JPH09328612A - Heat-resistant resin composition excellent in processability and adhesiveness - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain a rein composition extremely improved in adhesiveness/ moldability and processability without damaging excellent heat resistance, by blending a polyimide with an imide oligomer. SOLUTION: This composition is obtained by blending (A) a polyimide prepared by using a tetracarboxylic acid dianhydride having 0.90-0.99 molar ratio based on 1mol of a diamine component as raw material monomers, having >=0.30dL/g and <=1.2dL/g logarithmic viscosity with (B) an imide oligomer obtained by using a tetracarboxylic acid dianhydride component having 0.70-0.85 molecular ratio based on 1mol of the diamine component as raw material monomers, having >=0.05dL/g and <0.3dL/g logarithmic viscosity in the ratio of 80-99.9wt.% of the component A and 20-0.1wt.% of the component B. A diamine of the formula, H2 N-R1 -NH2 (R1 is a group of formula I or II) is contained as the diamine component in the raw material monomers of the component A. Consequently, a molding/a film/a yarn excellent in heat resistance, mechanical strength, etc., are prepared.

Description

Detailed Description of the Invention

[0001]

TECHNICAL FIELD The present invention relates to a resin composition having excellent processability and adhesiveness.

[0002]

2. Description of the Related Art In addition to its high heat resistance, polyimide has excellent mechanical strength, dimensional stability, flame retardancy and electrical insulation. Therefore, it is conventionally used in the fields of electric / electronic equipment, aerospace equipment, transportation equipment and the like, and is expected to be widely used in various fields requiring heat resistance in the future. For this reason, polyimides exhibiting various excellent properties have been developed. However, conventional polyimides have merits and demerits in their performances, some have excellent heat resistance while poor workability, and some have been developed mainly for the purpose of improving workability, so heat resistance and solvent resistance The current situation is that it is inferior to the above.

[0003] For example, in J. Polym. Sci. Mac
romol. Rev. , 11, 161 (1976), formula (15) [Chemical Formula 12]:

[Chemical 12] Polyimide having a basic skeleton represented by (Dupont, Kapton, Vespel) has no clear glass transition temperature and is a resin excellent in heat resistance.
When used as a molding material, processing is difficult, and it is necessary to use a technique such as sinter molding. It also has high water absorption that affects dimensional stability, insulation, solder heat resistance, etc.
It may be a problem when used as an electronic component material.

Therefore, the applicants of the present invention have disclosed Japanese Patent Laid-Open No. 62-205.
In Japanese Patent No. 124, the formula (16) [Chemical Formula 13]:

Embedded image A polyimide having a repeating structural unit represented by This polyimide has a glass transition temperature (hereinafter referred to as Tg) of 260 ° C, a crystallization temperature of 310 to 340 ° C,
A resin having a crystal melting temperature of 367 to 385 ° C., which can be melt-molded despite its excellent heat resistance, and has excellent chemical resistance and solvent resistance. However, as for this resin, one having a high molecular weight had a poor melt flowability and was inferior in adhesiveness. For adhesion, see Proceedings, Sympo
C. in sium on Polymers for Electronics, Tokyo (1988).
As described by J. Lee, the general formula (17)
[Chemical formula 14]:

[0005]

Embedded image It has been found that this can be improved by copolymerizing the polysiloxane unit represented by the formula (1), but the moldability cannot be solved by this method.

[0006]

SUMMARY OF THE INVENTION An object of the present invention is to greatly improve the adhesiveness and moldability of a polyimide resin without impairing its good heat resistance.

[0007]

Means for Solving the Problems As a result of intensive studies for achieving the above-mentioned object, the present inventors have found that mixing an imide oligomer with a polyimide greatly improves moldability, and further improves the polyimide and / or Further, they have found that the inclusion of siloxane in the imide oligomer improves the adhesiveness, and completed the present invention.

That is, the present invention comprises the following configurations (A) to (C). (A) (a) A polyimide obtained by a polymerization reaction from a diamine component which is a raw material monomer and a tetracarboxylic dianhydride component, wherein the tetracarboxylic acid has a molar ratio of 0.90 to 0.99 with respect to 1 mol of the diamine component. A polyimide having an inherent viscosity of 0.30 dl / g or more and 1.2 dl / g or less obtained by using an acid dianhydride component as a raw material monomer, and (b) a diamine component and a tetracarboxylic acid dianhydride component which are raw material monomers. Is an imide oligomer obtained by a polymerization reaction, and has a logarithmic viscosity of 0.05 dl obtained by using as a raw material monomer a tetracarboxylic dianhydride component in a 0.70 to 0.85 molar ratio with respect to 1 mol of a diamine component. / C or more and less than 0.3 dl / g of imide oligomer (c) Polyimide 80-99.9
20 to 0.1% by weight of imide oligomer relative to% by weight
The resin composition is obtained by mixing at a ratio of, and (d) the diamine component among the raw material monomers of the polyimide is represented by the general formula (1):

H ₂ N--R ₁ --NH ₂ (1) (wherein R ₁

Embedded image Diamine χ ₁ mol% represented by

And general formula (2): H ₂ N—R ₂ —NH ₂ (2) (wherein R ₂ [Chemical 16] is

Embedded image A diamine χ ₂ mol% represented by a divalent group different from R ₁ selected from the group consisting of

And the general formula (3):

Embedded image (However, in the formula, n is 0 or a mixed value of integers from 0 to 20,

R ₃ [Chemical Formula 18] is

Embedded image Consists diamine chi ₃ mol% represented by a kind of divalent group selected from the group) consisting of, chi _1, chi ₂ and chi ₃ is the sum of 100, the following equation (I ): 0 ≤ χ ₂ / χ ₁ ≤ 99 ………………………… (I) and formula (II): 0 ≤ χ ₃ / (χ ₁ + χ ₂ + χ ₃ ) ≤ 0.1 ... ……… A non-negative real number that satisfies (II),

(E) Of the raw material monomers of the polyimide, the tetracarboxylic dianhydride component is

Embedded image Consisting of one or two tetracarboxylic dianhydrides selected from the group consisting of

(F) Among the raw material monomers of the imide oligomer, the diamine component is represented by the general formula (4): H ₂ N—R ′ ₁ —NH ₂ (4) (In the formula, R ′ ₁ [Chemical Formula 20] is

Embedded image Diamine chi _'1 mol% represented by the a),

And general formula (5): H ₂ N—R ′ ₂ —NH ₂ (5) (wherein R ′ ₂ [Chemical Formula 21] is

[Chemical 21] Selected from the group consisting of the R _'1 is different from divalent a group) represented by diamine χ is' ₂ mol%

And the general formula (6) [Chemical Formula 22]:

Embedded image (In the formula, n is 0 or a mixed value of integers from 0 to 20,

[0017] R _'3 [of 23] is

Embedded image 'Consists _{of three} mol%, chi' diamine chi represented a kind of a divalent group) selected from the group consisting of _1, chi _'2 and chi' ₃ is the sum of 100, following Formula (III): 0 ≦ χ ′ ₂ / χ ′ ₁ ≦ 99 (III) and Formula (IV): 0 ≦ χ ′ ₃ / (χ ′ ₁ + χ ′ ₂ + χ ' ₃ ) <1 ……… (IV) is a non-negative real number,

(G) Of the raw material monomers of the imide oligomer, the tetracarboxylic dianhydride component is

Embedded image A resin composition comprising one or two tetracarboxylic acid dianhydrides selected from the group consisting of:

(B) A resin composition obtained by mixing the resin composition described above in an amount of 20 to 3% by weight of an imide oligomer with respect to 80 to 97% by weight of a polyimide.

(C) When synthesizing the polyimide and / or imide oligomer described in (A) or (B), the compound represented by the general formula (7):

Embedded image (Wherein, Z has 6 to 15 carbon atoms and is a monocyclic aromatic group,
An aromatic group represented by a condensed polycyclic aromatic group and a divalent group selected from the group consisting of non-condensed polycyclic aromatic groups in which aromatic groups are directly or linked to each other by a bridge member) A resin composition according to (A) or (B), characterized in that a polyimide and / or a polyimide oligomer containing one in which a polyimide and / or a polyimide oligomer molecule end is blocked is made to coexist with a dicarboxylic acid anhydride. is there.

[0021]

BEST MODE FOR CARRYING OUT THE INVENTION The present invention preferably includes the following (D) to
It can be implemented with the configuration of (N). (D) A diamine represented by the general formula (1) among the diamine components of the raw material monomer of the polyimide described in (A) or (B), and the raw material monomer of the imide oligomer described in (A) or (B). General formula (4) among diamine components
The diamines represented by both are represented by the formula (8):

[0022]

[Chemical formula 26] The resin composition according to (A) or (B), which is a diamine represented by:

(E) General formula (1) among the diamine components of the raw material monomer of the polyimide described in (A) or (B)
And the diamine represented by the general formula (4) among the diamine components of the raw material monomer of the imide oligomer described in (A) or (B), the diamine represented by the formula (8) A diamine represented by the general formula (2) among the diamine components of the raw material monomer of the polyimide described in (A) or (B), and the raw material monomer of the imide oligomer described in (A) or (B). Among the diamine components, the diamine represented by the general formula (5) is represented by the formula (9):

[0024]

Embedded image And a diamine represented by (A) or (B)
The tetracarboxylic dianhydride component of the raw material monomer of the polyimide described above and the tetracarboxylic dianhydride component of the raw material monomer of the imide oligomer described in (A) or (B) are both represented by the formula (10). [Chemical formula 28]:

[0025]

Embedded image And / or formula (11) [Chemical formula 29]:

[0026]

[Chemical 29] Consisting of a tetracarboxylic dianhydride represented by (A)
Alternatively, the resin composition according to (B).

(F) The diamine component of the raw material monomer of the polyimide described in (A) or (B) and the diamine component of the raw material monomer of the imide oligomer described in (A) or (B) respectively have the formula (8). And the diamine represented by the general formula (3) described in (A) or (B), and the diamine represented by the formula (8) and the general formula (6) described in (A) or (B). And a tetracarboxylic dianhydride component among the raw material monomers of the polyimide described in (A) or (B),
And (A) or (B), the tetracarboxylic acid dianhydride component of the raw material monomer of the imide oligomer is composed of only the tetracarboxylic acid dianhydride represented by the formula (10). Alternatively, the resin composition according to (B).

(G) General formula (1) among the diamine components of the raw material monomer of the polyimide described in (A) or (B)
And the diamine represented by the general formula (4) among the diamine components of the raw material monomer of the imide oligomer described in (A) or (B), the diamine represented by the formula (12)
[Chemical Formula 30]:

[0029]

Embedded image The resin composition according to (A) or (B), which is a diamine represented by:

(H) Of the diamine component of the raw material monomer of the polyimide described in (A) or (B), the general formula (1)
And the diamine represented by the general formula (4) among the diamine components of the raw material monomer of the imide oligomer described in (A) or (B), the diamine represented by the formula (12)
A diamine represented by the general formula (2) among the diamine components of the raw material monomer of the polyimide described in (A) or (B), and (A) or (B)
Among the diamine components of the raw material monomer of the imide oligomer described above, the diamine represented by the general formula (5) is both a diamine represented by the formula (9), and (A) or (B) The tetracarboxylic acid dianhydride component of the raw material monomer of the polyimide and the tetracarboxylic acid dianhydride component of the raw material monomer of the imide oligomer described in (A) or (B) are both represented by the formula (10) and the formula (1
1) and formula (13)

[0031]

[Chemical 31] The resin composition according to (A) or (B), which comprises one or two tetracarboxylic acid dianhydrides selected from the group consisting of:

(I) Of the diamine component of the raw material monomer of the polyimide described in (A) or (B), the general formula (3)
And the diamine represented by the general formula (6) among the diamine components of the raw material monomer of the imide oligomer described in (A) or (B) are both represented by the formula (14)
[Chemical Formula 32]:

[0033]

Embedded image The resin composition according to (A) or (B), which is a diamine represented by:

(J) General formula (1) among the diamine components of the raw material monomer of the polyimide described in (A) or (B)
And the diamine represented by the general formula (4) among the diamine components of the raw material monomer of the imide oligomer described in (A) or (B), the diamine represented by the formula (8) The resin composition according to (I), which is

(K) General formula (1) among the diamine components of the raw material monomer of the polyimide described in (A) or (B)
And the diamine represented by the general formula (4) among the diamine components of the raw material monomer of the imide oligomer described in (A) or (B), the diamine represented by the formula (8) A diamine represented by the general formula (2) among the diamine components of the raw material monomer of the polyimide described in (A) or (B), and the raw material monomer of the imide oligomer described in (A) or (B). Among the diamine components, the diamine represented by the general formula (5) is a diamine represented by the formula (9), and tetracarboxylic acid among the raw material monomers of the polyimide described in (A) or (B). Among the raw material monomers of the imide oligomer described in (A) or (B), the tetracarboxylic dianhydride component is represented by the formula (10) and / or the formula (11). That consists of tetracarboxylic acid dianhydride, (I) a resin composition.

