JP2000191908A - Polyimide resin composition for melt molding, having good thermal stability - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain the subject composition enabling stable melt-molding and manifesting high thermal stability or the like by including a crystalline polyimide having a specific repeating unit and a resin such as polyphenylene sulfide resin in a specified proportion. SOLUTION: This composition comprises (A) 50-95 wt.% crystalline polyimide having 90-100 mol% repeating unit of formula I, and 10-0 wt.% repeating unit of formula II (R1 is a divalent aromatic group) or formula III (R2 is a tetravalent aromatic group), and further having a molecular terminal of formulas IV (R3 is a monovalent aromatic group) and/or V (R4 is a divalent aromatic group), and <=50% variation of the melt viscosity after 30 min preservation at 420 deg.C compared to that after 5 min preservation at the temperature, and (B) 50-5 wt.% one or more kinds of resins selected from a polyphenylene sulfide resin, a liquid crystal polymer resin, a polyethersulfone resin, a polysulfone resin and the like.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

TECHNICAL FIELD The present invention has a melt viscosity suitable for use in melt molding and has a small decrease in fluidity during melting.
Furthermore, the crystallization rate is made of a crystalline polyimide and various resins having a large crystallization rate, and the product obtained by molding is sufficiently crystallized without heat treatment, and has a high heat resistance, that is, a sufficient temperature even at a temperature equal to or higher than the glass transition temperature. The present invention relates to a polyimide resin composition for melt molding having high mechanical stability and high thermal stability.

[0002]

2. Description of the Related Art In addition to its excellent heat resistance, polyimide has excellent properties in mechanical properties, chemical resistance, flame retardancy, electrical properties, and the like.
It is widely used in the field of electronic components and the like.

As a molding material and a polyimide for a composite material, Vespel (trade name, manufactured by DuPont) or Up
Although imol (manufactured by Ube Industries) is known, all polyimides are insoluble and infusible, so they must be molded using a special method such as sintering via the precursor polyamic acid. And has poor moldability. Furthermore, this method has a serious problem in processing steps, cost, and the like. For example, it is difficult to obtain a processed product having a complicated shape, and in order to obtain a satisfactory molded product, it is necessary to perform finishing by cutting or the like.

[0004] As a thermoplastic polyimide capable of being injection-molded with improved moldability, a product name Ultem (manufactured by General Electric Company) is known (US Pa.).
t3,847,867, 3,847,869). However, since this polyimide is completely amorphous and has a glass transition temperature (Tg) of 215 ° C., it cannot be said that the polyimide has sufficient heat resistance. That is, taking as an example the deflection temperature under load (DTUL), which is the practical use limit temperature, the neat Ultem is 200 ° C and contains 30 wt% of carbon fiber (CF
30) Ultem is 212 ° C, which is not a high value for super engineering plastic.

[0005] As a new thermoplastic polyimide capable of injection molding with improved moldability, the product name is AURU.
M (manufactured by Mitsui Chemicals, Inc.) was developed (Japanese Patent Laid-Open No. 62-688).
17). Since this polyimide has a glass transition temperature of 250 ° C, DTUL is neat AURUM at 238 ° C and CF30-
AURUM has a higher heat resistance of 248 ° C than the above-mentioned polyimide Ultem.

AURUM is crystalline having a melting point of 388 ° C., and is heat-treated (annealed) after molding.
Can be crystallized. The DUTL when crystallized is a neat AURUM at 260 ° C, CF30-
AURUM has a remarkably high heat resistance of 349 ° C.

However, heat treatment for crystallization significantly reduces productivity, and further has problems such as dimensional change and deformation due to crystallization and surface roughening.

[0008] These problems do not arise at all if the product obtained by molding is sufficiently crystallized without heat treatment. For this reason, a method for promoting crystallization by adding an organic low molecular weight substance or a crystalline resin has been devised (Japanese Patent Application Laid-open No.
-104756, JP-A-9-188813, etc.). However, these methods have a problem that heat resistance and chemical resistance are reduced because a low molecular weight substance and a resin having low heat resistance are added. Other examples of crystalline polyimides include JP-A-61-143433 and JP-A-6-143433.
JP-A-112-1727 and JP-A-63-172735 disclose a polyimide comprising 1,3-bis (4-aminophenoxy) benzene and 3,3 ′, 4,4′-biphenyltetracarboxylic dianhydride. And its copolymers are described, and their melting points are indicated. However, there is no description on the melt fluidity and crystallization rate of the polyimide.

Also, Macromolecules 1997, 30, 1012-1022
Discloses the melt fluidity of a polyimide consisting of 1,3-bis (4-aminophenoxy) benzene and 3,3 ', 4,4'-biphenyltetracarboxylic dianhydride, the terminal of which is inactivated. Has been described. However,
The melt fluidity and crystallization rate of the copolymer are not known.

[0010] Furthermore, the polyimide comprising 1,3-bis (4-aminophenoxy) benzene and 3,3 ', 4,4'-biphenyltetracarboxylic dianhydride has a problem that thermal stability upon melting is poor. Had. JP-A-1-1-1
No. 10530, JP-A-1-123830 and the like describe a method for improving the thermal stability of a polyimide resin by inactivating the terminal by reacting with an aromatic monoamine and / or an aromatic dicarboxylic anhydride. However, even if the polyimide is inactivated at the terminal, the fluidity of the polyimide decreases with time during melting. Therefore, for example, at the time of injection molding, the injection pressure increases or the flow length of the resin decreases with time after the start of molding, so that not only cannot stable molding be performed, but also a product having stable color tone and physical properties cannot be manufactured. Therefore, the polyimide cannot be used for melt molding such as extrusion molding and injection molding, and its use has been limited to hot melt adhesives.

