JPH0641424A - Polyimide resin composition - Google Patents

Abstract

PURPOSE:To obtain the polyimide resin composition which can be thermally treated at a low temp. in a short time and is excellent in dimensional stability, flowability, etc., by blending a given polyimide with a polyetheretherketone to cause the resulting composition to have a specific value of crystallization enthalpy after heat treatment. CONSTITUTION:The composition comprises 50-95 pts.wt. polyimide resin having a repeating unit represented by the formula (wherein X is a direct bond, a 1-10C divalent hydrocarbon group, hexafluoroisopropylidene, carbonyl, thio, sulfonyl, or oxo; Y1 to Y4 each is H, a 1-9C alkyl, a 1-9C alkoxy, Cl, or Br; and R1 is a 2-27C tetravalent group selected from among a (monocyclic) aliphatic group, a monocyclic aromatic group; a fused aromatic group, and a nonfused polycyclic aromatic group consisting of aromatic groups bonded together directly or through a crosslinking member) and 50-5 pts.wt. polyetheretherketone. It has a crystallization enthalpy of 0-6cal/g after heating at 250-330 deg.C (as measured with a differential scanning calorimeter at a heating rate of 10 deg.C/min).

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION The present invention improves the fluidity, stability and resin releasability at the time of molding by heat treatment under specific conditions, and especially mechanical properties, sliding characteristics and heat resistance at high temperature. It also relates to a polyimide resin composition having excellent chemical resistance.

[0002]

2. Description of the Related Art Conventionally, polyimide is extremely excellent in heat resistance and also has mechanical strength, flame retardancy, electric insulation, etc., so that electric / electronic equipment, aerospace equipment, transportation equipment, etc. Used in the field of. Further, it is expected that the application will be expanded to the field where heat resistance is required in the future, and a polyimide showing excellent properties has already been developed.

However, conventionally developed polyimides have, for example, excellent heat resistance but poor workability,
Further, for example, resins of the type developed for the purpose of improving workability have inferior heat resistance and solvent resistance.

Specifically, J. Polym. Sci. M
acromol, Rev. , 11, 161 (1976)
Or J. Elast. Plast. , 7,285 (1
975).

[0005]

[Chemical 5] Polyimide having a basic skeleton represented by (DuPont: trade name Kapton, Vespel) does not have a clear glass transition temperature and is a polyimide having excellent heat resistance, but it is difficult to process when used as a molding material. , It must be processed using a technique such as sintering. Further, when used as a material for electric / electronic parts, it has a drawback that dimensional stability, insulation, and solder heat resistance are adversely affected.

Further, the equation (6)

[0007]

[Chemical 6] Polyetherimide having a basic skeleton represented by (General Electric Co., Ltd .: trade name ULTEM) is a resin having excellent processability, but has a glass transition temperature of 217.
It is not a satisfactory resin in terms of solvent resistance because it is low at ℃ and inferior in heat resistance, soluble in halogenated hydrocarbons such as methylene chloride.

In order to solve these drawbacks, the applicant of the present invention has proposed the formula (1)

[0009]

[Chemical 7] (In the formula, X is a direct bond or is selected from the group consisting of a divalent hydrocarbon group having 1 to 10 carbon atoms, a hexafluorinated isopropylidene group, a carbonyl group, a thio group, a sulfonyl group and an oxo group. Represents a group, Y ₁ , Y ₂ , Y ₃ and Y ₄ are each hydrogen, a lower alkyl group having 1 to 9 carbon atoms,
It represents a group selected from the group consisting of a lower alkoxy group having 1 to 9 carbon atoms, chlorine and bromine, and R ₁ has 2 to 2 carbon atoms.
7, which is an aliphatic group, a monocyclic aliphatic group, a monocyclic aromatic group, a condensed polycyclic aromatic group, and a non-condensed polycyclic group in which aromatic groups are connected to each other directly or by a crosslinking member. It represents a tetravalent group selected from the group consisting of aromatic groups. ), A polyimide resin having a repeating unit represented by the following formula was developed and applied for a patent (JP-A-62-236858 and JP-A-62-253655).
issue).

This polyimide resin is used in a wide range of fields because it has excellent properties such as thermal properties and electrical properties. However, this resin has a slow crystallization rate, and a molded product obtained by injection molding at a mold temperature of 50 to 250 ° C. is usually amorphous. Therefore, when it is used as a crystallized product, heat treatment is necessary.
There is a heat treatment method described in Japanese Patent No. 0538. However, this method is carried out under conditions of long time and high temperature, and for example, 2
At 70 ° C., a long heat treatment of 12 hours or more is required. Further, there is a problem that the polyimide resin molded product is deformed during this heat treatment and the dimensional change is remarkable. Further, when heat treatment is performed for a short time, it is necessary to perform the heat treatment at a high temperature, and in this case, deterioration of the resin is promoted.

Furthermore, the applicant of the present application has found that it is effective to blend a thermotropic liquid crystal polymer with the above polyimide resin in order to improve the drawbacks of the above-mentioned polyimide resin molded product, and filed a patent application (Japanese Patent Laid-Open No. 04- 175373
issue). Since this resin composition is excellent in heat resistance, toughness, workability, etc., application development is being promoted in the fields conventionally considered to be in the area of metals or ceramics. However, a molded article obtained from this resin composition has a problem of large anisotropy. Furthermore, although the crystallization rate of polyimide increases due to the effect of adding a liquid crystal polymer and the liquid crystalization conditions are relaxed, the molded product tends to warp after heat treatment, and the layered dispersion of the liquid crystal polymer near the gate of the molded product causes the gate There is also a problem that a peeling phenomenon occurs in the part.