(L) The diamine component of the raw material monomer of the polyimide described in (A) or (B) and the diamine component of the raw material monomer of the imide oligomer described in (A) or (B) are both represented by the formula (8) ) And a diamine represented by the formula (14) described in (A) or (B), and a tetracarboxylic acid among the raw material monomers of the polyimide described in (A) or (B). Of the dianhydride component and the raw material monomer of the imide oligomer described in (A) or (B), the tetracarboxylic dianhydride component is composed of only the tetracarboxylic dianhydride represented by the formula (10). The resin composition according to (J).

(M) Of the diamine component of the raw material monomer of the polyimide described in (A) or (B), the general formula (1)
And the diamine represented by the general formula (4) among the diamine components of the raw material monomer of the imide oligomer described in (A) or (B), the diamine represented by the formula (12)
The resin composition according to (I), which is a diamine represented by:

(M) Of the diamine component of the raw material monomer of the polyimide described in (A) or (B), the general formula (1)
And the diamine represented by the general formula (4) among the diamine components of the raw material monomer of the imide oligomer described in (A) or (B), the diamine represented by the formula (12)
A diamine represented by the general formula (2) among the diamine components of the raw material monomer of the polyimide described in (A) or (B), and (A) or (B)
Among the diamine components of the raw material monomer of the imide oligomer described above, the diamine represented by the general formula (5) is both a diamine represented by the formula (9), and (A) or (B) The tetracarboxylic acid dianhydride component of the raw material monomer of the polyimide and the tetracarboxylic acid dianhydride component of the raw material monomer of the imide oligomer described in (A) or (B) are both represented by the formula (10) and the formula (1
1) The resin composition according to (I), which comprises one or two tetracarboxylic dianhydrides selected from the group consisting of [and formula (13).

The polyimide and imide oligomer contained in the resin composition of the present invention can be manufactured by almost the same method. To produce the polyimide contained in the resin resin composition of the present invention, a diamine represented by the general formula (1) and, if necessary, the diamine represented by the general formula (2), Further, the general formula (3)
A diamine represented by

[0040]

[Chemical 33] One or two tetracarboxylic dianhydrides selected from the group consisting of may be mixed in a predetermined amount and heated and melted, but particularly preferably, the reaction is carried out in an organic solvent.

Examples of the organic solvent used at this time include N, N-dimethylformamide, N, N-dimethylacetamide, N, N-diethylacetamide, N, N.
-Dimethylmethoxyacetamide, N-methyl-2-pyrrolidone, 1,3-dimethyl-2-imidazolidinone,
N-methylcaprolactam, 1,2-dimethoxyethane-bis (2-methoxyethyl) ether, 1,2-bis (2-methoxyethoxy) ethane, bis [2- (2-methoxyethoxy) ethyl] ether, tetrahydrofuran, 1,3-dioxane, 1,4-dioxane, xylene, pyridine, picoline, dimethyl sulfoxide, dimethyl sulfone, tetramethylurea, hexamethylphosphoramide, phenol, o-cresol, m-cresol, p-cresol, m- Examples include cresylic acid, p-chlorophenol, and anisole. These organic solvents may be used alone or in combination of two or more.

Also in the present invention, there is no problem even if an organic base catalyst, which is usually used when synthesizing a polyimide, coexists. As the organic base catalyst, triethylamine,
Tributylamine, tripentylamine, N, N-dimethylaniline, N, N-diethylaniline, pyridine,
α-picoline, β-picoline, γ-picoline, 2,4-
Examples thereof include lutidine, 2,6-lutidine, quinoline, and isoquinoline, and preferred examples thereof include pyridine and γ-picoline.

When the polyimide is produced, the reaction can be carried out in an organic solvent by any known method. That is, 1) by mixing each monomer in an organic solvent to synthesize a polyamic acid and removing the solvent at a low temperature using a method such as distillation under reduced pressure, or by discharging the obtained polyamic acid solution to a poor solvent. A method in which a polyamic acid is isolated and then heated to imidize to obtain a polyimide. 2) After preparing a polyamic acid solution in the same manner as in 1),
A method in which a dehydrating agent typified by acetic anhydride is added, and a catalyst is added as necessary to chemically imidize, and then a polyimide is isolated by a known method, followed by washing and drying as necessary. 3) A method in which a polyamic acid solution is obtained in the same manner as in 1), and then the solvent is removed by decompression or heat treatment, and at the same time, thermal imidization is performed. 4) A method in which a raw material is charged into an organic solvent, and then heated to simultaneously perform synthesis of a polyamic acid and an imidization reaction, and a catalyst, an azeotropic agent, and a dehydrating agent, if necessary. And the like.

When the polyimide is polymerized, the general formula (7) [Chemical Formula 34]:

Embedded image (Wherein, Z has 6 to 15 carbon atoms and is a monocyclic aromatic group,
An aromatic group represented by a condensed polycyclic aromatic group and a divalent group selected from the group consisting of non-condensed polycyclic aromatic groups in which aromatic groups are directly or linked to each other by a bridge member) A dicarboxylic acid anhydride can be made to coexist to obtain a polyimide containing a polyimide molecule terminal blocked.

As a method of coexisting the aromatic dicarboxylic acid anhydride represented by the general formula (7), (a) the tetracarboxylic acid dianhydride and the diamine are reacted, and then the dicarboxylic acid anhydride is added. To continue the reaction. (B) A method in which a dicarboxylic acid anhydride is added to a diamine to cause a reaction, and then a tetracarboxylic acid dianhydride is added to continue the reaction. (C) A method in which a tetracarboxylic acid dianhydride, a diamine and a dicarboxylic acid anhydride are simultaneously added to react. There is no problem using either method.

Examples of the aromatic dicarboxylic acid anhydride represented by the general formula (7) used at this time include phthalic anhydride, 2,3-benzophenone dicarboxylic acid anhydride and 3,4-benzophenone dicarboxylic acid anhydride. Thing 2,
3-dicarboxyphenyl phenyl ether acid anhydride, 3,4-dicarboxyphenyl phenyl ether acid anhydride, 2,3-biphenyl dicarboxylic acid anhydride,
3,4-biphenyldicarboxylic acid anhydride, 2,3-dicarboxyphenylphenylsulfone acid anhydride, 3,4
-An acid anhydride of dicarboxyphenyl phenyl sulfone,
2,3-dicarboxyphenyl phenyl sulfide acid anhydride, 3,4-dicarboxyphenyl phenyl sulfide acid anhydride, 1,2-naphthalene dicarboxylic acid anhydride, 2,3-naphthalene dicarboxylic acid anhydride, 1, 8-
Examples thereof include naphthalene dicarboxylic acid anhydride, 1,2-anthracene dicarboxylic acid anhydride, 2,3-anthracene dicarboxylic acid anhydride, and 1,9-anthracene dicarboxylic acid anhydride. Of these aromatic dicarboxylic anhydrides, phthalic anhydride is most preferred from the viewpoint of the performance and practicality of the resin from which phthalic anhydride is obtained.

The polyimide contained in the resin composition of the present invention can be produced by the above method, and the imide oligomer contained in the resin composition of the present invention can be produced by the same method. That is, it can be produced in exactly the same manner as above, using a predetermined amount of each monomer used in producing the oligomer.

The amount of each monomer used in the production of the polyimide contained in the resin composition of the present invention is ₁ mol of the amount of the diamine represented by the general formula (1), and the general formula (2) is used. The amount of the diamine represented by the formula is x ₂ mol, the amount of the diamine represented by the general formula (3) is x ₃ mol, and the total molar amount of the tetracarboxylic acid anhydride component used is y mol. , Formula (V), formula (VI) and formula (VI
I): 0 ≦ x ₂ / x ₁ ≦ 99 ………………………………… (V) 0 ≦ x ₃ / (x ₁ + x ₂ + x ₃ ) <0.1 ………… ( VI) in the range satisfying _{0.90 ≦ y / (x 1 +} x 2 + x 3) ≦ 0.99 ..................... the (VII) all.

The above formula (V) limits the structure and constitution of the diamine component used in the present invention. That is, the diamine having the structure of the general formula (1) is indispensable for the diamine component of the present invention.
The diamine of the general formula (2) can be added in a molar ratio range up to twice. If it deviates from this range, the mechanical properties and molding processability inherent to the resin and other excellent physical properties may be lost. This range is more preferably the following formula: 0 ≦ x ₂ / x ₁ ≦ 49, and most preferably the following formula: 0 ≦ x ₂ / x ₁ ≦ 19.

The above formula (VI) shows the upper and lower limits of the amount of the siloxane-containing diamine represented by the above general formula (3). The siloxane-containing diamine is effective in improving the adhesiveness, and when it is excessive, the mechanical properties and heat resistance inherent to the resin are lost. This range is more preferably the following formula: 0.0005 ≦ x ₃ / (x ₁ + x ₂ + x ₃ ) ≦ 0.09, and most preferably the following formula: 0.001 ≦ x ₃ / (x ₁ + x ₂ + x ₃ ) ≦ 0.08.

The above formula (VII) shows the range of the value of the ratio of the diamine component to the acid anhydride component. If it deviates from this molar ratio range, mechanical properties and heat resistance will deteriorate. This range is more preferably the following formula: 0.91 ≦ y / (x ₁ + x ₂ + x ₃ ) ≦ 0.99, and most preferably the following formula: 0.92 ≦ y / (x ₁ + x ₂ + x ₃ ) ≦ 0.985.

[0052] The amount of each monomer in the production of the imide oligomer contained in the resin composition of the present invention, x _'1 mole the amount of the diamine represented by general formula (4), the general formula ( x _'2 moles the amount of diamine represented by 5),
X the amount of diamine represented by the general formula (6) _'3 mol, the total molar amount y of the tetracarboxylic acid anhydride component used' mole, and when, (VIII), (IX), And formula (X): 0 ≦ x ′ ₂ / x ′ ₁ ≦ 99 (VIII) 0 ≦ x ′ ₃ / (x ′ ₁ + x ′ ₂ + x ′ ₃ ) <1. ……………… (IX) 0.70 ≦ y ′ / (x ′ ₁ + x ′ ₂ + x ′ ₃ ) ≦ 0.85 ……… (X).

The above formula (VIII) limits the structure and constitution of the diamine component used in the present invention. That is, the diamine having the structure of the general formula (4) is indispensable for the diamine component of the present invention.
The diamine of the general formula (5) can be added in a molar ratio range up to twice. If it deviates from this range, the mechanical properties and molding processability inherent to the resin and other excellent physical properties may be lost. This range is more preferably the following formula: 0 ≦ x ′ ₂ / x ′ ₁ ≦ 49, and most preferably the following formula: 0 ≦ x ′ ₂ / x ′ ₁ ≦ 19.

The above formula (IX) represents the lower limit of the amount of the siloxane-containing diamine represented by the above general formula (6). The siloxane-containing diamine has an effect of improving adhesiveness. This range is more preferably the following formula: 0.0005 ≦ x ′ ₃ / (x ′ ₁ + x ′ ₂ + x ′ ₃ ) <1, and most preferably the following formula: 0.001 ≦ x ′ ₃ / (x ′ ₁ + x ' ₂ + x' ₃ ) <1.