From the above, it can be seen that the crystallization rate is high, the decrease in fluidity during melting is small, stable melt molding is possible, and a product having stable color tone and physical properties can be produced. Crystalline polyimide resin with high viscosity has been demanded. Furthermore, it is possible to produce a product comprising the polyimide resin and various resins, capable of stable melt molding, having a stable color tone and physical properties, and having a product obtained by molding without heat treatment. Therefore, a polyimide resin composition for melt molding having high heat resistance, that is, having high mechanical stability even at a temperature equal to or higher than the glass transition temperature, and having high heat stability has been demanded.

[0012]

DISCLOSURE OF THE INVENTION The present invention is capable of producing a product having a stable color tone and physical properties that is capable of stable melt molding, and is capable of producing a product obtained by molding without heat treatment. Crystallized well, high heat resistance,
That is, an object of the present invention is to provide a polyimide resin composition for melt molding which has sufficient mechanical strength even at a temperature equal to or higher than the glass transition temperature and has high thermal stability.

[0013]

Means for Solving the Problems The present inventors have conducted intensive studies to solve the above-mentioned problems, and as a result, have found that 1,3-bis (4-aminophenoxy) benzene containing no high molecular weight impurities is used as a raw material monomer. 420 ° C only if
Compared with the melt viscosity when melted by holding for 5 minutes at 240 ° C.
90 to 100 mol% of the repeating unit represented by the formula (1), wherein the amount of change in the melt viscosity when kept at 30 ° C. for 30 minutes is within 50%, and the formula (2) or (3) A crystalline polyimide represented by the formula (4) and / or (5) having a molecular terminal represented by the formula (4) and / or (5) can be obtained. The resin composition is capable of stable melt molding, producing a product having stable color and physical properties, and the product obtained by molding is sufficiently crystallized without heat treatment, and has high heat resistance. That is, they have found that they have sufficient mechanical strength even at a temperature equal to or higher than the glass transition temperature, and have completed the present invention.

That is, in the present invention, 90 to 100 mol% of a repeating unit represented by the formula (1) (the same applies to the following formulas 2 to 5 by applying the formula (1) according to claim 1). And a repeating unit 10 represented by the formula (2) or (3):
30% at 420 ° C. as compared with the melt viscosity when held and melted at 420 ° C. for 5 minutes, the molecular end of which is represented by the formula (4) and / or (5). 50 to 95% by weight of crystalline polyimide having a change in melt viscosity of 50% or less when held, and polyphenylene sulfide resin, liquid crystal polymer resin, polyether sulfone resin, polysulfone resin, polyarylate resin, polyamide resin, poly The present invention relates to a polyimide resin composition for melt molding, comprising 50 to 5% by weight of one or more resins selected from ether resins, polyetherimide resins, polyamideimide resins, fluororesins, and polyimide resins.

More specifically, 90 to 100 mol% of a repeating unit represented by the formula (1) using 1,3-bis (4-aminophenoxy) benzene containing no high molecular weight impurities as a raw material monomer; 2) or (3)
And the molecular end thereof is compared with the melt viscosity at the time of melting at 420 ° C. for 5 minutes represented by the formula (4) and / or (5) at a molecular terminal represented by the formula (4) and / or (5). It is possible to carry out stable melt molding comprising a crystalline polyimide and various resins having a change in melt viscosity of 50% or less when held at 420 ° C. for 30 minutes, and to produce a product having stable color tone and physical properties. The present invention relates to a polyimide resin composition for melt molding, which is capable of crystallizing a product obtained by molding without heat treatment and having high heat resistance, that is, sufficient mechanical strength even at a temperature equal to or higher than the glass transition temperature.

In the present invention described above, the temperature at 420 ° C.
It is characteristic in that a crystalline polyimite having a change in melt viscosity of 50% or less when held at 420 ° C. for 30 minutes is within one component as compared with the melt viscosity when held and melted for one minute.

[0017]

BEST MODE FOR CARRYING OUT THE INVENTION The crystalline polyimide used in the present invention comprises 90 to 100 mol% of 1,3-bis (4-aminophenoxy) benzene and 10 to 0% of an aromatic diamine represented by the formula (8). Mol% and the polyamic acid obtained by reacting 3,3 ′, 4,4′-biphenyltetracarboxylic dianhydride is thermally or chemically imidized, or 1,3-bis (4- Aminophenoxy) benzene, 90 to 100 mol% of 3,3 ′, 4,4′-biphenyltetracarboxylic dianhydride and 10 to 0 mol% of tetracarboxylic dianhydride represented by the formula (9) It can be obtained by thermally or chemically imidizing a polyamic acid obtained by the reaction.