Further, Japanese Patent Application Laid-Open No. 04-175373 discloses a resin composition obtained by adding polyether ketone to the above polyimide resin. However, this resin composition has poor thermal stability and fluidity at high temperatures, and has a problem in molding conditions.

As described above, conventional polyimide resin compositions have not been satisfactory yet.

[0014]

DISCLOSURE OF THE INVENTION The object of the present invention is to remarkably relax the heat treatment conditions of a polyimide resin composition which has conventionally been required for a long time at a high temperature, and has good dimensional stability before and after heat treatment and excellent high temperature physical properties. , And fluidity during molding,
It is an object of the present invention to provide a polyimide resin composition having improved stability, anisotropy of a heat-treated product, and resin releasability.

[0015]

Means for Solving the Problems The inventors of the present invention have conducted extensive studies to achieve the above-mentioned object, and as a result, by adding a specific amount of polyetheretherketone to the polyimide resin, the polyimide resin at the time of heat treatment It was found that crystallization can be remarkably promoted, and the heat treatment conditions of the polyimide resin composition can be remarkably relaxed. Furthermore, the anisotropy of the obtained heat treatment product is small, the dimensional stability before and after the heat treatment is good, and the resin peels. The present invention has been completed by finding that it is a composition having no high temperature and excellent physical properties at high temperature.

That is, the present invention is a composition containing 50 to 5 parts by weight of a polyether ether ketone with respect to 50 to 95 parts by weight of a polyimide resin having a repeating unit represented by the formula (1). 250 ° C-330
The crystallization enthalpy value after the heat treatment at a temperature of 0 ° C., that is, the value measured by a differential scanning calorimeter at a temperature rising rate of 10 ° C./min is 0 to 6 cal / g. It is a polyimide resin composition.

[0017]

[Chemical 8] (In the formula, X is a direct bond or is selected from the group consisting of a divalent hydrocarbon group having 1 to 10 carbon atoms, a hexafluorinated isopropylidene group, a carbonyl group, a thio group, a sulfonyl group and an oxo group. Represents a group, Y ₁ , Y ₂ , Y ₃ and Y ₄ are each hydrogen, a lower alkyl group having 1 to 9 carbon atoms,
It represents a group selected from the group consisting of a lower alkoxy group having 1 to 9 carbon atoms, chlorine and bromine, and R ₁ has 2 to 2 carbon atoms.
7, which is an aliphatic group, a monocyclic aliphatic group, a monocyclic aromatic group, a condensed polycyclic aromatic group, and a non-condensed polycyclic group in which aromatic groups are connected to each other directly or by a crosslinking member. It represents a tetravalent group selected from the group consisting of aromatic groups. ).

Furthermore, the present invention is a fiber-reinforced polyimide resin composition containing 1 to 50 parts by weight of fibers based on 99 to 50 parts by weight of the above polyimide resin composition.

The polyimide resin having a repeating unit represented by the formula (1) as a basic skeleton, which is used in the present invention, has, for example, the formula (3)

[0020]

[Chemical 9] (Wherein, X and Y _{1 to} Y ₄ are the same as above) 1
At least one etherdiamine and formula (4)

[0021]

[Chemical 10] (In the formula, R ₁ is the same as above.) And one or more tetracarboxylic acid dianhydrides are reacted in the presence or absence of an organic solvent to chemically react the resulting polyamic acid. Alternatively, it can be produced by thermal imidization.

The reaction temperature is usually 250 ° C. or lower, and the reaction pressure is not particularly limited, and it can be sufficiently carried out at normal pressure. The reaction time varies depending on the tetracarboxylic dianhydride used, the type of solvent, and the reaction temperature, and the reaction is usually performed for a time sufficient to complete the production of the polyamic acid as an intermediate product.
A reaction time of 24 hours, sometimes 1 hour or less, is sufficient. By such a reaction, a polyamic acid corresponding to the repeating unit of the formula (1) is obtained, and then the polyamic acid is heated and dehydrated to 100 to 400 ° C. or chemically imidized by using a commonly used imidizing agent. As a result, a polyimide resin having the repeating unit of the formula (1) is obtained. Further, it is also possible to obtain a polyimide resin by simultaneously performing generation of polyamic acid and thermal imidization reaction.

Further, the ether diamine represented by the above formula (3) and the tetracarboxylic dianhydride represented by the above formula (4) are added to the formula (A).

[0024]

[Chemical 11] (In the formula, Z ₁ has 6 to 15 carbon atoms, and an aliphatic group, a cycloaliphatic group, a monocyclic aromatic group, a condensed polycyclic aromatic group, and an aromatic group are directly or crosslinked members. Represents a divalent group selected from the group consisting of non-condensed polycyclic aromatic groups interconnected with each other by a), or a dicarboxylic acid anhydride represented by the formula (B) Z ₂ —NH ₂ (B (In the formula, Z ₂ has 6 to 15 carbon atoms, and an aliphatic group, a cycloaliphatic group, a monocyclic aromatic group, a condensed polycyclic aromatic group, and an aromatic group are directly or crosslinked. A monovalent group selected from the group consisting of non-condensed polycyclic aromatic groups interconnected by a member), and the resulting polyamic acid is reacted thermally in the presence of an aromatic monoamine. Alternatively, the molecular end of the polymer obtained by chemical imidization has a dicarboxylic acid anhydride or an aromatic monoamine. It is also possible to use a sealed polyimide resin.

Specific examples of the etherdiamine represented by the formula (3), which is one of the raw materials for producing the polyimide resin represented by the formula (1), are shown below.