Further, the above formula (X) shows the range of the value of the ratio of the diamine component and the acid anhydride component. If the molar ratio is out of this range, the moldability, mechanical properties and heat resistance will deteriorate.
Further, this range is more preferably the following formula: 0.71 ≤ y '/ (x' ₁ + x ' ₂ + x' ₃ ) ≤ 0.845, and most preferably the following formula: 0.72 ≤ y '/ (x _{'1 + x' 2 + x} '3) is ≦ 0.84.

The resin composition of the present invention comprises polyimides 80 to 9
Imide oligomer 20-0.1 based on 9.9% by weight
The resin composition is obtained by mixing in a proportion of 80% by weight, preferably 80 to 97% by weight of polyimide and 20 to 3% by weight of imide oligomer. If the imide oligomer is added in excess of this range, the mechanical properties and heat resistance will decrease, and if it is less than this range, the effect of improving melt fluidity will be insufficient.

The aromatic dicarboxylic acid anhydride represented by the above general formula (7), which can be added for the purpose of blocking the end of the polymer chain when the polyimide contained in the resin composition of the present invention is produced. The amount used (in terms of z mol) is x (x = x ₁ + x ₂ +
x ₃ ) mol, where y mol is the total molar amount of the tetracarboxylic dianhydride used, the following formula: (x−y) × 2 × 0.2 ≦ z ≦ (x−y) × 2 It is preferably in the range represented by × 5.0. Further, it is more preferably a range represented by the following formula: (x−y) × 2 × 0.5 ≦ z ≦ (x−y) × 2 × 4.0, and most preferably the following formula: (x− y) × 2 × 0.7 ≦ z ≦ (x−y) × 2 × 3.0. If the aromatic dicarboxylic acid anhydride is used in a larger amount than this range, the mechanical properties are deteriorated, and if it is less than the molar ratio range, the thermal stability becomes poor and the workability is deteriorated.

An aromatic dicarboxylic acid anhydride represented by the general formula (7), which can be added for the purpose of blocking the end of the polymer chain when producing the imide oligomer contained in the resin composition of the present invention. Amount used (z 'mol)
Is the total molar amount of the diamine component used, x '(x' =
_{x '1 + x' 2 +} x when _'3) moles, the total molar amount of the tetracarboxylic dianhydride used y' and moles, and the following formula: (x '-y') × 2 × 0.2 ≤z '≤ (x'-y') ×
It is preferably in the range represented by 2 × 5.0. Further, more preferably, the following formula: (x'-y ') x 2 x 0.5 ≤ z' ≤ (x'-y ') x
It is a range represented by 2 × 4.0, and most preferably the following formula: (x′−y ′) × 2 × 0.7 ≦ z ′ ≦ (x′−y ′) ×
It is a range represented by 2 × 3.0. If the aromatic dicarboxylic acid anhydride is used in a larger amount than this range, the mechanical properties are deteriorated, and if it is less than the molar ratio range, the thermal stability becomes poor and the workability is deteriorated.

When the polymer (polyimide) or oligomer (imide oligomer) used in the present invention is polymerized by the above production method, a part of the diamine and tetracarboxylic acid dianhydride groups used as monomers is used in the method of the present invention. Other diamines and tetracarboxylic acid dianhydrides can be replaced with other diamines and tetracarboxylic acid dianhydrides, respectively, as long as they do not impair the excellent physical properties of.

As a diamine compound used as a partial substitute, a diamine represented by the general formula (18): H ₂ N—R—NH ₂ (18) is used. Specifically, R is an aliphatic group; ethylenediamine, 1,4-diaminobutane, etc .; R is a cycloaliphatic group; 1,4-diaminocyclohexane, etc., R is a monocyclic aromatic group. Yes; m-phenylenediamine,
o-phenylenediamine, p-phenylenediamine, m
-Aminobenzylamine, p-aminobenzylamine,
Diaminotoluene, etc., R is a condensed polycyclic aromatic group; 2,6-diaminonaphthalene, etc., R is a non-condensed cyclic aromatic group in which an aromatic group is directly linked; 4,4'-diaminobiphenyl , 4,3′-diaminobiphenyl, etc.,

R is a non-fused cyclic aromatic group in which aromatic groups are linked by a bridging member; 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- (4-aminophenoxy) phenyl] methane, 1,1-bis [4- (4-aminophenoxy) phenyl] ethane, 1,2-bis [4 -(4-Aminophenoxy) phenyl] ethane, 1,1-bis [4
-(4-aminophenoxy) phenyl] propane, 1,
2-bis [4- (4-aminophenoxy) phenyl] propane, 1,3-bis [4- (4-aminophenoxy)
Phenyl] propane, 2,2-bis [4- (4-aminophenoxy) phenyl] propane, 1,1-bis [4-
(4-aminophenoxy) phenyl] butane,

1,2-bis [4- (4-aminophenoxy) phenyl] butane, 1,3-bis [4- (4-aminophenoxy) phenyl] butane, 1,4-bis [4-]
(4-Aminophenoxy) phenyl] butane, 2,2-
Bis [4- (4-aminophenoxy) phenyl] butane, 2,3-bis [4- (4-aminophenoxy) phenyl] butane, 2- [4- (4-aminophenoxy) phenyl] -2- [4 -(4-aminophenoxy) -3-
Methylphenyl] propane, 2,2-bis [4- (4-
Aminophenoxy) -3-methylphenyl] propane,
2- [4- (4-aminophenoxy) phenyl] -2-
[4- (4-aminophenoxy) -3,5-dimethylphenyl] propane, 2,2-bis [4- (4-aminophenoxy) -3,5-dimethylphenyl] propane,
2,2-bis [4- (4-aminophenoxy) phenyl] -1,1,1,3,3,3-hexafluoropropane, 1,3-bis (3-aminophenoxy) benzene,
1,3-bis (4-aminophenoxy) benzene, 1,
4-bis (3-aminophenoxy) benzene, 1,4-
Bis (4-aminophenoxy) benzene, 4,4′-bis (4-aminophenoxy) biphenyl, bis [4-
(4-Aminophenoxy) phenyl] ketone, bis [4
-(4-Aminophenoxy) phenyl] sulfide, bis [4- (4-aminophenoxy) phenyl] sulfoxide, bis [4- (4-aminophenoxy) phenyl]
Sulfone, bis [4- (3-aminophenoxy) phenyl] ether, bis [4- (4-aminophenoxy) phenyl] ether, 1,3-bis [4- (4-aminophenoxy) benzoyl] benzene, 1,3-bis [4-
(3-Aminophenoxy) benzoyl] benzene, 1,
4-bis [4- (4-aminophenoxy) benzoyl]
Benzene, 1,4-bis [4- (3-aminophenoxy) benzoyl] benzene, 4,4′-bis (3-aminophenoxy) benzoyl] benzene, 4,4′-bis (3-aminophenoxy) -3 , 3'-dimethylbiphenyl, 4,4'-bis (3-aminophenoxy) -3,
5-dimethylbiphenyl,

4,4'-bis (3-aminophenoxy)
-3,3 ', 5,5'-tetramethylbiphenyl, 4,
4'-bis (3-aminophenoxy) -3,3'-dichlorobiphenyl, 4,4'-bis (3-aminophenoxy) -3,3 ', 5,5'-tetrachlorobiphenyl,
4,4'-bis (3-aminophenoxy) -3,5-dibromobiphenyl, 4,4'-bis (3-aminophenoxy) -3,3 ', 5,5'-tetrabromobiphenyl, bis [4 -(3-aminophenoxy) -3-methoxyphenyl] sulfide, [4- (3-aminophenoxy) phenyl] [4- (3-aminophenoxy) -3,
5-dimethoxyphenyl] sulfide, bis [4- (3
-Aminophenoxy) -3,5-dimethoxyphenyl]
Sulfide, 1,1-bis [4- (3-aminophenoxy) phenyl] propane, 1,3-bis [4- (3-aminophenoxy) phenyl] propane, 2,2-bis [4- (3-amino) Phenoxy) phenyl] propane,
2,2-bis [4- (3-aminophenoxy) phenyl] -1,1,1,3,3,3-hexafluoropropane, 4,4′-bis (3-aminophenoxy) biphenyl, bis [4 -(3-Aminophenoxy) phenyl] ketone, bis [4- (3-aminophenoxy) phenyl]
Sulfide, 1,3-bis [4- (4-aminophenoxy) -α, α-dimethylbenzyl] benzene, bis [4
-(3-aminophenoxy) phenyl] sulfone and the like can be mentioned.

The tetracarboxylic dianhydride used as a partial substitute is represented by the general formula (19):

Embedded image The tetracarboxylic dianhydride represented by is used. In particular,

R'is an aliphatic group; butanetetracarboxylic dianhydride, etc., R'is a cycloaliphatic group; cyclopentanetetracarboxylic dianhydride, cyclohexanetetracarboxylic dianhydride, etc. R'is a monocyclic aromatic group; 1,2,3,4-benzenetetracarboxylic dianhydride, etc., R'is a condensed polycyclic aromatic group; 2,3,6,7- Naphthalenetetracarboxylic dianhydride, 1,4,5,8-
Naphthalenetetracarboxylic dianhydride, 1,2,5,6
-Naphthalenetetracarboxylic dianhydride, 3,4,9,
10-perylene tetracarboxylic dianhydride, 2,3
6,7-anthracene tetracarboxylic dianhydride, 1,
2,7,8-phenanthrenetetracarboxylic acid dianhydride and the like, R'is a non-fused cyclic aromatic group in which an aromatic group is directly linked; 3,3 ', 4,4'-biphenyltetracarboxylic acid dianhydride Anhydride, 2,2 ', 3,3'-biphenyltetracarboxylic dianhydride, etc.,

R'is a non-fused cyclic aromatic group in which aromatic groups are linked by a bridging member; 3,3 ', 4,4'-benzophenonetetracarboxylic dianhydride, 2,2', 3,3
3'-benzophenone tetracarboxylic acid dianhydride, 2,
2-bis (3,4-dicarboxyphenyl) propane dianhydride, 2,2-bis (2,3-dicarboxyphenyl) propane dianhydride, bis (2,3-dicarboxyphenyl) ether dianhydride , Bis (3,4-dicarboxyphenyl) ether dianhydride, bis (2,3-dicarboxyphenyl) sulfone dianhydride, bis (3,4-dicarboxyphenyl) sulfone dianhydride, bis (2 3
-Dicarboxyphenyl) methane dianhydride, bis (3,
4-dicarboxyphenyl) methane dianhydride, 1,1-
Bis (2,3-dicarboxyphenyl) ethane dianhydride, 1,1-bis (3,4-dicarboxyphenyl) ethane dianhydride, 1,2-bis (2,3-dicarboxyphenyl) ethane dianhydride Anhydride, 1,2-bis (3,4-dicarboxyphenyl) ethane dianhydride, 1,3-bis (2,3-dicarboxyphenoxy) benzene dianhydride, 1,3-bis (3,4 -Dicarboxyphenoxy)
Benzene dianhydride, 1,4-bis (2,3-dicarboxyphenoxy) benzene dianhydride, 1,4-bis (3,
4-dicarboxyphenoxy) benzene dianhydride, 2,
2'-bis [4- (3,4-dicarboxyphenoxy)
Examples thereof include phenyl] propane dianhydride and bis [4- (3,4-dicarboxyphenoxy)] biphenyl dianhydride.

The logarithmic viscosity of the polymer (polyimide) used in the present invention is 0.3 considering mechanical properties and processability.
dl / g or more and 1.2 dl / g or less, preferably 0.3
It is 2 dl / g or more and 1.1 dl / g or less, more preferably 0.35 dl / g or more and 1.0 dl / g or less.
The logarithmic viscosity of the oligomer (imide oligomer) used in the present invention is 0.05 dl / g or more and less than 0.30 dl / g, preferably 0.06 dl / g or more and 0.30 dl considering mechanical properties and melt fluidity improving effects. It is less than / g. The logarithmic viscosity can be measured with a mixed solvent of p-chlorophenol and phenol (90:10 weight ratio).