[0018]

Embedded image (In the formula, R1 is a divalent aromatic group, and R2 is a tetravalent aromatic group.) 1,3-bis (4-aminophenoxy) used in the present invention
Benzene is substantially free of high molecular weight impurities 1,
3-bis (4-aminophenoxy) benzene. Specifically, 100 μl of a tetrahydrofuran solution having a 1,3-bis (4-aminophenoxy) benzene concentration of 5% by weight, more preferably 10% by weight, was subjected to gel permeation chromatography with an RI detector (column: polymer laboratory). Company PLgel 0.75 × 300mm 2 in series,
Moving bed: tetrahydrofuran, flow rate: 0.75 ml / min)
1,3-bis (4-aminophenoxy) benzene having no higher molecular weight peak than 1,3-bis (4-aminophenoxy) benzene when implanted and observed, and more preferably a) 1, Tetrahydrofuran solution 100 having a concentration of 3-bis (4-aminophenoxy) benzene of 5% by weight or more
μl of gel permeation chromatography with RI detector (column: PLgel manufactured by Polymer Laboratory)
0.75 x 300mm two in series, moving bed: tetrahydrofuran, flow rate: 0.75ml / min)
There is no peak higher in molecular weight than 1,3-bis (4-aminophenoxy) benzene, and b) light transmission at 450 nm of a 10% by weight solution of 1,3-bis (4-aminophenoxy) benzene in dimethylformamide. When the transmittance was measured by an extra-visible visible altimeter having a cell length of 10 mm, the light transmittance was 60% or more,
Preferably, it is 70% or more, more preferably 80% or more of 1,3-bis (4-aminophenoxy) benzene.

1,3-Bis (4-aminophenoxy) benzene is obtained by reacting resorcinol and p-nitrochlorobenzene in an aprotic polar solvent in the presence of a base to obtain 1,3-bis (4-aminophenoxy) benzene. Produced by reducing nitrophenoxy) benzene with hydrogen. However, 1,3-bis (4-aminophenoxy) benzene obtained by the above method contains high molecular weight impurities and is further colored yellow or brown. Like this one
Polyimides obtained using 3-bis (4-aminophenoxy) benzene have poor thermal stability during melting and are difficult to use in melt molding applications. That is, even if such a polyimide is inactivated at the terminal by reacting with an aromatic monoamine and / or an aromatic dicarboxylic acid anhydride, its fluidity decreases with time during melting. Therefore, for example, at the time of injection molding, the injection pressure increases or the flow length of the resin decreases with time after the start of molding, and stable molding cannot be performed. Further, a molded product obtained by injection molding or the like has a problem that, for example, the color tone and physical properties are different between the first shot and the 100th shot. On the other hand, polyimide obtained by using 1,3-bis (4-aminophenoxy) benzene containing no high molecular weight impurities has good thermal stability at the time of melting.

1,3-Bis (4-aminophenoxy) benzene containing no high molecular weight impurities can be obtained by distilling 1,3-bis (4-aminophenoxy) benzene obtained by a conventional method. Distillation may be precision distillation or molecular distillation using a distillation column, or simple evaporation using a thin film evaporator, as long as high boiling point impurities can be removed. The distillation conditions are not particularly limited. For example, 240 ° C., 13.3 Pa or 300 ° C., 67 P
By distilling at a, 1,3-bis (4-aminophenoxy) benzene containing no high molecular weight impurities in a molten state is obtained as a distillate. In addition, 1,3 of the molten state
Since bis- (4-aminophenoxy) benzene is easily colored by oxygen, it is desirable to handle it in a vacuum or in an inert gas atmosphere. The 1,3-bis (4-aminophenoxy) benzene containing no high molecular weight impurities used in the present invention may be obtained by a method other than distillation as long as no high molecular weight impurities are contained.

Examples of the aromatic diamine represented by the formula (8) used in the present invention include: a) p-phenylenediamine, m-phenylenediamine having one benzene ring, b) benzene ring 2 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′-diaminodiphenylsulfone, 4,4′-diaminodiphenylsulfone, 3,3′-diaminobenzophenone, 3,4′-diaminobenzophenone, 4,
4'-diaminobenzophenone, 3,3'-diaminodiphenylmethane, 3,4'-diaminodiphenylmethane, 4,4'-diaminodiphenylmethane, 2,2-di (3-aminophenyl) propane, 2,2-di (4 -Aminophenyl) propane, 2- (3-aminophenyl)
-2- (4-aminophenyl) propane, 2,2-di (3-aminophenyl) -1,1,1,3,3,3-hexafluoropropane, 2,2-di (4-aminophenyl) -1,1,1,3,3,3-hexafluoropropane, 2- (3-aminophenyl) -2- (4-aminophenyl) -1,1,1,3,3,3-hexafluoropropane 1,1-di (3-aminophenyl) -1-phenylethane, 1,1-di (4-aminophenyl) -1-
Phenylethane, 1- (3-aminophenyl) -1-
(4-aminophenyl) -1-phenylethane, c) 1,3-bis (3-aminophenoxy) benzene, 1,4-bis (3-aminophenoxy) benzene having three benzene rings, 1,4 -Bis (4-aminophenoxy) benzene, 1,3-bis (3-aminobenzoyl) benzene, 1,3-bis (4-aminobenzoyl)
Benzene, 1,4-bis (3-aminobenzoyl) benzene, 1,4-bis (4-aminobenzoyl) benzene, 1,3-bis (3-amino-α, α-dimethylbenzyl) benzene, 1,3 -Bis (4-amino-α, α-
Dimethylbenzyl) benzene, 1,4-bis (3-amino-α, α-dimethylbenzyl) benzene, 1,4-bis (4-amino-α, α-dimethylbenzyl) benzene, 1,3-bis (3 -Amino-α, α-ditrifluoromethylbenzyl) benzene, 1,3-bis (4-amino-α, α-ditrifluoromethylbenzyl) benzene, 1,4-bis (3-amino-α, α-ditri Fluoromethylbenzyl) benzene, 1,4-bis (4-amino-α, α-ditrifluoromethylbenzyl) benzene, 2,6-bis (3-aminophenoxy) benzonitrile, 2,6-bis (3-amino Phenoxy) pyridine, d) 4,4′-bis (3-aminophenoxy) biphenyl, 4,4′-bis (4-aminophenoxy) biphenyl, biphenyl having four benzene rings [4- (3-aminophenoxy) phenyl] ketone, bis [4- (4-aminophenoxy) phenyl] ketone, bis [4- (3-aminophenoxy) phenyl] sulfide, bis [4-
(4-aminophenoxy) phenyl] sulfide, bis [4- (3-aminophenoxy) phenyl] sulfone,
Bis [4- (4-aminophenoxy) phenyl] sulfone, bis [4- (3-aminophenoxy) phenyl] ether, bis [4- (4-aminophenoxy) phenyl] ether, 2,2-bis [4- (3-aminophenoxy) phenyl] propane, 2,2-bis [4- (4-
Aminophenoxy) phenyl] propane, 2,2-bis [3- (3-aminophenoxy) phenyl] -1,1,1
1,3,3,3-hexafluoropropane, 2,2-bis [4- (4-aminophenoxy) phenyl] -1,
1,1,3,3,3-hexafluoropropane and the like can be mentioned. In the present invention, among the above aromatic diamines, 4,4′-bis (3-aminophenoxy) biphenyl is particularly preferred.