Examples of the diamine in which X in the formula (3) is an aliphatic group include bis [4- (3-aminophenoxy) phenyl] methane and 1,1-bis [4- (3-aminophenoxy) phenyl]. Ethane, 1,2-bis [4- (3-aminophenoxy) phenyl] ethane, 2,2-bis [4-
(3-Aminophenoxy) phenyl] propane, 2-
[4- (3-aminophenoxy) phenyl] -2- [4
-(3-Aminophenoxy) -3-methylphenyl] propane, 2,2-bis [4- (3-aminophenoxy)
-3-methylphenyl] propane, 2- [4- (3-aminophenoxy) phenyl] -2- [4- (3-aminophenoxy) -3,5-dimethylphenyl] propane,
2,2-bis [4- (3-aminophenoxy) -3,5
-Dimethylphenyl] propane, 2,2-bis [4-
(3-Aminophenoxy) -phenyl] butane, 2,2
-Bis [4- (3-aminophenoxy) -phenyl]-
1,1,1,3,3,3-hexafluoropropane and the like can be mentioned.

As the diamine in which X in the formula (3) is a direct bond, 4,4'-bis (3-aminophenoxy) biphenyl and 4,4'-bis (3-aminophenoxy)-
3-methylbiphenyl, 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)
-3,5-dichlorobiphenyl, 4,4'-bis (3-
Aminophenoxy) -3,3 ', 5,5'-tetrachlorobiphenyl, 4,4'-bis (3-aminophenoxy) -3,3'-dibromobiphenyl, 4,4'-bis (3-aminophenoxy) ) -3,5-Dibromobiphenyl, 4,4'-bis (3-aminophenoxy) -3,
3 ', 5,5'- tetrabromobiphenyl etc. are mentioned.

Examples of the diamine in which X in the formula (3) is -CO- include bis [4- (3-aminophenoxy) phenyl] ketone.

Examples of the diamine in which X in the formula (3) is -S- include bis [4- (3-aminophenoxy) phenyl] sulfide and bis [4- (3-aminophenoxy).
-3-methoxyphenyl] sulfide, bis [4- (3
-Aminophenoxy) phenyl] [4- (3-aminophenoxy) 3,5-dimethoxyphenyl] sulfide,
Examples thereof include bis [4- (3-aminophenoxy) -3,5-dimethoxyphenyl] sulfide.

Examples of the diamine in which X in the formula (3) is --SO ₂ --include bis [4- (3-aminophenoxy) phenyl] sulfone.

Examples of the diamine wherein X in the formula (3) is —O— include bis [4- (3-aminophenoxy) phenyl] ether and the like.

These ether diamines may be used alone or in 2
A mixture of two or more species can be used.

Further, other diamines can be mixed and used within a range that does not impair the melt fluidity of the thermoplastic polyimide resin. Examples of diamines that can be mixed and used include m-aminobenzylamine, p-aminobenzylamine, 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 sulfone, 3,4'-diaminodiphenyl sulfone, 4,4'-diaminodiphenyl sulfone, 3,3'-diaminobenzophenone, 3,
4'-diaminobenzophenone, 4,4'-diaminobenzophenone, 1,3-bis (3-aminophenoxy)
Benzene, 1,3-bis (4-aminophenoxy) benzene, 1,4-bis (3-aminophenoxy) benzene, 1,4-bis (4-aminophenoxy) benzene,
2,2-bis- [4- (4-aminophenoxy) phenyl] propane, 4,4′-bis (4-aminophenoxy) biphenyl, 4,4′-bis (4-aminophenoxy) phenyl] ketone, bis [4-aminophenoxy)
Phenyl] sulfide, bis [4- (4-aminophenoxy) phenyl] sulfone, bis [4- {4- (4-aminophenoxy) phenoxy} phenyl] ketone, bis [4- {4- (4-aminophenoxy) Phenoxy} phenyl] sulfone, bis [4- (4-aminophenoxy) phenyl] ether, 1,4-bis [4- (3-aminophenoxy) phenoxy] benzene, 1,4-bis [4- (4-amino) Phenoxy) phenoxy] benzene, 1,4-bis [4- (3-aminophenoxy) benzoyl] benzene, 1,3-bis [4- (3-aminophenoxy) benzoyl] benzene, bis [4- {4-
(4-aminophenoxy) phenoxy} phenyl] sulfone and the like.

These diamines are usually used by mixing 30% by weight or less, preferably 5% by weight or less.

As the tetracarboxylic acid dianhydride represented by the formula (4) which is the other raw material for producing the polyimide resin represented by the formula (1), R ₁ in the formula (4) is, for example, A compound that is at least one group selected from the group consisting of a) to (e) is used. (A) C2-C9 aliphatic group (b) C4-C10 cycloaliphatic group (c) Monocyclic aromatic group represented by the following formula.

[0036]

[Chemical 12] (D) Fused polycyclic aromatic group represented by the following formula

[0037]

[Chemical 13] (E) A non-condensed polycyclic aromatic group in which aromatic groups represented by the following formulas are connected to each other directly or by a crosslinking member.

[0038]

[Chemical 14] As the anhydride in which R ₁ in the formula (4) is an aliphatic group,
1,1,2,2-ethylenetetracarboxylic dianhydride,
1,2,1,2-ethylenetetracarboxylic dianhydride,
Examples of the anhydrides in which butanetetracarboxylic dianhydride is R ₁ is a cycloaliphatic group include cyclopentanetetracarboxylic acid dianhydride, and those in which R ₁ is a monocyclic aromatic group are anhydrous. Pyromellitic dianhydride, 1,
2,3,4-benzenetetracarboxylic dianhydride can be mentioned.