If necessary, additives can be added to the resin composition of the present invention within a range that does not impair the various physical properties of the resin composition of the present invention. For example, as the thermoplastic resin, polyethylene, polyester, polypropylene, polycarbonate, polysulfone, polyethersulfone, polyetherketone, polyphenylene sulfide, polyamide, polyimide, polyamideimide, polyetherimide, modified polyphenylene oxide and the like as a main component And those obtained by copolymerizing two or more kinds of these thermoplastic resins.

As the filler, a wear resistance improver such as fluororesin, graphite, carborundum, silica powder, molybdenum disulfide, carbon fiber, graphite, glass fiber, carbon fiber, boron fiber, silicon carbide fiber. , Carbon whiskers, asbestos, metal fibers, reinforcing agents such as ceramic fibers, antimony trioxide, magnesium carbonate,
Flame retardant improver such as calcium carbonate, electrical property improver such as clay and mica, tracking resistance improver such as asbestos, silica and graphite, acid resistance improver such as barium sulfate, silica and calcium metasilicate, iron powder , Zinc powder,
Thermal conductivity improvers such as aluminum powder, copper powder and other metal powders, various crystallization rate accelerators or crystallization rate inhibitors, various compatibilization accelerators, other, glass beads, glass spheres, talc, diatomaceous earth , Alumina, silica balun, hydrated alumina, metal oxides, coloring agents, and the like. Any number of the above additives can be added as needed.

Further, in the present invention, the means for mixing the raw materials such as the polymer (polyimide) and the oligomer (imide oligomer) and the additives added as necessary is not particularly limited, and the raw materials are individually melt-mixed. Any method may be used, such as a method of supplying to the above, a method of using a general-purpose mixer such as a Henschel mixer, a ball mixer, and a ribbon blender.

The resin composition of the present invention is excellent not only in processability but also in excellent adhesion to various mating materials. For this reason, it is particularly useful as an adhesive for the production of circuit boards and the like. Although the bonding method is not limited, for example, it can be performed by the following methods a) to c). a) A method in which a powder of the resin composition produced by the method of the present invention is evenly dispersed on an adhesive surface, and the powder is adhered by applying heat and pressure. b) After dissolving or suspending the resin composition produced by the method of the present invention in a solvent and uniformly applying the mixture on the adhesive surface,
A method in which the solvent is removed by heating or drying under reduced pressure and then bonded by heating and pressurizing, or a method in which the solvent is removed by heating and pressurizing while simultaneously removing the solvent. c) A method in which the resin composition produced by the method of the present invention is formed into a film by a method such as extrusion, and is bonded by heating and pressing.

The heating temperature at the time of heating / pressurizing described in each of the above methods is from 100 ° C to 420 ° C, preferably from 150 ° C.
It is 400 ° C. Further, the bonding pressure is not limited, but is preferably in the range of 0.1 to 1000 kg / cm ² . The method of heating and pressurizing is not limited, either. For example, a known method such as a hot press, a hot roll, a double belt press, an autoclave, or induction heating by high frequency is used. After heating and pressurizing, if cured under the condition of 150 ° C. to 400 ° C., it is possible to adhere more firmly.

As a method of applying the powder in the above method a), a method such as electrostatic charging is used. Further, the solvent used in the above method b) is not limited, but examples of the solvent to be used after being dissolved include N, N-dimethylformamide, N, N-dimethylacetamide, N, N-diethyl. Acetamide,
N, N-dimethylmethoxyacetamide, N-methyl-
2-pyrrolidone, 1,3-dimethyl-2-imidazolidinone, N-methylcaprolactam, 1,2-dimethoxyethane-bis (2-methoxyethyl) ether, 1,2
-Bis (2-methoxyethoxy) ethane, bis [2-
(2-Methoxyethoxy) ethyl] ether, tetrahydrofuran, 1,3-dioxane, 1,4-dioxane, xylene, pyridine, picoline, dimethyl sulfoxide, dimethyl sulfone, tetramethylurea, hexamethylphosphoramide, phenol, o- Cresol, m
-Cresol, p-cresol, m-cresylic acid, p
-Chlorophenol, anisole and the like. Further, as the solvent used by suspending, in addition to the above, water,
Common solvents such as acetone, methanol, ethanol, propyl alcohol, benzene and toluene are used. These organic solvents may be used alone or in combination of two or more.

The method of forming a film in the above-mentioned method c) is not limited, but for example, a method of forming a film by extrusion after pelletizing, a method of forming a film by casting after dissolving in a solvent, Etc. In addition to the above, the resin composition of the present invention is also excellent in heat resistance, chemical resistance, mechanical strength, electrical properties, solvent resistance, water absorption rate, moisture resistance, and radiation resistance, and therefore can be used in various applications.

[0075]

The present invention will be described below in detail with reference to examples and comparative examples. The test methods for various tests in Examples and Comparative Examples are as follows. 1) Logarithmic viscosity 0.50 g of a sample was heated and dissolved in 100 ml of a mixed solvent of p-chlorophenol and phenol (90:10 weight ratio), and then cooled to 35 ° C and measured. 2) Melt viscosity enhancement type flow tester (CFT-50 manufactured by Shimadzu Corporation)
0, orifice diameter 0.1 cm, length 1 cm, pressure 10
Measured using 0 Kg / cm ² ). 3) 5% weight loss temperature In air DTA-TG (Shimadzu DT-40 series, 4
0M), and the heating rate is 10 ° C./min. Measured with 4) Glass transition temperature (Tg) Measured by DSC (Shimadzu DT-40 series, DSC-41M). 5) Adhesive strength According to JIS K-6848 and 6850.

In the synthesis examples, the siloxane-containing diamine is represented by the formula (14):

Embedded image Represents a diamine represented by

(Synthesis Examples 1 to 5) In a vessel equipped with a stirrer, a reflux condenser, a water separator and a nitrogen inlet tube, 4,
4'-bis (3-aminophenoxy) biphenyl 36
8.4 g (1.00 mol), pyromellitic dianhydride (PMDA) and phthalic anhydride (PA) are shown in Table 1.
In addition, the amount of γ-picoline 1.38 g (1.5
x10 ^-2 mol) and 2300 g of cresol,
In a nitrogen atmosphere, the temperature was raised to 145 ° C. with stirring and the reaction was carried out at 140 to 150 ° C. for 4 hours. Thereafter, the mixture was cooled to room temperature, discharged into 10.0 kg of methyl ethyl ketone, and filtered. This polyimide powder is further washed with methyl ethyl ketone, under a nitrogen atmosphere,
After preliminary drying at 50 ° C. for 24 hours, it was dried at 200 ° C. for 6 hours to obtain a polyimide powder. The logarithmic viscosity and glass transition temperature (Tg) of this polyimide powder were as shown in Table 1 together.

[0078]

[Table 1]

(Synthesis Examples 6 to 10) In a container equipped with a stirrer, a reflux condenser, a water separator and a nitrogen introducing pipe, 4,
4'-bis (3-aminophenoxy) biphenyl 36
8.4 g (1.00 mol), pyromellitic dianhydride (PMDA), and phthalic anhydride (PA) in the amounts shown in Table 2, respectively, and 1.38 g (1.5x) of γ-picoline.
10 ⁻² mol) and 2300 g of cresol were charged, and imide oligomer powder was obtained in exactly the same manner as in Synthesis Examples 1 to 5. The logarithmic viscosity and glass transition temperature (Tg) of this imide oligomer powder were as shown in Table 2 together.

[0080]

[Table 2]

(Examples 1 to 3, Comparative Examples 1 and 2) The polyimide obtained in Synthesis Example 3 and the imide oligomer obtained in Synthesis Example 8 were mixed in a mixing ratio shown in Table 3 using a Henschel mixer. After extrusion and pelletization at 400 ° C, the melt viscosity at 400 ° C and the 5% weight loss temperature were measured. The results are also shown in Table 3. In addition, each pellet was used to perform injection molding at 420 ° C., and a test piece for measuring heat distortion temperature (according to ASTM D-648).
And a test piece for measuring tensile strength (ASTM D-638
According to). Furthermore, the heat distortion temperature and the tensile strength were measured using each test piece. The results are summarized in Table 3.

[0082]

[Table 3]

From these results, as compared with the case of using only polyimide (Comparative Example 1), the polyimide (Examples 1 to 3) to which the imide oligomer was added in an amount of 0.1 to 20% by weight was heat resistant. Although the properties (5% weight loss temperature and heat distortion temperature) and mechanical strength (tensile strength) are hardly changed, the melt viscosity is greatly reduced and the workability (melt flowability) is remarkably improved. However, when the amount of imide oligomer added was excessive (Comparative Example 2), heat resistance (5
% Weight loss temperature and heat distortion temperature) and mechanical strength (tensile strength) are significantly reduced.

(Examples 4.5 and 5 and Comparative Examples 3 and 4) The polyimides obtained in the above Synthesis Example 3 and Synthesis Examples 6, 7, 9 and 1
The imide oligomer obtained in No. 0 was mixed in the mixing ratio shown in Table 4 in exactly the same manner as in Examples 1 to 3, and after pelletization, the melt viscosity and the 5% weight loss temperature were measured. The results are collectively shown in Table 4 together with the results of Example 2. Moreover, injection molding was performed using each of the pellets in the same manner as in Examples 1 to 3 to obtain each test piece. Furthermore, the heat distortion temperature and the tensile strength were measured using each test piece. The results are summarized in Table 4.

[0085]

[Table 4]

From these results, a polyimide / imide oligomer obtained by adding 10% of an imide oligomer obtained by using, as a raw material monomer, a tetracarboxylic dianhydride component in a molar ratio of 0.70 to 0.85 with respect to 1 mol of a diamine component. Although the mixture (Examples 4 and 5) hardly changed in heat resistance (5% weight loss temperature and heat distortion temperature) and mechanical strength (tensile strength) as compared with the case of using only polyimide (Comparative Example 1). However, the melt viscosity is greatly reduced, and the workability (melt flowability) is remarkably improved. However, a polyimide-imide oligomer mixture obtained by adding 10% of an imide oligomer obtained by using a tetracarboxylic dianhydride component in an amount exceeding 0.85 mol ratio per 1 mol of a diamine component as a raw material monomer (Comparative Example 3). Does not have a remarkable effect of improving melt fluidity, and 10% of an imide oligomer obtained by using a tetracarboxylic dianhydride component in an amount of less than 0.70 mol ratio per 1 mol of diamine component as a raw material monomer. It is clear that the added polyimide / imide oligomer mixture (Comparative Example 4) has a large drop in heat resistance (5% weight loss temperature and heat distortion temperature) and mechanical strength (tensile strength).

(Examples 6 and 7, Comparative Examples 5 and 6) Polyimides obtained by the above Synthetic Examples 1, 2, 4, and 5, and Synthetic Example 8
The imide oligomer obtained in Example 1 was mixed in the mixing ratio shown in Table 5 in Example 1.
After mixing and pelletizing, melt viscosity and 5% weight loss temperature were measured exactly as in ~ 3. The results are collectively shown in Table 5 together with the results of Example 2. Also, using the respective pellets, injection molding is performed in exactly the same manner as in Examples 1 to 3,
Each test piece was obtained. Furthermore, the heat distortion temperature and the tensile strength were measured using each test piece. The results are summarized in Table 5.

[0088]

[Table 5]

From these results, it was found that a polyimide obtained by adding 10% of an imide oligomer to a polyimide obtained using a tetracarboxylic dianhydride component as a raw material monomer in a molar ratio of 0.90 to 0.99 to 1 mol of a diamine component. Compared to Comparative Example 1, the imide oligomer mixture (Examples 6 and 7) showed almost no change in heat resistance (5% weight loss temperature and heat distortion temperature) and mechanical strength (tensile strength).
The melt viscosity is greatly reduced, and the workability (melt flowability) is remarkably improved. However, a polyimide obtained by adding 10% of an imide oligomer to a polyimide obtained by using a tetracarboxylic dianhydride component in excess of 0.99 mol ratio per 1 mol of a diamine component as a raw material monomer.
The imide oligomer mixture (Comparative Example 5) had very poor melt flowability and could not be injection-molded, and the diamine component 1
A polyimide / imide oligomer mixture (Comparative Example 6) obtained by adding 10% of an imide oligomer to a polyimide obtained by using a tetracarboxylic dianhydride component in an amount of less than 0.90 molar ratio as a raw material monomer with respect to mol is heat resistant. It is clear that (5% weight loss temperature and heat distortion temperature) and mechanical strength (tensile strength) are greatly reduced.

