90 kg / cm was maintained. Further, when the adhesion test piece was immersed in a solder bath at 260 ° C. for 10 seconds to evaluate the solder heat resistance, the copper plate and the copper foil were not separated, and no abnormality such as swelling was observed on the adhesion surface. . Further, an adhesive test piece was prepared under the same adhesive conditions except that a kapton (polyimide film manufactured by DuPont) film was used instead of the copper foil, and the peel strength was measured in the same manner. As a result, it was 0.64 kg / cm. It was
The results are shown in Table 1.

(Examples 2 to 4) A block copolymer solution was obtained in the same manner as in Example 1 except that the weight ratio of polyamide to polyimide was as shown in Table 1, and the same evaluation as in Example 1 was performed. I went. Table 1 shows the results.

Example 5 The block copolymer solution obtained in Example 1 was cast on a mold-released glass plate and the solvent was removed by heating to obtain a film having a thickness of 10 μm.

The obtained film was sandwiched between the copper surface of the copper-clad laminate and the copper foil, an adhesion test piece was prepared under the same adhesion conditions as in Example 1, and the peel strength was measured. Peel strength is 1.9
kg / cm.

Similarly, an adhesion test piece of copper-clad laminate-Kapton was prepared and the peel strength was measured.
It was 68 kg / cm. The results are shown in Table 1.

The film was sandwiched between a silicon chip having a size of 5 mm × 5 mm and a copper-clad laminate, and the temperature was set to 200 ° C.
When a load of 250 g was applied on the hot plate of No. 3 and pressure was applied for 10 seconds to prepare an adhesion test piece, and the shear adhesion strength was measured, it was 35 kg / cm ² .

[0041]

[Table 1] Composition Logarithmic viscosity Adhesive strength Example Polyamid / polyimid (dl / g) (kg / cm) (weight ratio) Copper foil copper foil film 1 (varnish coating type) 40/60 1.49 2.1 0.64 2 (〃) 60 / 40 1.44 2.4 0.48 3 (〃) 80/20 1.30 2.5 0.44 4 (〃) 20/80 1.35 1.4 0.26 5 (Film type) 40/60 1.49 1.9 0.68 (Comparative Example 1) Block obtained in Example 1 Polyamide and polyimide corresponding to the composition of the polyamide segment and the polyimide segment of the polymer were blended in m-cresol at a ratio of polyamide / polyimide = 40/60 (weight ratio). A copper-clad laminate-copper foil adhesion test piece was prepared in the same manner as in Example 5, and the peel strength was measured and found to be 0.53 kg / cm.

(Comparative Example 2) An adhesive test piece was prepared in the same manner as in Example 1 except that only the polyimide used in Comparative Example 1 was used, and the peel strength was measured. There was no Noh.

Comparative Example 3 An adhesive test piece was prepared and evaluated in the same manner as in Example 1 except that the polyamide 12-nylon used in Comparative Example 1 was used. Copper-clad laminate at room temperature-
The peel strength of the copper foil was 1.9 kg / cm, and the peel strength of the copper-clad laminate-Kapton was 2.0 kg / cm, which showed good adhesiveness. The peel strength decreased to 0.60 kg / cm. Also, the temperature is 85
The peel strength after holding for 1 week under the condition of ℃ and humidity of 85% RH has a large variation in the peel strength including the peeled test piece on the adhesive surface. The average of the five test pieces is 0.35 kg / c.
The peeling strength was m.

In the evaluation of solder heat resistance, abnormalities such as swelling were observed on the adhesive surface.

[0045]

INDUSTRIAL APPLICABILITY The novel polyamide / polyimide block copolymer soluble in the phenolic solvent of the present invention has excellent heat resistance, adhesiveness and processability, and is particularly useful as a heat resistant adhesive. In addition, it is useful for a wide range of applications such as covered electric wire materials, insulating materials, and molding materials.

Claims (2)

[Claims] 1. A block copolymer comprising a polyamide segment and a polyimide segment, which is soluble in a phenolic solvent, wherein the thermal transition temperature relationship between the polyamide segment and the polyimide segment is a. When the polyamide segment is crystalline and the polyimide segment is crystalline, the melting point of the polyamide segment is lower than the melting point of the crystalline polyimide segment, and when the polyimide segment is amorphous, the melting point of the polyamide segment. Is a temperature lower than the glass transition temperature of the amorphous polyimide segment, and b. When the polyamide segment is amorphous and the polyimide segment is crystalline, the glass transition temperature of the polyamide segment is lower than the melting point of the crystalline polyimide segment, and when the polyimide segment is amorphous, the polyamide segment is The block copolymer, wherein the glass transition temperature of the segment is lower than the glass transition temperature of the amorphous polyimide segment. 2. A polyamide soluble in a phenolic solvent and a tetracarboxylic dianhydride component and a diamine component in the phenolic solvent are mixed at a tetracarboxylic dianhydride / diamine molar ratio of 2/1 to 1/1 /. 2. A method of ligating each molecular end of a polyimide soluble in a phenolic solvent, which is obtained by a polyaddition condensation reaction so as to be 2, to a coupling reaction in the phenolic solvent. A method for producing the block copolymer described.