R ₁ in the formula is represented by the following formula,

[0040]

[Chemical 15] An anhydride in which X _{1 in} the formula is a —CO— group is 3,
3 ', 4,4'-benzophenone tetracarboxylic acid dianhydride, 2,2', 3,3'-benzophenone tetracarboxylic acid dianhydride, and the anhydride in which X _{1 in} the formula is a direct bond Include 3,3 ', 4,4'-biphenyltetracarboxylic dianhydride and 2,2', 3,3'-biphenyltetracarboxylic dianhydride, wherein X _{1 in} the formula is a fat As the anhydride that is a group, 2,2-bis (3,4-dicarboxyphenyl) propane dianhydride,
2,2-bis (2,3-dicarboxyphenyl) propane dianhydride, 1,1- (2,3-dicarboxyphenyl) ethane dianhydride, bis (2,3-dicarboxyphenyl) methane dianhydride And bis (3,4-dicarboxyphenyl) methane dianhydride, wherein X _{1 in} the formula is-
Examples of the anhydride that is an O-group include bis (3,4-dicarboxyphenyl) ether dianhydride, and examples of the anhydride that X _{1 in} the formula is a -SO ₂ -group include bis (3 ，
4-dicarboxyphenyl) sulfone dianhydride can be mentioned.

As the anhydride in which R ₁ in the formula (4) is a condensed polycyclic aromatic group, 2,3,6,7-naphthalenetetracarboxylic dianhydride, 1,4,5,5 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-phenanthrene tetracarboxylic acid dianhydride may be mentioned.

These may be used alone or in admixture of two or more.

Examples of the dicarboxylic acid anhydride of the formula (A) optionally used as an end capping agent include phthalic anhydride, 2,3-benzophenone dicarboxylic acid anhydride,
3,4-benzophenone dicarboxylic acid anhydride, 2,3-
Dicarboxyphenyl phenyl ether anhydride, 3,4
-Dicarboxyphenyl phenyl ether anhydride, 2,
3-biphenyldicarboxylic acid anhydride, 3,4-biphenyldicarboxylic acid anhydride, 2,3-dicarboxyphenylphenyl sulfone anhydride, 3,4-dicarboxyphenylphenyl sulfone anhydride, 2,3-dicarboxyphenylphenyl Sulfide anhydride, 3,4-dicarboxyphenylphenyl sulfide anhydride, 1,2-naphthalenedicarboxylic acid anhydride, 2,3-naphthalenedicarboxylic acid anhydride, 1,8-naphthalenedicarboxylic acid anhydride,
1,2-anthracene dicarboxylic acid anhydride, 2,3-anthracene dicarboxylic acid anhydride, 1,9-anthracene dicarboxylic acid anhydride and the like can be mentioned. These dicarboxylic acid anhydrides may be substituted with groups that are not reactive with amines or dicarboxylic acid anhydrides.

Among these dicarboxylic acid anhydrides, phthalic anhydride is most preferable from the viewpoint of properties and practical use of the polyimide. That is, when phthalic anhydride is used, a polyimide having excellent molding stability during high-temperature molding can be obtained, which is extremely useful in view of the above excellent processability. When phthalic anhydride is used, there is no problem in substituting a part of it with another dicarboxylic acid anhydride as long as the good physical properties of the polyimide are not impaired.

The amount of the dicarboxylic acid anhydride used is 0.001 to 1 mol per 1 mol of the ether diamine represented by the formula (2).
It is 1.0 mol. If it is less than 0.001 mol, the viscosity will increase during high temperature molding, which will cause deterioration of molding processability. Also,
If it exceeds 1.0 mol, the mechanical properties deteriorate. The preferred amount used is 0.01 to 0.5 mol.

Examples of the aromatic monoamine of the above formula (B) optionally used as an end-capping agent include aniline, o-toluidine, m-toluidine, p-toluidine, 2,3-xylidine, and 2,6-xylidine. , 3, 4
-Xylidine, 3,5-xylidine, o-chloroaniline, m-chloroaniline, p-chloroaniline, o-bromoaniline, m-bromoaniline, p-bromoaniline, o-nitroaniline, m-nitroaniline, p -Nitroaniline, o-aminophenol, m-aminophenol, p-aminophenol, o-anisidine, m-
Anisidine, p-anisidine, o-phenidine, m-phenidine, p-phenidine, o-aminobenzaldehyde, m-aminobenzaldehyde, p-aminobenzaldehyde, o-aminobenzonitrile, m-aminobenzonitrile, p- Aminobenzonitrile, 2-aminobiphenyl, 3-aminobiphenyl, 4-aminobiphenyl, 2-aminophenylphenyl ether, 3-aminophenylphenyl ether, 4-aminophenylphenyl ether, 2-aminobenzophenone, 3-aminobenzophenone, 4-aminobenzophenone, 2-aminophenylphenyl sulfide, 3-aminophenylphenyl sulfide, 4-aminophenylphenyl sulfide, 2-aminophenylphenyl sulfone, 3-aminophenylphenyl Sulfone, 4-aminophenyl phenyl sulfone, alpha-naphthylamine, beta-naphthylamine, 1-amino-2-naphthol, 2-amino-1-naphthol, 4-amino-1-naphthol, 5-amino -
1-naphthol, 5-amino-2-naphthol, 7-amino-2-naphthol, 8-amino-1-naphthol,
8-amino-2-naphthol, 1-aminoanthracene, 2-aminoanthracene, 9-aminoanthracene and the like can be mentioned. These aromatic monoamines may be substituted with groups that are not reactive with amines or dicarboxylic acid anhydrides.

The amount of the aromatic monoamine used is 1 mol of tetracarboxylic dianhydride represented by the formula (3).
The molar ratio is 0.001 to 1.0. If it is less than 0.001 mol, the viscosity will increase during high temperature molding, which will cause deterioration of molding processability. On the other hand, if it exceeds 1.0 mol, the mechanical properties will deteriorate.
The preferred amount used is 0.01 to 0.5 mol.