(Synthesis Examples 11 and 12) In a vessel equipped with a stirrer, a reflux condenser, a water separator and a nitrogen inlet tube, 4,
4'-bis (3-aminophenoxy) biphenyl 36
8.4 g (1.00 mol) and pyromellitic dianhydride (PMDA), 3,3 ′, 4,4′-biphenyltetracarboxylic dianhydride (BPDA), phthalic anhydride (P
A) in the amounts shown in Table 6, respectively, and further γ-picoline 1.38 g (1.5 × 10 ^-2 mol) and cresol 2
400 g was charged, the temperature was raised to 145 ° C. with stirring under a nitrogen atmosphere, and the reaction was carried out at 140 to 150 ° C. for 4 hours. Thereafter, the mixture was cooled to room temperature, discharged into 10.0 kg of methyl ethyl ketone, and filtered. This polyimide powder was further washed with methyl ethyl ketone and pre-dried in a nitrogen atmosphere at 50 ° C. for 24 hours, and then 2
It was dried at 00 ° C. for 6 hours to obtain a polyimide powder (Synthesis Example 11) or an imide oligomer powder (Synthesis Example 12).

[0091]

[Table 6]

(Synthesis Examples 13 and 14) In a container equipped with a stirrer, a reflux condenser, a water separator and a nitrogen inlet tube, 4,
4'-bis (3-aminophenoxy) biphenyl 29
4.8 g (0.80 mol), 4,4'-diaminodiphenyl ether 40.1 g (0.20 mol), pyromellitic dianhydride (PMDA), phthalic anhydride (PA)
In the respective amounts shown in Table 7, and γ-picoline 1.
38 g (1.5 x 10 ^-2 mol) and cresol 210
0 g was charged, and polyimide powder (Synthesis Example 13) or imide oligomer powder (Synthesis Example 14) was obtained in exactly the same manner as in Synthesis Examples 11 and 12.

[0093]

[Table 7]

(Examples 8 and 9, Comparative Examples 7 and 8) Polyimides obtained by the above Synthesis Examples 11 and 13, and Synthesis Example 12,
The imide oligomer obtained in 14 was mixed at the mixing ratio shown in Table 8 in exactly the same manner as in Examples 1 to 3, and after pelletization, the melt viscosity and the 5% weight loss temperature were measured. The results are summarized in Table 8. Also, using each pellet, Example 1
Injection molding was carried out in the same manner as in Nos. 3 to 3 to obtain test pieces. Furthermore, the heat distortion temperature and the tensile strength were measured using each test piece. The results are summarized in Table 8.

[0095]

[Table 8]

From these results, even when the diamine component / tetracarboxylic dianhydride component having these structures / structures was used, the polyimide was treated with the imide oligomer as compared with the case where only the polyimide was used (Comparative Examples 7 and 8). Those added in an amount of 0.1 to 20% by weight (Examples 8 and 9) showed almost no change in heat resistance (5% weight loss temperature and heat distortion temperature) and mechanical strength (tensile strength) (Examples). 8 / in the case of Comparative Example 7), the melt viscosity is greatly reduced, and the workability (melt flowability) is significantly improved.

(Synthesis Examples 15 and 16) In a vessel equipped with a stirrer, a reflux condenser, a water separator and a nitrogen inlet tube, 4,
4'-bis (3-aminophenoxy) biphenyl 36
8.4 g (1.00 mol) and 3,3'4,4'-benzophenone tetracarboxylic dianhydride (BTDA),
Phthalic anhydride (PA) was added in the amounts shown in Table 9, 1.38 g (1.5 × 10 ^-2 mol) of γ-picoline, and 2700 g of cresol, and synthesizing Example 11.12.
A polyimide powder (Synthesis Example 15) or an imide oligomer powder (Synthesis Example 16) was obtained in exactly the same manner as.

[0098]

[Table 9]

(Examples 10 to 12, Comparative Example 9) Polyimides obtained by the above Synthesis Example 15, and Synthesis Examples 12, 14,
The imide oligomer obtained in Example 16 was mixed at the mixing ratio shown in Table 10 in exactly the same manner as in Examples 1 to 3, and after pelletization, the melt viscosity and the 5% weight loss temperature were measured. Table 10 shows the results.
Are shown together.

[0100]

[Table 10]

From these results, even when the diamine component / tetracarboxylic dianhydride component having these structures / structures was used, as compared with the case of using only polyimide (Comparative Example 9),
Those obtained by adding an imide oligomer to polyimide in an amount of 0.1 to 20% by weight (Examples 10 to 12) had a large melt viscosity although the heat resistance (5% weight loss temperature) hardly changed. And the workability (melt flowability) is remarkably improved.

(Synthesis Examples 17 to 20) In a vessel equipped with a stirrer, a reflux condenser, a water separator and a nitrogen inlet tube, 1,
3-bis (3-aminophenoxy) benzene 292.4
g (1.00 mol) and 3,3 ′, 4,4′-biphenyltetracarboxylic dianhydride (BPDA), 3,3 ′
Table 4 shows 4,4′-benzophenone tetracarboxylic acid dianhydride (BTDA) and phthalic anhydride (PA), respectively.
In addition, the amount of γ-picoline 1.38 g (1.5
x10 ^-2 mol) and 2700 g of cresol were charged,
Polyimide powder (Synthesis Examples 17 and 19) or imide oligomer powder (Synthesis Example 18) was carried out in the same manner as in Synthesis Examples 11 and 12.
・ 20) was obtained.

[0103]

[Table 11]

(Examples 13 and 14, Comparative Examples 10 and 11)
The polyimides obtained in Synthetic Examples 17 and 19 and the imide oligomers obtained in Synthetic Examples 18 and 20 were mixed at the mixing ratios shown in Table 12 in exactly the same manner as in Examples 1 to 3, pelletized, and then melt viscosity and 5 The% weight loss temperature was measured. The results are summarized in Table 12.

[0105]

[Table 12]

From these results, even when the diamine component / tetracarboxylic dianhydride component having these structures / structures was used, the polyimide was treated with the imide oligomer as compared with the case where only the polyimide was used (Comparative Examples 10 and 11). 0.1-20
What was added so that it became the weight% (Examples 13 and 14)
In spite of the fact that the heat resistance (5% weight loss temperature) hardly changes, the melt viscosity is greatly reduced and the workability (melt fluidity) is remarkably improved.

(Synthesis Examples 21 to 24) In a vessel equipped with a stirrer, a reflux condenser, a water separator and a nitrogen inlet tube, 4,
200.3 g of 4'-diaminodiphenyl ether (1.
00 mol) and pyromellitic dianhydride (PMD
A), 3,3′4,4′-benzophenonetetracarboxylic dianhydride (BTDA), and phthalic anhydride (PA) in the amounts shown in Table 13, respectively, and γ-picoline 1.3.
8 g (1.5x10 ^-2 mol) and cresol 2000
g was charged and polyimide powder (Synthesis Examples 21 and 23) or imide oligomer powder (Synthesis Examples 22 and 24) were obtained in exactly the same manner as in (Synthesis Examples 11 and 12).

[0108]

[Table 13]

Comparative Examples 12 to 15 Synthesis Examples 21 and 2
The polyimides obtained in Example 3 and the imide oligomers obtained in Synthetic Examples 22 and 24 were mixed in the mixing ratios shown in Table 14 in Examples 1 to 3.
Attempts were made to perform mixing and pelletization in exactly the same manner as above, but neither could be extruded.

[0110]

[Table 14]

From these results, it is apparent that the moldability is remarkably inferior when the diamine component / tetracarboxylic dianhydride component having these structures not included in the scope of the present invention is used.

(Synthesis Examples 25 to 29) In a vessel equipped with a stirrer, a reflux condenser, a water separator and a nitrogen inlet tube, 4,
4'-bis (3-aminophenoxy) biphenyl 36
Table 15 shows 1.1 g (0.98 mol) and 4.97 g (0.02 mol) of siloxane-containing diamine, pyromellitic dianhydride (PMDA) and phthalic anhydride (PA), respectively.
In addition, the amount of γ-picoline 1.38 g (1.5
x10 ^-2 mol) and 2300 g of cresol,
Imide oligomer powder was obtained in exactly the same manner as in Synthesis Examples 6 to 10. The logarithmic viscosity and the glass transition temperature (Tg) of this imide oligomer powder were as shown in Table 15 together.

[0113]

[Table 15]

(Examples 15 to 17, Comparative Example 16) The polyimide obtained in Synthesis Example 3 and the siloxane-containing imide oligomer obtained in Synthesis Example 27 were mixed at a mixing ratio shown in Table 16 using a Henschel mixer. , Extruded pelletized at 400 ℃, melt viscosity at 400 ℃ and 5%
The weight loss temperature was measured. The results are also shown in Table 16.

[0115]

[Table 16]

From these results, as compared with the case of using only polyimide (Comparative Example 1), those obtained by adding the siloxane-containing imide oligomer to the polyimide in an amount of 0.1 to 20% by weight (Examples 15 to 17) Although the heat resistance (5% weight loss temperature) hardly changed, the melt viscosity was greatly reduced, and the workability (melt flowability) was remarkably improved. However, it is clear that the heat resistance (5% weight loss temperature) is significantly lowered when the addition amount of the siloxane-containing imide oligomer is excessive (Comparative Example 16).

(Examples 18 and 19, Comparative Examples 17 and 18)
Polyimide obtained in Synthesis Example 3 and Synthesis Examples 27 to
The siloxane-containing imide oligomer obtained in 29 was mixed at the mixing ratio shown in Table 17 in exactly the same manner as in Examples 1 to 3, and after pelletization, the melt viscosity and the 5% weight loss temperature were measured. The results are shown in Table 17 together with the result of Example 16.

[0118]

[Table 17]

From this result, a polyimide containing 10% of a siloxane-containing imide oligomer obtained by using as a raw material monomer a tetracarboxylic dianhydride component in a molar ratio of 0.70 to 0.85 with respect to 1 mol of a diamine component was prepared. The imide oligomer mixture (Examples 18 and 19) showed a significant decrease in melt viscosity as compared with the case where only polyimide was used (Comparative Example 1), although the heat resistance (5% weight loss temperature) was not significantly changed. The remarkably improved meltability (melt flowability). However, a polyimide-imide oligomer mixture obtained by adding 10% of a siloxane-containing imide oligomer obtained by using a tetracarboxylic dianhydride component in an amount exceeding 0.85 mol ratio to 1 mol of a diamine component as a raw material monomer (Comparative Example 17) does not have a remarkable effect of improving melt fluidity, and is a siloxane-containing imide obtained by using a tetracarboxylic dianhydride component in an amount of less than 0.70 mol ratio per 1 mol of diamine component as a raw material monomer. It is clear that the heat resistance (5% weight loss temperature) of the polyimide / imide oligomer mixture (Comparative Example 18) in which 10% of the oligomer is added is significantly lowered.

(Examples 20 and 21, Comparative Examples 19 and 20)
Polyimide obtained by the above Synthesis Examples 1 to 5, and Synthesis Example 2
The siloxane-containing imide oligomer obtained in Example 7 was mixed and pelletized in the same mixing ratio as shown in Table 18 in the same manner as in Examples 1 to 3, and then the melt viscosity and the 5% weight loss temperature were measured. The results are shown in Table 18 together with the result of Example 16.