Examples of the tetracarboxylic dianhydride represented by the formula (9) used in the present invention include pyromellitic dianhydride, 3,3 ', 4,4'-benzophenonetetracarboxylic acid Dianhydride, 2,2 ′, 3,3′-benzophenonetetracarboxylic dianhydride, 2,3 ′, 3
4'-biphenyltetracarboxylic dianhydride, 2,
2 ', 3,3'-biphenyltetracarboxylic dianhydride, 2,2-bis (3,4-dicarboxyphenyl) propane dianhydride, 2,2-bis (2,3-dicarboxyphenyl) propane Dianhydride, bis (3,4-dicarboxyphenyl) ether dianhydride, bis (3,4-dicarboxyphenyl) sulfone dianhydride, bis (3,4-
Dicarboxyphenyl) sulfide dianhydride, 1,1-
Bis (2,3-dicarboxyphenyl) ethane dianhydride, 1,1-bis (3,4-dicarboxyphenyl) ethane dianhydride, bis (2,3-dicarboxyphenyl)
Methane dianhydride, bis (3,4-dicarboxyphenyl) methane dianhydride, 2,2-bis (3,4-dicarboxyphenyl) -1,1,1,3,3,3-hexafluoropropane Dianhydride, 2,2-bis (2,3-dicarboxyphenyl) -1,1,1,3,3,3-hexafluoropropane dianhydride, 1,3-bis (3,4-dicarboxy) Benzoyl) benzene dianhydride, 1,4-bis (3,4-dicarboxybenzoyl) benzene dianhydride, 1,3-bis (3,4-dicarboxyphenoxy)
Benzene dianhydride, 1,4-bis (3,4-dicarboxyphenoxy) benzene dianhydride, 2,2-bis [4-
(3,4-dicarboxyphenoxy) phenyl] propane dianhydride, 2,2-bis [3- (3,4-dicarboxyphenoxy) phenyl] propane dianhydride, bis [4
-(3,4-dicarboxyphenoxy) phenyl] ketone dianhydride, bis [3- (3,4-dicarboxyphenoxy) phenyl] ketone dianhydride, 4,4′-bis (3,4-dicarboxy) Phenoxy) biphenyl dianhydride, 3,3′-bis (3,4-dicarboxyphenoxy) biphenyl dianhydride, bis [4- (3,4-dicarboxyphenoxy) phenyl] ether dianhydride, bis [3 -(3,4-dicarboxyphenoxy) phenyl]
Ether dianhydride, bis [4- (3,4-dicarboxyphenoxy) phenyl] sulfone dianhydride, bis [3-
(3,4-dicarboxyphenoxy) phenyl] sulfone dianhydride, bis [4- (3,4-dicarboxyphenoxy) phenyl] sulfide dianhydride, bis [3-
(3,4-dicarboxyphenoxy) phenyl] sulfide dianhydride, 2,2-bis [4- (3,4-dicarboxyphenoxy) phenyl] -1,1,1,3,3,3
-Hexafluoropropane dianhydride, 2,2-bis [3
-(3,4-dicarboxyphenoxy) phenyl]-
1,1,1,3,3,3-hexafluoropropane dianhydride, 2,3,6,7-naphthalenetetracarboxylic dianhydride, 1,4,5,8-naphthalenetetracarboxylic dianhydride , 1,2,5,6-naphthalenetetracarboxylic dianhydride and the like. In the present invention, among the above tetracarboxylic dianhydrides, pyromellitic dianhydride is particularly preferred.

The crystalline polyimide used in the present invention has a repeating unit represented by the formula (1) of 90 to 100 mol%, preferably 95 to 100 mol%, and a repeating unit of the formula (2) or (3). It is a polyimide comprising 10 to 0 mol%, preferably 5 to 0 mol% of repeating units. Equation (2)
Or the amount of the repeating unit represented by (3) is 10 mol%
If it exceeds, the resulting polyimide has a low crystallization rate, and the product obtained by molding does not sufficiently crystallize, so that heat treatment is required, which is not preferable.

The repeating unit represented by the formula (1) and the repeating unit represented by the formula (2) have a mole fraction of 1,3-bis (4-aminophenoxy) benzene used as a monomer. It can be controlled by adjusting the mole fraction of the aromatic diamine represented by (8). That is, for example, polyimide composed of 95 mol% of the repeating unit represented by the formula (1) and 5 mol% of the repeating unit represented by the formula (2) is obtained by using 1,3-bis (4-aminophenoxy) benzene as a raw material. 0.05 mol of the aromatic diamine represented by the formula (8) and 3,3 ′, 4 per 0.95 mol
4'-biphenyltetracarboxylic dianhydride 0.9 to
It can be obtained by using 1.1 mol.