The logarithmic viscosity of the polyimide resin having the repeating unit represented by the formula (1) is usually 0.35 to 0.65 dl /
g, preferably in the range of 0.40 to 0.60 dl / g. If the logarithmic viscosity is less than 0.35 dl / g, mechanical properties and durability tend to be insufficient, and 0.65 dl / g
If it exceeds g, the moldability tends to deteriorate and injection molding tends to be difficult. This logarithmic viscosity is 0.5 g / 10 in a mixed solvent of parachlorophenol / phenol (90/10 weight ratio).
After being dissolved by heating in 0 ml of a solvent, it is cooled to 35 ° C. and measured.

The polyether ether ketone used in the present invention is a thermoplastic resin having the basic structure of the formula (2).

[0050]

[Chemical 16] The representative commercially available polyetheretherketone is "VICTREX PEEK" manufactured by ICI of the United Kingdom.
450P "" VICTREX PEEK 380P "
“VICTREX PEEK 150P” (above, trade name) and the like can be mentioned.

In the present invention, the mixing ratio of the polyimide resin and the polyether ether ketone is 50 to 5 parts by weight of the polyether resin to 50 to 95 parts by weight of the polyimide resin (the total of both is 100 parts by weight). To). If the blending ratio of the polyetheretherketone exceeds 40 parts by weight, the high temperature mechanical properties of the heat-treated product obtained will deteriorate and the excellent high temperature properties of the polyimide resin will be impaired. Also, the mixing ratio of polyetheretherketone is 5
If it is less than part by weight, the crystallization-promoting effect is lowered, and it is not possible to expect a reduction in the heat treatment temperature and time, and the resulting heat-treated product undergoes significant dimensional changes. A desirable mixing ratio is 40 to 5 parts by weight of polyether ether ketone with respect to 60 to 95 parts by weight of polyimide resin. A more preferable blending ratio is
Polyether ether ketone is 40 to 10 parts by weight with respect to 60 to 90 parts by weight of the polyimide resin.

The polyimide resin composition of the present invention is 25
It was heat-treated at a temperature of 0 ° C to 330 ° C. Also,
Temperature rise measurement (10 ° C./mi) of the polyimide resin composition after heat treatment by a differential scanning calorimeter (hereinafter referred to as DSC).
In n), the crystallization enthalpy of the polyimide component in the heat-treated product is in the range of 0 to 6 cal / g.

The heat treatment conditions that bring about the above DSC measurement result are, for example, 250 ° C. for 20 hours or longer, 260 ° C. for 5 hours or longer, 270 ° C. for 3 hours or longer, and 290 ° C. for 3 hours.
0 minutes or longer, 300 ° C. for 30 seconds or longer, 320 ° C. for 10 seconds or longer, etc. If the heat treatment temperature is less than 250 ° C., 3
It requires 00 hours and is not practical. Further, when the heat treatment temperature exceeds 330 ° C., remarkable deformation occurs, which is also not practical. Considering practicality and transformation, 260 more
C.-310.degree. C. is desirable, and 260.degree. C.-290.degree. C. is more preferable.

The crystallization enthalpy of the polyimide component by this DSC measurement shows how much the polyimide component during the heat treatment has a crystallinity. For example, the crystallization enthalpy value (ΔHc) measured by DSC is 0 cal / g
In the case of, the crystallinity of the polyimide component reached the maximum crystallinity due to the heat treatment, and it was not crystallized at all in the DSC measurement. That is, since the maximum crystallinity of this polyimide resin is 30 to 40%, ΔHc = 0 cal / g of the polyimide component means that the crystallinity of the polyimide resin is 30 to 40%.

The crystallization enthalpy value (ΔHc) of the amorphous polyimide measured by DSC is 8 to 10 cal / g.
Therefore, ΔHc = 8 to 10 cal / g means that the crystallinity of the polyimide resin is 0%.

That is, the smaller the crystallization enthalpy value (ΔHc) of the polyimide component measured by DSC, the more the crystallization progressed by the heat treatment.

Further, the polyimide resin composition 9 of the present invention
It is also possible to obtain a fiber-reinforced polyimide resin composition containing 9 to 50 parts by weight and 1 to 50 parts by weight of fibers. If the blending ratio of the fibers is less than 1 part by weight, the reinforcing effect of the fibers is insufficient, and if it exceeds 50 parts by weight, the surface smoothness during crystallization after molding remarkably deteriorates.

The fibers are not particularly limited, and include, for example, PAN-based and pitch-based carbon fibers, glass fibers, metal fibers, aramid fibers represented by Kevlar (trade name), potassium titanate fibers, aluminum borate fibers. , Tyranno fiber and the like.

Furthermore, if necessary, the polyimide resin composition of the present invention may have a fibrous reinforcing material other than those mentioned above (for example,
Optical fiber, ceramic fiber, boron fiber, silicon carbide fiber, asbestos, rock wool, etc.); calcium carbonate,
Mica, glass beads, graphite, molybdenum disulfide, clay, silica, alumina, talc, diatomaceous earth,
Fillers such as hydrated alumina and shirasu balloons; lubricants, release agents, stabilizers, colorants, crystal nucleating agents; other thermoplastic resins (eg, polyphenylene sulfide, polyetherimide, polyether sulfone, etc.); You may use together thermosetting resin (for example, epoxy resin, silicone resin, polyamide imide resin, etc.) and / or fluororesin such as polytetrafluoroethane.

[0060]

EXAMPLES The present invention will now be described in detail with reference to Examples and Comparative Examples.