[0121]

[Table 18]

From this result, 10% of the siloxane-containing imide oligomer was added to the polyimide obtained by using the tetracarboxylic dianhydride component in a molar ratio of 0.90 to 0.99 with respect to 1 mol of the diamine component as the raw material monomer. Polyimide / imide oligomer mixture (Example 20.2)
In 1), compared with Comparative Example 1, although the heat resistance hardly changed, the melt viscosity was greatly reduced, and the workability was remarkably improved. However, a polyimide / imide oligomer mixture obtained by adding 10% of a siloxane-containing imide oligomer to a polyimide obtained by using a tetracarboxylic dianhydride component in excess of 0.99 mol ratio per 1 mol of diamine component as a raw material monomer. (Comparative Example 19)
Has very poor melt fluidity, and a siloxane-containing imide oligomer is added to a polyimide obtained by using a tetracarboxylic dianhydride component in an amount of less than 0.90 mol ratio per mol of diamine component as a raw material monomer. % Polyimide / imide oligomer mixture (Comparative Example 20)
Then, it is clear that the heat resistance will drop significantly.

(Synthesis Example 30) In exactly the same manner as in Synthesis Examples 6 to 10, 361.1 g (0.98 mol) of 4,4'-bis (3-aminophenoxy) biphenyl and 4.97 g (0. 02 mol) and 87.2 g (0.400 mol) of pyromellitic dianhydride, 3,3 ′,
4,4'-biphenyltetracarboxylic dianhydride 11
7.7 g (0.400 mol), phthalic anhydride 88.9 g
(0.60 mol), γ-picoline 1.38 g (1.5x
To obtain a 10 ^-2 mol) and imide oligomer powder cresols 2400 g.

(Synthesis Example 31) 288.9 g (0.784 mol) of 4,4'-bis (3-aminophenoxy) biphenyl and 4,4'-diaminodiphenyl ether 39.same as in Synthesis Examples 6 to 10. 3 g (0.196 mol),
4.97 g (0.02 mol) of siloxane-containing diamine and 174.5 g (0.800) of pyromellitic dianhydride
), Phthalic anhydride 88.9 g (0.600 mol),
Imide oligomer powder was obtained from 1.38 g (1.5 × 10 ⁻² mol) of γ-picoline and 2100 g of cresol.

(Examples 22 and 23, Comparative Examples 21 and 22)
The polyimide obtained in each of Synthesis Examples 11 and 13 and the siloxane-containing imide oligomer or the siloxane-free imide oligomer obtained in Synthesis Examples 30 and 31 were mixed in the mixing ratio shown in Table 19 in exactly the same manner as in Examples 1 to 3, After pelletization, melt viscosity and 5% weight loss temperature were measured. The results are summarized in Table 19. Further, the obtained pellets were extruded into a film at 400 ° C. to obtain a film having a thickness of 35 μm. Two cold-rolled steel sheets (JIS G-314) obtained by preheating this film to 130 ° C.
1, SPCC / SD, 25 × 100 × 1.6 mm), and pressed under the conditions of 340 ° C. and 20 kg / cm ² for 5 minutes to perform pressure bonding. The adhesive strength of this test piece was measured at 25 ° C. The results are summarized in Table 19.

[0126]

[Table 19]

From these results, even when the diamine component / tetracarboxylic dianhydride component having these structures / structures was used, the siloxane-containing imide was added to the polyimide as compared with the case where only the polyimide was used (Comparative Examples 21 and 22). In the case of adding the oligomer in an amount of 0.1 to 20% by weight (Examples 22 and 23), although the heat resistance hardly changed, the melt viscosity was significantly decreased and the melt fluidity was significantly improved. , The adhesive strength is also greatly improved.

(Synthesis Example 32) In exactly the same manner as in Synthesis Examples 6 to 10, 361.1 g (0.98 mol) of 4,4'-bis (3-aminophenoxy) biphenyl and 4.97 g (0 of a siloxane-containing diamine). .02 mol) and 3,3 '
4,4'-benzophenone tetracarboxylic acid dianhydride 2
57.8 g (0.800 mol), phthalic anhydride 88.9
g (0.600 mol), 1.38 g (1.
An imide oligomer powder was obtained from 5 × 10 ⁻² mol) and 2700 g of cresol.

(Examples 24 to 26) The polyimide obtained in Synthesis Example 15 and the siloxane-containing imide oligomer obtained in Synthesis Examples 30 to 32 were mixed in the mixing ratio shown in Table 20 in exactly the same manner as in Examples 1 to 3. After pelletizing, melt viscosity and 5% weight loss temperature were measured. The results are summarized in Table 20.

[0130]

[Table 20]

From these results, even when the diamine component / tetracarboxylic dianhydride component having these structures / structures was used, as compared with the case of only polyimide (Comparative Example 9),
Add siloxane-containing imide oligomer to polyimide to 0.1
Added in an amount of 20% by weight (Example 24-
In No. 26), although the heat resistance (5% weight loss temperature) hardly changed, the melt viscosity was greatly reduced, and the workability (melt flowability) was remarkably improved.

(Synthesis Examples 33 and 34) The above Synthesis Examples 6 to 10
1,3-bis (3-aminophenoxy)
286.6 g (0.98 mol) of benzene, 4.97 g (0.02 mol) of diamine containing siloxane, and 3,
3 ', 4,4'-biphenyltetracarboxylic dianhydride (BPDA), 3,3'4,4'-benzophenone tetracarboxylic dianhydride (BTDA), phthalic anhydride (P
Imide oligomer powder was obtained from the amounts of A) shown in Table 21, and further 1.38 g (1.5 × 10 ⁻² mol) of γ-picoline and 2700 g of cresol.

[0133]

[Table 21]

(Examples 27 and 28, Comparative Examples 23 and 24)
The polyimides obtained in Synthetic Examples 17 and 19 and the siloxane-containing imide oligomers obtained in Synthetic Examples 33 and 34 were mixed in the mixing ratio shown in Table 22 in exactly the same manner as in Examples 1 to 3.
After pelletization, melt viscosity and 5% weight loss temperature were measured. The results are summarized in Table 22. Further Example 2
For 7 and Comparative Example 23, two cold rolled steel sheets (JIS) were prepared by mixing polyimide and a siloxane-containing imide oligomer in the mixing ratios shown in Table 22 in exactly the same manner as in Example 3, and then preheating to 130 ° C. G-3141, SPC
C / SD, 25 × 100 × 1.6 mm) was uniformly applied to one side of the adhesive surface, and pressure was applied for 10 minutes under the conditions of 310 ° C. and 20 kg / cm ² , and pressure was applied. In addition, 2
Cure at 50 ° C for 3 hours and then cool to 25 ° C and 1
The adhesive strength was measured at 50 ° C. The results are summarized in Table 22. In addition, in Example 28 and Comparative Example 24, the polyimide and the siloxane-containing imide oligomer were mixed in N-methyl-2-pyrrolidone at 25 at a mixing ratio shown in Table 22.
After being mixed so as to have a weight percentage, two cold rolled steel plates (JIS G-3141, SPCC / SD, 25 × 10
(0 x 1.6 mm), apply evenly on one side of the adhesive surface, and
After preheating at 0 ° C. for 2 hours to almost remove the solvent, 310
Pressure was applied for 5 minutes under the conditions of ° C and 20 kg / cm ² for pressure bonding. The adhesive strength of this test piece was measured at 25 ° C and 150 ° C. The results are summarized in Table 22.

[0135]

[Table 22]

From these results, even when the diamine component / tetracarboxylic dianhydride component having these structures / structures was used, the siloxane-containing imide was added to the polyimide in comparison with the case of using only the polyimide (Comparative Examples 23 and 24). In the case of adding the oligomer in an amount of 0.1 to 20% by weight (Examples 27 and 28), although the heat resistance (5% weight loss temperature) hardly changed, the melt viscosity was significantly reduced,
It can be seen that the workability (melt flowability) is remarkably improved and both the adhesive strength at room temperature and the adhesive strength at high temperature are excellent.

(Synthesis Examples 35 and 36) The above Synthesis Examples 6 to 10
In exactly the same manner, 4,4'-diaminodiphenyl ether 196.3 g (0.98 mol), siloxane-containing diamine 4.97 g (0.02 mol), and pyromellitic dianhydride (PMDA), 3,3 '. The amounts of 4,4′-benzophenonetetracarboxylic dianhydride (BTDA) and phthalic anhydride (PA) shown in Table 23, respectively, and γ-
An imide oligomer powder was obtained from 1.38 g (1.5 × 10 ^-2 mol) of picoline and 2000 g of cresol.

[0138]

[Table 23]

Comparative Examples 25 and 26 Synthesis Examples 21 and 2
The polyimide obtained in Example 3 and the siloxane-containing imide oligomer obtained in Synthesis Examples 35 and 36 were mixed at the mixing ratio shown in Table 24 in exactly the same manner as in Examples 1 to 3, and pelletization was performed. It was impossible.

[0140]

[Table 24]

From these results, it is apparent that the moldability is remarkably inferior when the diamine component / tetracarboxylic dianhydride component having these structures not included in the scope of the present invention is used.

(Synthesis Examples 37 to 41) In a vessel equipped with a stirrer, a reflux condenser, a water separator and a nitrogen inlet tube, 4,
4'-bis (3-aminophenoxy) biphenyl 36
1.1 g (0.98 mol) and 4.97 g (0.02 mol) of a siloxane-containing diamine, and pyromellitic dianhydride (PMDA) and phthalic anhydride (PA) in the amounts shown in Table 25, respectively. , Γ-picoline 1.38g
(1.5 × 10 ⁻² mol) and 2300 g of cresol were charged, and the mixture was heated to 145 ° C. with stirring under a nitrogen atmosphere and reacted at 140 to 150 ° C. for 4 hours. Thereafter, the mixture was cooled to room temperature, discharged into 10.0 kg of methyl ethyl ketone, and filtered. This polyimide powder was further washed with methyl ethyl ketone, preliminarily dried at 50 ° C. for 24 hours under a nitrogen atmosphere, and then dried at 200 ° C. for 6 hours to obtain a polyimide powder. The logarithmic viscosity and glass transition temperature (Tg) of this polyimide powder are shown in Table 25.
Was also shown.

[0143]

[Table 25]

(Examples 29 to 31, Comparative Examples 27 and 28)
The polyimide obtained in Synthesis Example 39 and the siloxane-containing imide oligomer obtained in Synthesis Example 8 were mixed at a mixing ratio shown in Table 26 using a Henschel mixer, and the mixture was heated to 400 ° C.
After extruding and pelletizing at, melt viscosity at 400 ° C. and 5% weight loss temperature were measured. The results are also shown in Table 26.

[0145]

[Table 26]

From these results, as compared with the case where only the siloxane-containing polyimide was used (Comparative Example 27), the imide oligomer added to the polyimide in an amount of 0.1 to 20% by weight (Examples 29 to 31) was obtained. Although the heat resistance (5% weight loss temperature) hardly changed, the melt viscosity was greatly reduced, and the workability (melt flowability) was remarkably improved. However, it is clear that the heat resistance (5% weight loss temperature) is significantly lowered when the addition amount of the siloxane-containing imide oligomer is excessive (Comparative Example 28).

(Examples 32 and 33, Comparative Examples 29 and 30)
Polyimide obtained in Synthesis Example 39, and Synthesis Examples 6 to
The imide oligomer obtained in 10 was mixed and pelletized in exactly the same manner as in Examples 1 to 3 at the mixing ratios shown in Table 27, and then the melt viscosity and the 5% weight loss temperature were measured. The results are shown in Example 30.
The results are collectively shown in Table 27.

[0148]

[Table 27]

From these results, a polyimide / imide oligomer obtained by adding 10% of an imide oligomer obtained by using as a raw material monomer a tetracarboxylic dianhydride component in a molar ratio of 0.70 to 0.85 with respect to 1 mol of a diamine component. Although the mixture (Examples 32 and 33) had substantially no change in heat resistance (5% weight loss temperature) as compared with the case of using only polyimide (Comparative Example 27), the melt viscosity was significantly reduced and the processability ( The melt fluidity) is remarkably improved.
However, the imide oligomer obtained by using the tetracarboxylic acid dianhydride component in an amount exceeding 0.85 mol ratio per mol of the diamine component as a raw material monomer is 10
%, The polyimide / imide oligomer mixture (Comparative Example 29) did not have a remarkable effect of improving melt fluidity, and the amount of the tetracarboxylic dianhydride component was less than 0.70 mol ratio per mol of the diamine component. It is clear that the heat resistance (5% weight loss temperature) of the polyimide / imide oligomer mixture (Comparative Example 30) obtained by adding 10% of the imide oligomer obtained by using as a raw material monomer is significantly lowered.