The molar ratio of the repeating unit represented by the formula (1) and the repeating unit represented by the formula (3) is determined by the following formula: 3,3 ′, 4,4′-biphenyltetracarboxylic acid used as a monomer It can be controlled by adjusting the molar fraction of the dianhydride and the tetracarboxylic dianhydride represented by the formula (9). That is, for example, a polyimide composed of 95 mol% of the repeating unit represented by the formula (1) and 5 mol% of the repeating unit represented by the formula (3) has 3,3 as a raw material.
0.05 mol of tetracarboxylic dianhydride represented by formula (9) and 1,3-bis (4-aminophenoxy) per 0.95 mol of 3 ', 4,4'-biphenyltetracarboxylic dianhydride It can be obtained by using 0.9 to 1.1 mol of benzene.

The crystalline polyimide used in the present invention is:
The terminal of the repeating unit represented by the formula (1) and the repeating unit represented by the formula (2) or (3) is reacted with an aromatic monoamine and / or an aromatic dicarboxylic anhydride to form a thermal and chemical compound. To be inactivated. More specifically, by reacting with an aromatic monoamine and / or an aromatic dicarboxylic anhydride, the molecular terminal thereof is thermally and chemically inactive represented by the formula (4) and / or (5). Structure.

[0027]

Embedded image (Where R3 is the following formula (10), and R4 is the following formula (11)
Indicated by

[0028]

Embedded image R5 represents hydrogen and / or fluorine, chlorine, bromine, methyl, ethyl, propyl, butyl, phenyl, phenoxy, benzoyl, phenylthio, benzenesulfonyl. Polyimides whose terminals are not inactivated have poor thermal stability during melting and cannot be used for melt molding. That is,
When a polyimide having an amino group and / or an acid anhydride group at the end is melted in a cylinder, the fluidity of the polyimide is rapidly reduced, and molding is extremely difficult or impossible.

The aromatic monoamine used in the present invention includes, for example, aniline, o-toluidine, m-toluidine, p-toluidine, 2,3-xylidine, 2,6-xylidine, 3,4-xylidine, 3,5 -Xylidine, o-chloroaniline, m-chloroaniline, p-chloroaniline, o-bromoaniline, m-bromoaniline, p-bromoaniline, o-anisidine, m-anisidine, p-anisidine, o-phenezine,
m-phenezine, p-phenezine, 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-aminophenylphenyl sulfone, α-naphthylamine, β-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 and the like can be mentioned. These aromatic monoamines may be substituted with a group having no reactivity with amine or dicarboxylic anhydride.

As the aromatic dicarboxylic anhydride used in the present invention, phthalic anhydride, chlorophthalic anhydride, bromophthalic anhydride, fluorophthalic anhydride, 2,3-
Benzophenone dicarboxylic anhydride, 3,4-benzophenone dicarboxylic anhydride, 2,3-dicarboxyphenyl phenyl ether anhydride, 3,4-dicarboxyphenyl phenyl ether anhydride, 2,3-biphenyl dicarboxylic anhydride, 3,4-biphenyldicarboxylic anhydride, 2,3-dicarboxyphenylphenylsulfone anhydride, 3,4-dicarboxyphenylphenylsulfone anhydride, 2,3-dicarboxyphenylphenylsulfide anhydride, 3,4- Examples thereof include dicarboxyphenylphenyl sulfide anhydride, 1,2-naphthalenedicarboxylic anhydride, 2,3-naphthalenedicarboxylic anhydride, and 1,8-naphthalenedicarboxylic anhydride. These aromatic dicarboxylic anhydrides may be substituted with a group having no reactivity with amine or dicarboxylic anhydride.

The crystalline polyimide used in the present invention may be 1,3-bis (4-aminophenoxy) benzene, an aromatic diamine represented by the formula (8) or a tetracarboxylic acid diamine represented by the formula (9). Anhydrous, 3,3 ', 4,4'-
By adjusting the amount ratio of biphenyltetracarboxylic dianhydride, aromatic monoamine and / or aromatic dicarboxylic anhydride, the molecular weight of the resulting polyimide can be adjusted. In the present invention, 1,3-bis (4-aminophenoxy) benzene, an aromatic diamine represented by the formula (8) or a tetracarboxylic dianhydride represented by the formula (9), 3,3 ′, The molar ratio of 4,4′-biphenyltetracarboxylic dianhydride, aromatic monoamine and / or aromatic dicarboxylic anhydride is such that when the diamines are in excess, 1,3-bis (4-aminophenoxy) benzene and For each mole of the aromatic diamine represented by the formula (8), 3,3 ′, 4,4′-biphenyltetracarboxylic dianhydride and the tetracarboxylic dianhydride represented by the formula (9) are 0 in total. 0.9 to 1.0 mole, and 0.001 to 1.0 mole of aromatic dicarboxylic anhydride. When the amount of the acid dianhydride is excessive, the amount of 3,3 ′, 4,4′-biphenyltetracarboxylic dianhydride and the total amount of the tetracarboxylic dianhydride represented by the formula (9) are 1.0 mol. 1,3-bis (4-aminophenoxy) benzene and an aromatic diamine represented by the formula (8) in a total amount of 0.9 to 1.0 mol, and an aromatic monoamine of 0.00
1 to 1.0 mol. When the amount of the aromatic monoamine and / or the aromatic dicarboxylic anhydride is less than 0.001 mol, the viscosity is increased at the time of high-temperature molding, which causes a reduction in moldability. On the other hand, if it exceeds 1.0 mol, the mechanical properties deteriorate. The preferred amount is 0.01 to 0.5 mol.