The polyether ether ketone (PEEK), polyether ketone (PEK) and liquid crystal polymer (LCP) used in the examples and comparative examples are as follows. (1) Polyetheretherketone ICI's PEEK 450P ICI's PEEK 380P (2) Polyetherketone ICI's PEK 220P (3) Liquid crystal polymer Nippon Petrochemical Zyder SRT500 Sumitomo Chemical's Econol E6000 <Example 1 To 12> 4,4′-bis (3-aminophenoxy) biphenyl and pyromellitic dianhydride as raw materials, polyimide resin having logarithmic viscosity of 0.52 dl / g 80
Parts by weight and polyetheretherketone (PEEK 45
0P) 20 parts by weight are dry-mixed and then extruded at 370 to 400 ° C. using a twin-screw extruder to granulate, and the obtained pellets are injection-molded (cylinder temperature 370-410 ° C., injection pressure 900 kg / cm ² , the mold temperature 180 ℃),
A test piece defined by each test method described later was molded. First
After performing the heat treatment under the conditions shown in the table, various measurements were performed by the methods described below, and the results shown in Table 1 were obtained. As a heat treatment device, an inert oven DN4 manufactured by Yamato Scientific Co., Ltd.
3HI / 63HI (trade name) was used. Each test method is as follows.

1) Dimension measurement: The dimensional change rate before and after the heat treatment in the flow direction of a 75 mm × 100 mm × 2 ^t flat plate and in the direction perpendicular to the flow was measured. 2) Roundness measurement: external shape 75mm,
The roundness of a ring having an inner diameter of 45 mm and a thickness of 2 mm after heat treatment was measured.

3) Tensile strength: Performed according to ASTM-638.

4) Flexural Modulus It was conducted according to ASTM-790.

5) DSC measurement Using a differential scanning calorimeter, 2 of heating process (10 ° C./min)
The amount of heat of the peak (crystallization enthalpy) detected at 90 ° C to 320 ° C was measured. Further, this measured value was converted into the heat quantity of the polyimide component according to the following formula, and the value was taken as the crystallization enthalpy value of the polyimide component in the heat-treated product.

Crystallization enthalpy value of polyimide component during heat treatment A × 100 ÷ (parts by weight of polyimide in resin composition) where A is the amount of heat of the peak at which the peak top is detected at 290 ° C. to 320 ° C. The unit is cal / g.

6) Presence or absence of peeling Bending stress was applied to the vicinity of the gate of the tensile test piece with a nipper, and the presence or absence of peeling of the surface layer at that time was confirmed.

<Examples 13 to 24> Test pieces were prepared in the same manner as in Example 1 except that the mixing ratios of the raw materials were as shown in Table 2, and the properties of each were measured. The obtained results are also shown in Table 2. In addition, PEE
380P was used for K.

<Examples 25 to 36> Test pieces were prepared in the same manner as in Example 1 except that the mixing ratios of raw materials and the heat treatment conditions were as shown in Table 3. The properties were measured, and the obtained results are also shown in Table 3. In addition, 450P was used for PEEK.

<Examples 37 to 48> Test pieces were prepared in the same manner as in Example 1 except that the mixing ratios of raw materials and the heat treatment conditions were as shown in Table 4. The properties were measured, and the obtained results are also shown in Table 4. In addition, 450P was used for PEEK.

<Comparative Examples 1 to 9> Example 1 was repeated except that the polyether ether ketone was not used and the polyimide resin was used alone and the heat treatment conditions were as shown in Table 5.
The test pieces were prepared in the same manner as above, the properties of each were measured, and the obtained results are also shown in Table 5. still,
450P was used for PEEK.

Comparative Examples 10 to 21 All the same operations as in Example 1 were carried out except that the heat treatment conditions were insufficient and the crystallization enthalpy was outside the range of the present invention as shown in Table 6. Test pieces were prepared, their properties were measured, and the obtained results are also shown in Table 6. In addition, it is 45 for PEEK
0P was used.

<Comparative Examples 22 to 23> Tests were conducted in the same manner as in Example 1 except that the amount of polyether ether ketone was increased as shown in Table 7 to fall outside the range of the present invention. Pieces were prepared, their properties were measured, and the obtained results are also shown in Table 7. In addition, 450 for PEEK
P was used.

Comparative Examples 24 to 25 Tests were carried out in the same manner as in Example 1 except that the amount of polyether ether ketone was increased as shown in Table 8 to fall outside the range of the present invention. Pieces were prepared, their properties were measured, and the obtained results are also shown in Table 8. 380 for PEEK
P was used.

<Comparative Examples 26 to 27> As shown in Table 9, test pieces were prepared in the same manner as in Example 1 except that a liquid crystal polymer (LCP) was used instead of the polyether ether ketone. Made, measured each property,
The results obtained are also shown in Table 9.

<Evaluation of Examples 1 to 48 and Comparative Examples 1 to 27> Comparing Tables 1 to 4 (Examples 1 to 48) and Table 5 (Comparative Examples 1 to 9) of the present invention, the polyimide Comparative Examples 1 to 9 in which the resin was used alone did not reach the predetermined enthalpy of crystallization even when subjected to heat treatment at high temperature for a long time, and the physical properties of the resulting compositions were poor, while the present invention It can be seen that crystallization is completed in a short time.

Comparing Tables 1 to 4 (Examples 1 to 48) of the present invention with Table 6 (Comparative Examples 10 to 21), Comparative Examples 10 to 21 which do not reach a predetermined crystallization enthalpy show crystallization. It is found that the tensile strength at 230 ° C., particularly the bending elastic modulus, is extremely lowered as a result, and the mechanical properties at high temperature are significantly lowered.

Comparing Tables 1 to 4 (Examples 1 to 48) of the present invention with Tables 7 to 8 (Comparative Examples 22 to 25), the blending amount of polyether ether ketone exceeds the range of the present invention. In Comparative Examples 22 to 25, it can be seen that the tensile strength at 230 ° C., especially the flexural modulus, etc., are extremely reduced, and the mechanical properties at high temperatures are significantly reduced.