(Examples 34 and 35, Comparative Examples 31 and 32)
The polyimides obtained in Synthetic Examples 37, 38, 40, 41 and the imide oligomers obtained in Synthetic Example 8 were mixed at the mixing ratios shown in Table 28 in exactly the same manner as in Examples 1 to 3, and after pelletization, the melt viscosity and The 5% weight loss temperature was measured. The results are shown in Table 28 together with the result of Example 30.

[0151]

[Table 28]

From these results, a polyimide obtained by adding 10% of an imide oligomer to a polyimide obtained by using a tetracarboxylic dianhydride component as a raw material monomer in a molar ratio of 0.90 to 0.99 with respect to 1 mol of a diamine component. The imide oligomer mixture (Examples 34 and 35) was Comparative Example 27.
In comparison with, although the heat resistance hardly changes,
The melt viscosity is greatly reduced, and the workability is remarkably improved.
However, a polyimide / imide oligomer mixture obtained by adding 10% of an imide oligomer to a polyimide obtained by using a tetracarboxylic dianhydride component in excess of 0.99 mol ratio per 1 mol of a diamine component as a raw material monomer (comparison In Example 31), the melt fluidity is very poor, and an imide oligomer is added to a polyimide obtained by using a tetracarboxylic dianhydride component in an amount of less than 0.90 mol ratio per mol of the diamine component as a raw material monomer. 10
%, It is clear that the polyimide / imide oligomer mixture (Comparative Example 32) has a significantly reduced heat resistance.

(Synthesis Example 42) Stirrer, reflux condenser,
In a container equipped with a water separator and a nitrogen inlet tube, 4,4'-
Bis (3-aminophenoxy) biphenyl 361.1 g
(0.98 mol), siloxane-containing diamine 4.97 g
(0.02 mol) and pyromellitic dianhydride 10
3.6 g (0.475 mol), 13,3 ', 4,4'-biphenyltetracarboxylic dianhydride 139.8 g (0.
475 mol), phthalic anhydride 22.2 g (0.15 mol), γ-picoline 1.38 g (1.5 × 10 ^-2 mol)
Then, 2400 g of cresol was charged, and polyimide powder was obtained in exactly the same manner as in Synthesis Examples 1 to 5.

(Synthesis Example 43) 288.9 g (0.784 mol) of 4,4'-bis (3-aminophenoxy) biphenyl and 4,4'-diaminodiphenyl ether 39.same as in Synthesis Examples 1-5. 3 g (0.196 mol),
4.97 g (0.02 mol) of siloxane-containing diamine and 208.3 g (0.955) of pyromellitic dianhydride.
20.0 g (0.135 mol) of phthalic anhydride,
A polyimide powder was obtained from 1.38 g (1.5 × 10 ^-2 mol) of γ-picoline and 2100 g of cresol.

(Examples 36 and 37, Comparative Examples 33 to 34)
The polyimides obtained in the respective Synthesis Examples 42 and 43 and the imide oligomers obtained in the Synthesis Examples 12 and 14 were mixed at the mixing ratios shown in Table 29 in exactly the same manner as in Examples 1 to 3, and after pelletization, the melt viscosity and The 5% weight loss temperature was measured. The results are summarized in Table 29.

Further, using the obtained pellets, 40
The film was extruded at 0 ° C. to obtain a film having a thickness of 35 μm. Two cold-rolled steel sheets (JIS G-3141, SPCC) obtained by preheating this film to 130 ° C.
/ SD, 25 × 100 × 1.6 mm) and insert 3
Pressure was applied for 5 minutes under the conditions of 40 ° C. and 20 kg / cm ² for pressure bonding. The adhesive strength of this test piece was measured at 25 ° C. The results are summarized in Table 29.

[0157]

[Table 29]

From these results, even when the diamine component / tetracarboxylic dianhydride component having these structures / structures was used, the polyimide was treated with the imide oligomer as compared with the case where only the polyimide was used (Comparative Examples 33 and 34). 0.1-20
What was added so that it became the weight% (Examples 36 and 37)
Despite having almost no change in heat resistance, the melt viscosity was greatly reduced, the melt fluidity was significantly improved, and the adhesive strength was also significantly improved.

(Synthesis Example 44) 361.1 g (0.98 mol) of 4,4'-bis (3-aminophenoxy) biphenyl and 4.97 g (0 of siloxane-containing diamine) were prepared in the same manner as in Synthesis Examples 1 to 5. .02 mol) and 3,3'4.
4'-benzophenone tetracarboxylic acid dianhydride 30
7.7 g (0.955 mol), phthalic anhydride 20.0 g
(0.135 mol), 1.38 g (1.5
(x10 ⁻² mol) and 2700 g of cresol to obtain a polyimide powder.

(Examples 38 to 40, Comparative Example 35) Polyimides obtained in the above Synthesis Example 44, and Synthesis Examples 12 and 1
The imide oligomers obtained in Nos. 4 and 16 were mixed at the mixing ratio shown in Table 30 in exactly the same manner as in Examples 1 to 3, and after pelletization, the melt viscosity and the 5% weight loss temperature were measured. Table 30 shows the results.
Are shown together.

[0161]

[Table 30]

From these results, even when the diamine component / tetracarboxylic dianhydride component having these structures / structures was used, the imide oligomer was added to the polyimide in an amount of 0. 0 as compared with the case where only the polyimide was used (Comparative Example 35). Those added in an amount of 1 to 20% by weight (Examples 38 to 40) are
Although the heat resistance (5% weight loss temperature) hardly changes, the melt viscosity is greatly reduced, and the workability (melt flowability) is remarkably improved.

(Synthesis Examples 45 and 46) 286.6 g (0.98 mol) of 1,3-bis (3-aminophenoxy) benzene and 4.97 g of siloxane-containing diamine were prepared in the same manner as in Synthesis Examples 1 to 5 above. 0.02 mol) and 3,3 ′,
4,4'-biphenyltetracarboxylic dianhydride (BP
DA), 3,3′4,4′-benzophenonetetracarboxylic dianhydride (BTDA), and phthalic anhydride (PA) in the amounts shown in Table 31, respectively, and γ-picoline 1.
38 g (1.5 x 10 ^-2 mol) and cresol 270
A polyimide powder was obtained from 0 g.

[0164]

[Table 31]

(Examples 41 and 42, Comparative Examples 36 and 37)
The polyimides obtained in Synthetic Examples 45 and 46 and the imide oligomers obtained in Synthetic Examples 18 and 20 were mixed in the mixing ratios shown in Table 32 in exactly the same manner as in Examples 1 to 3, pelletized, and then melt viscosity and 5 The% weight loss temperature was measured. The results are summarized in Table 32. Furthermore (Example 41, Comparative Example 3
Regarding 6), two cold-rolled steel sheets (J) were prepared by mixing polyimide and imide oligomer at the mixing ratios shown in Table 32 in exactly the same manner as in Examples 1 to 3 and then preheating to 130 ° C.
IS G-3141, SPCC / SD, 25 x 100 x
1.6 mm) evenly applied to one side of the adhesive surface, 310
Pressure was applied for 10 minutes under the conditions of 20 ° C. and 20 kg / cm ² for pressure bonding. Further, this test piece was cured at 250 ° C. for 3 hours and then cooled, and the adhesive strength was measured at 25 ° C. and 150 ° C. The results are summarized in Table 32. Example 4
2, For Comparative Example 37, polyimide and imide oligomer were mixed in N-methyl-2-pyrrolidone at a mixing ratio shown in Table 32 to be 25% by weight, and then two cold-rolled steel sheets (JIS G- 3141, SPCC / SD,
(25 × 100 × 1.6 mm) is evenly applied to one side of the adhesive surface, preheated at 200 ° C. for 2 hours to remove the solvent, and then pressed at 310 ° C. and 20 kg / cm ² for 5 minutes for pressure bonding. Let 25 ° C and 15 for this test piece
The adhesive strength was measured at 0 ° C. The results are summarized in Table 32.

[0166]

[Table 32]

From these results, even when the diamine component / tetracarboxylic dianhydride component having these structures / structures was used, the polyimide was compared with the imide oligomer as compared with the case of only the polyimide (Comparative Examples 36 and 37). 0.1-20
What was added so that it became the weight% (Examples 41 and 42)
Although the heat resistance (5% weight loss temperature) hardly changes, the melt viscosity is greatly reduced and the workability (melt flowability) is significantly improved. The adhesive strength at room temperature and the adhesive strength at high temperature It turns out that both are excellent.

(Synthesis Examples 47, 48) In exactly the same manner as in Examples 1 to 5, 196.3 g (0.98 mol) of 4,4'-diaminodiphenyl ether and 4.97 g (0.02 mol) of a siloxane-containing diamine. ) And pyromellitic dianhydride (PMDA), 3,3′4,4′-benzophenonetetracarboxylic dianhydride (BTDA), and phthalic anhydride (PA) in the amounts shown in Table 33, respectively, γ
A polyimide powder was obtained from 1.38 g (1.5 × 10 ^-2 mol) of picoline and 2000 g of cresol.

[0169]

[Table 33]

Comparative Examples 38 to 41 Synthesis Examples 47 and 4 above
The polyimides obtained in Example 8 and the imide oligomers obtained in Synthesis Examples 22 and 24 were mixed in the mixing ratios shown in Table 34 in Examples 1-3.
Attempts were made to perform mixing and pelletization in exactly the same manner as above, but neither could be extruded.

[0171]

[Table 34]

From these results, it is apparent that the molding processability is remarkably inferior when the diamine component / tetracarboxylic dianhydride component having these structures not included in the scope of the present invention is used.

(Examples 43 to 45, Comparative Example 42) The polyimide obtained in Synthesis Example 39 and the siloxane-containing imide oligomer obtained in Synthesis Example 27 were mixed at a mixing ratio shown in Table 35 using a Henschel mixer. , Extruded pelletized at 400 ℃, melt viscosity at 400 ℃ and 5
The% weight loss temperature was measured. The results are also shown in Table 35.

[0174]

[Table 35]

From these results, as compared with the case of using only the siloxane-containing polyimide (Comparative Example 27), the siloxane-containing imide oligomer was added to the polyimide in an amount of 0.1 to 20% by weight (Examples 43 to 45). ), Although the heat resistance (5% weight loss temperature) hardly changes, the melt viscosity is greatly reduced, and the workability (melt fluidity) is significantly improved. However, it is clear that the heat resistance (5% weight loss temperature) is significantly lowered when the addition amount of the siloxane-containing imide oligomer is excessive (Comparative Example 42).

(Examples 46 and 47, Comparative Examples 43 and 44)
Polyimide obtained in Synthesis Example 39, and Synthesis Example 2
The imide oligomers obtained in 5, 26, 28 and 29 are shown in Table 36.
After mixing and pelletizing in the same mixing ratio as shown in Examples 1 to 3, melt viscosity and 5% weight loss temperature were measured.
The results are shown in Table 36 together with the result of Example 44.

[0177]

[Table 36]

From these results, a polyimide / imide oligomer obtained by adding 10% of an imide oligomer obtained by using as a raw material monomer a tetracarboxylic dianhydride component in a molar ratio of 0.70 to 0.85 with respect to 1 mol of a diamine component. Compared with the case where only the polyimide (Comparative Example 27), the mixture (Examples 46 and 47) had substantially no change in heat resistance (5% weight loss temperature), but the melt viscosity was significantly reduced and the processability ( The melt fluidity) is remarkably improved.
However, the imide oligomer obtained by using the tetracarboxylic acid dianhydride component in an amount exceeding 0.85 mol ratio per mol of the diamine component as a raw material monomer is 10
%, The polyimide / imide oligomer mixture (Comparative Example 43) did not have a remarkable effect of improving the melt fluidity, and the amount of the tetracarboxylic dianhydride component was less than 0.70 mol ratio to 1 mol of the diamine component. It is clear that the polyimide / imide oligomer mixture (Comparative Example 44) obtained by adding 10% of the imide oligomer obtained by using as a raw material monomer, the heat resistance (5% weight loss temperature) is significantly lowered.