As a method for producing a polyimide used in the present invention, any method capable of producing a polyimide can be applied, including known methods. Among them, it is particularly preferable to carry out the reaction in an organic solvent. Solvents that can be used in such reactions include, for example, N, N-dimethylformamide, N,
N-diethylacetamide, N, N-dimethoxyacetamide, 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, pyrroline, picoline, dimethylsulfoxide, dimethylsulfone, tetramethylurea, hexamethylphospho Luamide, phenol, o-cresol, m-cresol, p-cresol, 3,5-xylenol, 2,3-xylenol, 2,4-xylenol, 2,6-xylenol, 3,4-xylenol, o
-Chlorophenol, p-chlorophenol, sulfolane, o-dichlorobenzene, diphenyl ether, anisole, benzene, toluene, xylene and the like. Particularly preferred are phenol, o-cresol, m-cresol, p-cresol and p-chlorophenol.
These organic solvents may be used alone or as a mixture of two or more.

In the present invention, a diamine,
As a method for adding and reacting an aromatic tetracarboxylic dianhydride, an aromatic dicarboxylic anhydride and / or an aromatic monoamine, (a) after reacting an aromatic tetracarboxylic dianhydride with a diamine, A method in which an aromatic dicarboxylic acid anhydride or an aromatic monoamine is added to continue the reaction; (b) an aromatic dicarboxylic acid anhydride is added to a diamine to cause a reaction, and then an aromatic tetracarboxylic dianhydride is added. (C) a method in which an aromatic monoamine is added to an aromatic tetracarboxylic dianhydride to cause a reaction, and then a diamine is added thereto, and the reaction is further continued; (d) an aromatic tetracarboxylic acid A method in which dianhydrides, diamines, aromatic dicarboxylic anhydrides or aromatic monoamines are simultaneously added and reacted, and the like. No problem. Further, 1,3-bis (4-aminophenoxy) benzene which is a diamine and an aromatic diamine represented by the formula (8), or 3,
3 ′, 4,4′-biphenyltetracarboxylic dianhydride and the tetracarboxylic dianhydride represented by the formula (9) may be added at the same time. The other may be added and the reaction further continued.

The reaction temperature is usually from normal temperature to 250 ° C. The reaction pressure is not particularly limited, and the reaction can be sufficiently performed at normal pressure. In addition, by performing the reaction under pressure, the boiling point of the solvent can be increased and the reaction temperature can be increased. The reaction time varies depending on the type of the solvent and the reaction temperature, but usually 4 to 48 hours is sufficient.

By carrying out the reaction at a temperature between room temperature and 130 ° C.,
Polyamic acid, which is a precursor of polyimide, is produced.
The polyamic acid is dehydrated by heating to 100 to 400 ° C. or chemically imidized using a commonly used imidizing agent, for example, triethylamine and acetic anhydride, so that the repeating unit 90 to 100
%, And 10 to 0 mol% of a repeating unit represented by the formula (2) or (3), and a crystalline polyimide whose molecular terminal is represented by the formula (4) and / or (5) is obtained. Can be

Further, by conducting the reaction at 130 to 250 ° C., the polyamic acid generation and the thermal imidization reaction proceed simultaneously, and the polyimide of the present invention can be obtained. That is, diamines, aromatic tetracarboxylic dianhydride,
The aromatic monoamine and / or aromatic dicarboxylic anhydride is suspended or dissolved in an organic solvent, and
The reaction is carried out under heating at 0 ° C., so that the polyamic acid is formed and the dehydration imidization is carried out simultaneously, so that 90 to 100 mol% of the repeating unit represented by the formula (1) and the formula (2) or (3) The molecular polyimide is composed of 10 to 0 mol% of a repeating unit represented by the following formula, and a crystalline polyimide represented by the formula (4) and / or (5) can be obtained. Although there is no particular limitation on the melt viscosity of the crystalline polyimide used in the present invention, preferably the melt viscosity when melted while held at 420 ° C. for 5 minutes is 400 to 5000 Pa · sec, more preferably 600 to 2000 Pa · sec. is there. Polyimide having a melt viscosity of less than 400 Pa · sec is extremely brittle and cannot withstand use as a molded product. 5000P
Polyimides larger than a · sec have extremely poor fluidity, so that injection molding is difficult. The crystalline polyimide used in the present invention has a melt viscosity by adjusting the ratio of diamines, aromatic tetracarboxylic dianhydrides, aromatic monoamines and / or aromatic dicarboxylic anhydrides during polymerization. Can be set to a desired value.

The crystalline polyimide used in the present invention is:
The amount of change in the melt viscosity when held at 420 ° C. for 30 minutes is within 50%, preferably within 40%, more preferably within 30% as compared with the melt viscosity when held at 420 ° C. for 5 minutes and melted. . If the amount of change in the melt viscosity is greater than 50%, its fluidity decreases with time during melting,
For example, at the time of injection molding, the injection pressure increases or the flow length of the resin decreases with time after the start of molding, so that not only stable molding cannot be performed, but also a product having stable color tone and physical properties cannot be manufactured. The polyimide having a repeating unit represented by the formula (1) uses 1,3-bis (4-aminophenoxy) benzene containing no high molecular weight impurities as a raw material monomer, and the terminal of the repeating structural unit is an aromatic monoamine. And / or by reacting with an aromatic dicarboxylic anhydride, the change in melt viscosity can be kept within 50% only when the molecular terminal has a thermally and chemically inactive structure. .