Tables 1 to 4 (Examples 1 to 48) of the present invention and Table 9 (Comparative Example 26) which is a resin composition with a liquid crystal polymer.
~ 27), Examples 1 to 48, which are compositions of polyimide resin and polyether ether ketone, undergo isotropic dimensional changes during heat treatment and have a small roundness, and die designs of various molded products. Easy, good dimensional stability,
Further, the resin is not separated from each other, whereas the composition of the polyimide resin and the liquid crystal polymer is Comparative Example 26-
It was found that in No. 27, the roundness was poor and a peeling phenomenon occurred.

<Examples 49 to 50, Comparative Examples 28 to 29>
Except for changing the blending ratio of the raw materials as shown in Table 10, the same operation as in Example 1 was performed to prepare a resin composition and compare the thermal stability. The thermal stability was evaluated by measuring the spiral flow length. The spiral flow length is measured at a cylinder temperature of 410 ° C., a mold temperature of 180 ° C., an injection pressure of 1500 kg / cm ² , and a wall thickness of 1 mm (no retention), and then at 410 ° C. for 10 minutes with a resin (composition). It was made to stay in the cylinder, and the spiral flow length was measured again under the above conditions (after 10 minutes of stay).

As shown in Table 10, the spiral flow lengths of Examples 49 and 50 after 10 minutes of residence were as shown in Comparative Example 28,
It is larger than that of No. 29, and it can be seen that the polyimide resin / PEEK is remarkably improved in fluidity and thermal stability during molding as compared with the polyimide resin / PEEK.

Next, the fiber-reinforced polyimide resin composition will be described in detail with reference to Examples and Comparative Examples. The measurements in the following examples and comparative examples were carried out by the following methods.

Ra: According to the center line average roughness measurement of JIS-B0601.

HDT: According to ASTM D-648.

<Examples 51 to 55, Comparative Examples 30 to 32>
Polyimide resin powder obtained by using 4,4′-bis (3-aminophenoxy) biphenyl and pyromellitic dianhydride as raw materials, polyether ether ketone (manufactured by ICI, VICTREX PEEK 450P Natural), and Table 11 40 m after dry-blending each of the fiber bundles having a length of 3 mm with the composition shown in Table 11
An extruding operation was performed with an m-diameter extruder while melt-kneading at an extrusion temperature of 380 to 400 ° C. to obtain a uniform blended pellet.

Then, dumbbell test pieces were prepared from the above-mentioned uniformly compounded pellets using an ordinary injection molding machine, and the average surface roughness was measured. Then, the dumbbell test piece was subjected to 260 ° C / 2.
Crystallization was carried out by heating for 0 hour and further at 320 ° C./2 hours, and the average surface roughness was measured again. The results are shown in Table 11.

Example 56 A test piece (6 mm × 70 mm × 3 mm) was molded using the pellets obtained in Example 51 and crystallized in the same manner as in Example 51, and HDT was measured.
It was 0 ° C.

<Comparative Example 33> HDT was measured in the same manner as in Example 56 except that the resin composition was changed to 40 parts by weight of polyimide resin and 60 parts by weight of PEEK.
Met. That is, the heat resistance of the polyimide resin was impaired as compared with Example 56.

<Examples 57 to 58 and Comparative Example 34> Polyimide resin powder, polyetheretherketone, and the second product obtained by using bis [4- (3-aminophenoxy) phenyl] sulfide and pyromellitic dianhydride as raw materials. 1
The fibers shown in Table 2 were dry blended, and then treated in the same manner as in Example 51 to measure Ra. The results are shown in Table 12.

<Examples 59 to 60, Comparative Example 35> 2,2
-Bis [4- (3-aminophenoxy) phenyl] propane and 3,3 ', 4,4'-benzophenone tetracarboxylic acid dianhydride as a raw material, polyimide resin powder obtained, polyetheretherketone and Table 12 The fiber shown in 1 was dry blended and treated in the same manner as in Example 51 to measure Ra. The results are shown in Table 12.

<Example 61> 70 parts by weight of the polyimide resin powder of Example 51 and 30 parts by weight of carbon fiber having a length of 3 mm were dry blended, and then extruded while melt-kneading at an extrusion temperature of 400 ° C to form pellets. Got On the other hand, 70 parts by weight of polyether ether ketone of Example 51 and a length of 3
After 30 parts by weight of mm carbon fiber was dry-blended, it was extruded while melt-kneading at an extrusion temperature of 380 ° C. to obtain pellets. 70 parts by weight of the fiber-reinforced polyimide resin pellets thus obtained and 30 parts by weight of the fiber-reinforced polyether ether ketone pellets were dry-blended and injection-molded to prepare a dumbbell test piece.
It was heated for / 5 hours for crystallization, and then Ra was measured in the same manner as in Example 51. As a result, Ra before crystallization was 0.72.
The Ra after crystallization was 1.40 μm, which was almost the same as in Example 51.

[0092]

[Table 1]

[0093]

[Table 2]

[0094]

[Table 3]

[0095]

[Table 4]

[0096]

[Table 5]

[0097]

[Table 6]

[0098]

[Table 7]

[0099]

[Table 8]

[0100]

[Table 9]

[0101]

[Table 10]

[0102]

[Table 11]

[0103]

[Table 12]

[0104]

EFFECTS OF THE INVENTION The polyimide resin composition of the present invention can be used without impairing the properties of the polyimide resin as the base resin.
It can be heat-treated at low temperature for a short time, and the obtained heat-treated product has excellent dimensional stability with small dimensional change and roundness, and excellent high-temperature physical properties. Furthermore, since the fluidity and stability during molding are good, the molding conditions can be relaxed. Furthermore, the anisotropy of the heat-treated product is small, and the resin does not peel off.