(Examples 48 and 49, Comparative Examples 45 and 46)
The polyimides obtained in Synthesis Examples 37, 38, 40, 41 and the imide oligomers obtained in Synthesis Example 27 were mixed at the mixing ratios shown in Table 37 in exactly the same manner as in Examples 1 to 3, pelletized, and then the melt viscosity was changed. And 5% weight loss temperature was measured. The results are collectively shown in Table 37 together with the result of Example 44.

[0180]

[Table 37]

From these results, a polyimide obtained by adding 10% of an imide oligomer to a polyimide obtained by using a tetracarboxylic dianhydride component in a molar ratio of 0.90 to 0.99 with respect to 1 mol of a diamine component as a raw material monomer. The imide oligomer mixture (Examples 48 and 49) was Comparative Example 27.
In comparison with, although the heat resistance hardly changes,
The melt viscosity is greatly reduced, and the workability is remarkably improved.
However, a polyimide / imide oligomer mixture obtained by adding 10% of an imide oligomer to a polyimide obtained by using a tetracarboxylic dianhydride component in excess of 0.99 mol ratio per 1 mol of a diamine component as a raw material monomer (comparison Example 45) has very poor melt fluidity, and the polyimide obtained by using the tetracarboxylic dianhydride component in an amount of less than 0.90 mol ratio per mol of the diamine component as a raw material monomer is an imide oligomer. 10
%, It is clear that the polyimide / imide oligomer mixture (Comparative Example 46) in which the heat resistance is significantly deteriorated.

(Examples 50 and 51) The respective synthesis examples 42,
The polyimide obtained in Example 43 and the siloxane-containing imide oligomer or the siloxane-free imide oligomer obtained in Synthesis Examples 30 and 31 were mixed at the mixing ratios shown in Table 38.
After mixing and pelletizing, melt viscosity and 5% weight loss temperature were measured exactly as in ~ 3. The results are summarized in Table 38. Further, the obtained pellets were extruded into a film at 400 ° C. to obtain a film having a thickness of 35 μm. Two cold-rolled steel sheets (JIS G-3141, SPCC / S) obtained by preheating this film to 130 ° C.
D, 25 x 100 x 1.6 mm) and insert 340
Pressure was applied for 5 minutes under the conditions of ° C and 20 kg / cm ² for pressure bonding. The adhesive strength of this test piece was measured at 25 ° C. The results are summarized in Table 38.

[0183]

[Table 38]

From these results, even when the diamine component / tetracarboxylic dianhydride component having these structures / structures was used, the polyimide was treated with the imide oligomer as compared with the case where only the polyimide was used (Comparative Examples 33 and 34). 0.1-20
What was added so that it became the weight% (Examples 50 and 51)
Despite having almost no change in heat resistance, the melt viscosity was greatly reduced, the melt fluidity was significantly improved, and the adhesive strength was also significantly improved.

(Examples 52 to 54) The polyimide obtained in Synthesis Example 44 and the imide oligomer obtained in Synthesis Examples 30 to 32 were mixed at the mixing ratio shown in Table 39 in exactly the same manner as in Examples 1 to 3, and pelletized. After conversion, the melt viscosity and the 5% weight loss temperature were measured. The results are summarized in Table 39.

[0186]

[Table 39]

From these results, even when the diamine component / tetracarboxylic dianhydride component having these structures / structures was used, the imide oligomer was added to the polyimide in an amount of 0.1% compared to the case of using only the polyimide (Comparative Example 35). Those added in an amount of 1 to 20% by weight (Examples 52 to 54) are
Although the heat resistance (5% weight loss temperature) hardly changes, the melt viscosity is greatly reduced, and the workability (melt flowability) is remarkably improved.

(Examples 55 and 56) Synthetic Examples 45 and 4
The polyimides obtained in Example 6 and the imide oligomers obtained in Synthesis Examples 33 and 34 were mixed in the mixing ratios shown in Table 40 in Examples 1 to 3.
Melt viscosity and 5% after mixing and pelletizing just like
The weight loss temperature was measured. The results are summarized in Table 40. Further, in Example 55 and Comparative Example 36, two cold-rolled steel sheets (preliminarily heated to 130 ° C.) were prepared by mixing polyimide and imide oligomer in the mixing ratios shown in Table 40 in exactly the same manner as in Examples 1 to 3. JIS G-3141, S
(PCC / SD, 25 × 100 × 1.6 mm) was evenly applied to one side of the adhesive surface, and pressure was applied for 10 minutes under the conditions of 310 ° C. and 20 kg / cm ² for pressure bonding. Further, this test piece was cured at 250 ° C. for 3 hours and then cooled, and the adhesive strength was measured at 25 ° C. and 150 ° C. The results are summarized in Table 40.

For Example 56 and Comparative Example 37, the polyimide and imide oligomer were mixed in N-methyl-2-pyrrolidone at a mixing ratio shown in Table 40 to a concentration of 25% by weight, and then two cold sheets were cooled. Hot rolled steel sheet (JIS G
-3141, SPCC / SD, 25 × 100 × 1.6m
m) is uniformly applied to one side of the adhesive surface, preheated at 200 ° C for 2 hours to remove the solvent, and then 310 ° C, 20 kg.
The pressure was applied for 5 minutes under the condition of / cm ² for pressure bonding. The adhesive strength of this test piece was measured at 25 ° C and 150 ° C. The results are summarized in Table 40.

[0190]

[Table 40]

From these results, even when the diamine component / tetracarboxylic dianhydride component having these structures / structures was used, the polyimide was compared with the imide oligomer as compared with the case of only the polyimide (Comparative Examples 36 and 37). 0.1-20
What was added so that it became the weight% (Examples 55 and 56)
Although the heat resistance (5% weight loss temperature) hardly changes, the melt viscosity is greatly reduced and the workability (melt flowability) is significantly improved. The adhesive strength at room temperature and the adhesive strength at high temperature It turns out that both are excellent.

Comparative Examples 47 and 48 Synthesis Examples 47 and 4
The polyimide obtained in Example 8 and the siloxane-containing imide oligomers obtained in Synthesis Examples 35 and 36 were mixed and pelletized in exactly the same manner as in Examples 1 to 3 at the mixing ratios shown in Table 41. It was impossible.

[0193]

[Table 41]

From these results, it is apparent that the moldability is remarkably inferior when the diamine component / tetracarboxylic dianhydride component having these structures not included in the scope of the present invention is used.

[0195]

According to the present invention, a resin composition having extremely excellent workability and adhesiveness in addition to excellent heat resistance and mechanical properties is provided. This resin composition has good low hygroscopicity,
It has both electrical properties, solvent resistance, and chemical resistance, and has excellent dimensional stability during processing, and is suitable for melt processing. Molded products, films, fibers, etc. that have this as a main component have extremely good heat resistance and mechanical strength. , Fatigue strength, low moisture absorption, sliding properties, electrical properties, solvent resistance, chemical resistance, radiation resistance, and dimensional stability.

Continuation of front page (31) Priority claim number Japanese Patent Application No. 8-91180 (32) Priority Day Hei 8 (1996) April 12 (33) Country of priority claim Japan (JP) (72) Inventor Wataru Yamashita Kanagawa 1190 Kasama-cho, Sakae-ku, Yokohama-shi, Mitsui Within Mitsui Toatsu Chemical Co., Ltd. 1190 Kasama Town Mitsui Toatsu Chemical Co., Ltd.

Claims (3)

[Claims] 1. A polyimide obtained by a polymerization reaction from a diamine component and a tetracarboxylic dianhydride component, which are (a) raw material monomers, and having a molar ratio of 0.90 to 0.99 relative to 1 mol of the diamine component. A polyimide having a logarithmic viscosity of 0.30 dl / g or more and 1.2 dl / g or less obtained by using a tetracarboxylic dianhydride component as a raw material monomer, and (b) a diamine component and a tetracarboxylic dianhydride which are raw material monomers. Which is an imide oligomer obtained by a polymerization reaction from a diamine component and has a logarithmic viscosity of 0 obtained by using a tetracarboxylic dianhydride component in a molar ratio of 0.70 to 0.85 with respect to 1 mol of a diamine component as a raw material monomer. (C) Polyimide 80 to 9 with an imide oligomer of 0.05 dl / g or more and less than 0.3 dl / g
Imide oligomer 20-0.1 based on 9.9% by weight
It is a resin composition obtained by mixing in a weight% ratio, and (d) the diamine component in the raw material monomer of the polyimide is represented by the general formula (1): H ₂ N—R ₁ —NH. ₂ (1) (However, in the formula, R ₁ [Chemical formula 1] is In a diamine chi ₁ mol% represented by), and the general formula _{(2): H 2 N-} R 2 -NH 2 (2) ( In the formula, R ₂ [Formula 2] [Formula 2] A diamine χ ₂ mol% represented by a divalent group different from R ₁ selected from the group consisting of: and a compound represented by the general formula (3) [Chemical Formula 3]: (In the formula, n is 0 or a mixed value of integers from 0 to 20, and R ₃ [Chemical Formula 4] is Is a divalent group selected from the group consisting of) diamine represented by χ ₃ mol%, χ ₁ , χ ₂ and χ
₃ has a total of 100, and the following formula (I): 0 ≦ χ ₂ / χ ₁ ≦ 99 ………………………… (I) and formula (II): 0 ≦ χ ₃ / (χ ₁ + χ ₂ + χ ₃ ) ≦ 0.1 A real non-negative number that satisfies (II), and (e) the tetracarboxylic dianhydride component of the raw material monomer of the polyimide is 5] (F) The diamine component of the raw material monomer of the imide oligomer is represented by the general formula (4): H ₂ N—R ′ ₁ —NH _{2 and} is composed of one or two tetracarboxylic acid dianhydrides selected from the group consisting of: (4) (However, in the formula, R ′ ₁ [Chemical Formula 6] is Diamine chi _'1 mol% and the general formula _{(5): H 2 N-} R' represented by a is) ₂ -NH ₂ (5) (In the formula, R _'2 [Formula 7] is embedded ] A diamine χ ′ ₂ mol% represented by a divalent group different from R ′ ₁ selected from the group consisting of: and a general formula (6) [Chemical formula 8]: (In the formula, n is 0 or a mixed value of integers from 0 to 20, and R ′ ₃ [Chemical formula 9] is 'Consists _{of three} mol%, chi' diamine chi represented a kind of a divalent group) selected from the group consisting of _1, chi _'2 and chi' ₃ is the sum of 100, following Formula (III): 0 ≦ χ ′ ₂ / χ ′ ₁ ≦ 99 ………………………………… (III) and Formula (IV): 0 ≦ χ ′ ₃ / (χ ′ ₁ + χ _'2 + χ' ₃₎ <a non-negative real satisfying 1 ............ the (IV), (g) a tetracarboxylic acid dianhydride component of the raw material monomer of the imide oligomer is embedded image A resin composition comprising one or two tetracarboxylic acid dianhydrides selected from the group consisting of: 2. A resin composition obtained by mixing 80 to 97% by weight of the polyimide with 20 to 3% by weight of the imide oligomer in the resin composition according to claim 1. 3. When synthesizing the polyimide and / or imide oligomer according to claim 1 or 2, the general formula (7) is used.
[Chemical formula 11]: (Wherein, Z has 6 to 15 carbon atoms and is a monocyclic aromatic group,
An aromatic group represented by a condensed polycyclic aromatic group and a divalent group selected from the group consisting of non-condensed polycyclic aromatic groups in which aromatic groups are directly or linked to each other by a bridge member) The resin composition according to claim 1 or 2, wherein a dicarboxylic acid anhydride is allowed to coexist to form a polyimide and / or a polyimide oligomer containing a polyimide and / or a polyimide oligomer whose molecular ends are blocked.