Here, the melt viscosity of polyimide is Jis
According to the K7210 flow test method (reference test), a load of 1 was applied using a Shimadzu elevated flow tester (CFT500A).
It is measured at 420 ° C. at 00 kg (pressure 9.8 MPa).
Further, the change amount of the melt viscosity is obtained by the following equation. Change in melt viscosity (%) = (melt viscosity when held at 420 ° C for 30 minutes-melt viscosity when held at 420 ° C for 5 minutes and melted) / (when melted while held at 420 ° C for 5 minutes) Melt viscosity of × 100 × 100 ° C. for 5 minutes and 30 minutes at 420 ° C.
Fill the sample into the cylinder of the flow tester at 0 ° C,
For 30 minutes and 30 minutes.

The crystalline polyimide used in the present invention is:
This is a crystalline polyimide for melt molding, which exhibits crystallization when cooled at a cooling rate of 50 ° C./min from a molten state.
A resin having a high crystallization rate, in which crystallization develops even under such cooling conditions, can be obtained into a sufficiently crystallized molded article by appropriate melt molding. On the other hand, a resin that does not exhibit crystallization when cooled at a cooling rate of 50 ° C./min from a molten state is subjected to a heat treatment for crystallization such as gradually cooling in a mold during molding, annealing in an oven after molding, and the like. Since it is necessary, productivity is extremely low. The onset of crystallization is determined, for example, by cooling the sample in the molten state at a cooling rate of 50%.
It can be confirmed by observing the presence or absence of an exothermic peak due to crystallization in DSC measurement at a cooling rate of ° C./min.

The polyimide resin composition for melt molding according to the present invention comprises 50 to 95% by weight of the above crystalline polyimide, polyphenylene sulfide resin, liquid crystal polymer resin, polyether sulfone resin, polysulfone resin, polyarylate resin, polyamide resin, Polyether resin, polyetherimide resin, polyamideimide resin, fluororesin,
A polyimide resin composition for melt molding, comprising 50 to 5% by weight of one or more resins selected from polyimide resins. The crystalline polyimide has excellent heat resistance and mechanical strength, but has low tensile elongation and impact resistance, and is liable to be oriented and crystallized, and thus tends to have anisotropy in strength and molding shrinkage. The polyimide resin composition for melt molding of the present invention, the above crystalline polyimide polyphenylene sulfide resin, liquid crystal polymer resin, polyether sulfone resin, polysulfone resin, polyarylate resin, polyamide resin, polyether resin, polyetherimide resin, By adding 50 to 5% by weight of one or more resins selected from polyamideimide resin, fluorine resin and polyimide resin, the tensile elongation and impact resistance of the crystalline polyimide are improved, and the strength is further improved. In addition, the anisotropy of the molding shrinkage can be reduced. Here, the type and amount of the various resins used can be appropriately selected according to the purpose of the composition. That is,
The resin to be used can be appropriately selected from thermoplastic or non-thermoplastic, crystalline or amorphous depending on the purpose. Examples of the polyphenylene sulfide resin used in the present invention include Dainippon Ink and Chemicals “DIC.PPS”, Polyplastics “Fortron”, Toray “Torrelina”, Tosoh “Sastile PPS”, Idemitsu Material “Idemitsu P
PS ", Mitsubishi Engineering Plastics" Novaps ", Asahi Glass" ASAHI.PPS ", Ube Industries" UB "
EPPS "and Toyobo" Toyobo PPS ".

The liquid crystal polymer resin used in the present invention includes Polyplastics "Vectra", Sumitomo Chemical Industries "Sumika Super LCP", Nippon Petrochemical "Zyder", Unitika "Rodrun", Toray "Siveras", Mitsubishi Engineering Corp. Plastics "Novacute",
Ueno Pharmaceutical "UENO LCP", Dupont "Zenite"
And the like.

As the polyether sulfone resin used in the present invention, Sumitomo Chemical Industries Sumika Excel PE
S ", Mitsui Chemicals" Ultrazone ", Teijin Amoco Engineering Plastics" RADEL ", BAS
F Engineering Plastics "Ultra Zone"
And the like.

Examples of the polysulfone resin used in the present invention include Teijin Amoco Engineering Plastics "UDEL" and "MINDEL".

Examples of the polyarylate resin used in the present invention include Unitika "U-Polymer", UCC "Adel", Solvay "Ariref", Bayer "APE", Hooker "Durer", Kanegafuchi Chemical "NAP resin", and DuPont. "Arylon", Sumitomo Chemical "Econol" and the like.

The polyamide resin used in the present invention includes DSM Engineering Plastics "Stanil", Mitsubishi Engineering Plastics "Lenny", Teijin Amoco Engineering Plastics "Lenny", Mitsui Chemicals "Ahren", Toyobo Co., Ltd. Toyobo aromatic nylon ", Dupont" Zytel HTN ", Bayer" Duretan "and the like.

The polyether resin used in the present invention includes VICTREX "VICTREX PEEK",
Sumitomo Chemical “VICTREX PEEK” and the like.

As the polyetherimide resin used in the present invention, Nippon GE Plastics "Ultem"
And the like.

Examples of the polyamideimide resin used in the present invention include Teijin Amoco Engineering Plastics "TORLON", Toray "TI-5000", Sumitomo Chemical "Sumika PAI" and the like.