Since the heat-treated product of this polyimide resin composition is very excellent in high-temperature physical properties, sliding properties, heat resistance and chemical resistance, mechanical parts such as gears, cams, pushings, pulleys, sleeves, bearings, etc. , Connector, bobbin,
It can be widely used for electric / electronic parts such as IC sockets, automobile parts such as impellers, manifolds, valve guides, valve systems, piston skirts, oil pans, front covers, rocker covers, and sliding parts for various other devices. Therefore, the significance of the present invention can be said to be extremely great.

Further, in the fiber-reinforced polyimide resin composition of the present invention containing fibers, the effect that the heat resistance can be greatly improved by crystallization without impairing the surface smoothness can be obtained.

 ─────────────────────────────────────────────────── ─── Continuation of the front page (72) Inventor Kayako Ito 1190 Kasama-cho, Sakae-ku, Yokohama-shi, Kanagawa Mitsui Toatsu Chemicals, Inc. (72) Inventor Katsushi Shimamura 1190, Kasama-cho, Sakae-ku, Yokohama, Kanagawa Prefecture Mitsui Higashi Within the pressure chemistry Co., Ltd. (72) Inventor Hiroyasu Daichi 1190 Kasama-cho, Sakae-ku, Yokohama-shi, Kanagawa Mitsui Toatsu Chemicals Within (72) Inventor Hiroaki Tomimoto 1190 Kasama-cho, Sakae-ku, Yokohama-shi, Kanagawa Mitsui Toatsu Chemical Co., Ltd. In-house (72) Inventor Nobuhiro Takizawa 1190 Kasama-cho, Sakae-ku, Yokohama-shi, Kanagawa Mitsui Toatsu Chemical Co., Ltd. (72) Inventor Yoshihisa Goto 1190 Kasama-cho, Sakae-ku, Yokohama, Kanagawa Mitsui Toatsu Chemical Co., Ltd.

Claims (8)

[Claims] 1. 50 to 95 parts by weight of a polyimide resin having a repeating unit represented by the formula (1)
A composition containing 5 parts by weight of polyetheretherketone, further heat-treated at a temperature of 250 ° C. to 330 ° C., and showing a difference in the crystallization enthalpy value after the heat treatment, that is, a temperature rising rate of 10 ° C./min. The value measured by a scanning calorimeter is 0-6 cal / g, The polyimide resin composition characterized by the above-mentioned. [Chemical 1] (In the formula, X is a direct bond or is selected from the group consisting of a divalent hydrocarbon group having 1 to 10 carbon atoms, a hexafluorinated isopropylidene group, a carbonyl group, a thio group, a sulfonyl group and an oxo group. Represents a group, Y ₁ , Y ₂ , Y ₃ and Y ₄ are each hydrogen, a lower alkyl group having 1 to 9 carbon atoms,
It represents a group selected from the group consisting of a lower alkoxy group having 1 to 9 carbon atoms, chlorine and bromine, and R ₁ has 2 to 2 carbon atoms.
7, which is an aliphatic group, a monocyclic aliphatic group, a monocyclic aromatic group, a condensed polycyclic aromatic group, and a non-condensed polycyclic group in which aromatic groups are connected to each other directly or by a crosslinking member. It represents a tetravalent group selected from the group consisting of aromatic groups. ) 2. The polyimide resin having a repeating unit represented by the formula (1) is a dicarboxylic acid anhydride represented by the formula (A) or an aromatic monoamine represented by the formula (B) at the terminal of the polymer molecule. The polyimide resin composition according to claim 1, which is substituted or contains the substituted one. [Chemical 2] (In the formula, Z ₁ has 6 to 15 carbon atoms, and an aliphatic group, a cycloaliphatic group, a monocyclic aromatic group, a condensed polycyclic aromatic group, and an aromatic group are directly or crosslinked members. Represents a divalent group selected from the group consisting of non-fused polycyclic aromatic groups interconnected with each other.) Z ₂ —NH ₂ (B) (In the formula, Z ₂ has 6 to 15 carbon atoms. Yes, an aliphatic group, a cycloaliphatic group, a monocyclic aromatic group, a condensed polycyclic aromatic group, and a non-condensed polycyclic aromatic group in which aromatic groups are directly or cross-linked with each other. A monovalent group selected from the group consisting of groups is shown.) 3. The repeating unit of the polyimide resin comprises:
The polyimide resin composition according to claim 1, which has the formula (1 ′). [Chemical 3] (In the formula, X and R ₁ are the same as those in the formula (1).) 4. The polyimide resin composition according to claim 1, wherein the polyether ether ketone has a repeating unit of the formula (2) in the molecule. [Chemical 4] 5. The polyimide resin composition according to claim 1, wherein the compounding ratio of the polyimide resin and the polyether ether ketone is 40 to 5 parts by weight of polyether ether ketone to 60 to 95 parts by weight of the polyimide resin. 6. The polyimide resin composition according to claim 1, wherein the compounding ratio of the polyimide resin and the polyether ether ketone is 40 to 10 parts by weight of the polyether ether ketone with respect to 60 to 90 parts by weight of the polyimide resin. 7. A fiber-reinforced polyimide resin composition containing 1 to 50 parts by weight of fibers relative to 99 to 50 parts by weight of the resin composition according to claim 1. 8. The fiber according to claim 7, wherein the fiber is at least one selected from the group consisting of carbon fiber, glass fiber, metal fiber, aramid fiber, potassium titanate fiber, aluminum borate fiber and tyrano fiber. Fiber-reinforced polyimide resin composition.