The fluororesin used in the present invention includes:
Polytetrafluoroethylene, poly (trifluorochloroethylene), polyvinylidene fluoride, polyvinyl fluoride, ethylene tetrafluoride-propylene hexafluoride copolymer, ethylene tetrafluoride-perfluoroalkyl vinyl ether copolymer, ethylene-tetrafluoroethylene Ethylene copolymer, ethylene trifluoride chloride-ethylene copolymer, ethylene tetrafluoride-propylene hexafluoride-perfluoroalkyl vinyl ether copolymer, and the like, and as trade names, DuPont "Viton""Kalrez"Viton", 3M
"Fluorel""Kel-FElastme"
r ", Ausimont" Technoflon ", Daikin Industries" Daiel "" Perflo "" Daiel Thermoplastic ", Asahi Glass" Afras ", Dow Cor
ning “Silastic”, central glass “Sefralsoft” and the like.

The polyimide resins used in the present invention include DuPont "Vespel", Nitto Denko "Nid Mid", Mitsubishi Chemical "PI-2080""Novax", Toray "TI Polymer", Ube Industries "Upilex" and "Upimor". And Kanebuchi Chemical "Apical".

The polyimide resin composition of the present invention comprises 50 to 95% by weight of a crystalline polyimide for melt molding and 50 to 5% by weight of one or more kinds of resins in combination of two or more. The weight% value is determined depending on the purpose and required performance, but the preferable amount of each resin is 10 to 30 weight%.
It is. If the amount of the various resins is less than 5% by weight, the effect of modifying the tensile elongation and impact resistance, which are the weak points of the crystalline resin, is small. Conversely, if the amount exceeds 50% by weight, the crystalline resin is advantageous. It is not preferable because it becomes difficult to maintain the elastic modulus above Tg.

The polyimide resin composition according to the present invention can be produced by a generally known method, but the following method is particularly preferable. Mortar, Henschel mixer, drum blender, tumbler blender, ball mill, after pre-mixing using a polyimide blender and various resins to be used with the polyimide powder, usually kneading with a known melt mixer, hot rolls and the like, pellets or Make powder. Polyimide powder is dissolved or suspended in an organic solvent in advance, and after adding various resins used in this solution or suspension, the organic solvent is removed by drying in an appropriate method,
Pellet or powder in the same manner as described above. There are no particular restrictions on the type of organic solvent used and the concentration of the solution, and the organic solvent may be used alone or as a mixture of two or more organic solvents.

In the polyimide resin composition of the present invention, the following fillers and the like used in ordinary resin compositions can be used as long as the object of the present invention is not impaired. Examples of the filler used include abrasion resistance improvers such as graphite, carborundum, silica stone powder, and molybdenum disulfide, reinforcing agents such as glass fiber and carbon fiber, and flame retardant such as antimony trioxide, magnesium carbonate, and calcium carbonate. Property improver, electric property improver such as clay, mica, etc., tracking resistance improver such as asbestos, silica, graphite, etc., acid resistance improver such as barium sulfate, silica, calcium metasilicate, iron powder, zinc powder, aluminum powder And heat conduction improvers such as copper powder, other glass beads, glass spheres, talc, diatomaceous earth, alumina, shirasubarun, hydrated alumina, metal oxides, coloring agents and the like.

The polyimide resin composition for melt molding of the present invention is molded by a known melt molding method such as extrusion molding, injection molding, compression molding, transfer molding and the like, and put into practical use. Since the polyimide resin composition for melt molding of the present invention has a high crystallization rate, a sufficiently crystallized molded article can be obtained by performing molding under appropriate conditions. Further, it can be crystallized by performing a heat treatment (annealing treatment) after molding. By crystallizing the polyimide resin composition for melt molding of the present invention, the softening temperature is significantly increased as compared with the amorphous state, and it is possible to use at a high temperature. The crystalline polyimide used in the present invention thus formed has excellent heat resistance and mechanical properties, can be used for structural members, machine parts, automobile parts, and the like, and is very useful.

[0055]

EXAMPLES Hereinafter, the present invention will be described specifically with reference to Examples, but the present invention is not limited thereto.

Incidentally, 1,3-bis (4-nitrophenoxy) benzene and 1,3-bis (4-aminophenoxy) benzene were analyzed by the following method. Apparent purity: A 25 wt ppm acetonitrile solution of the sample was prepared and subjected to high performance liquid chromatography (column: ODS column CrestPak C18T-5 manufactured by JASCO).
4.6 × 250 mm, moving layer: acetonitrile / water = 6/4, flow rate 1.0 ml / min, injection amount 20 μl), and the absorption area percentage at a measurement wavelength of 250 nm was used. Presence / absence of high molecular weight impurities: A 5% by weight solution of the sample in tetrahydrofuran was prepared and subjected to gel permeation chromatography (column: PLgel manufactured by Polymer Laboratory Co., Ltd.).
0.75 × 300mm 2 in series, moving bed: tetrahydrofuran,
Flow rate: 0.75 ml / min, injection volume: 100 μl), and confirmed by an RI detector. Color tone: A 10% by weight dimethylformamide solution of the sample was prepared, and the light transmittance (T%) at 450 nm was measured using an extra-visible and visible spectrophotometer (cell length: 10 mm).

The physical properties of the polyimide were measured by the following methods. 5% weight loss temperature: DTG (Shimadzu DT-40) in the air
Series, DTG-40M). Logarithmic viscosity (ηinh): 0.5 parts of polyimide powder in a mixed solvent of p-chlorophenol / phenol (weight ratio 9/1)
g / 100 g, then measured at 35 ° C. Melt viscosity: JisK7210 flow test method (reference test)
Compliant, Shimadzu elevated flow tester (CFT500
A), a load of 100 kg (pressure 9.8 MPa), 4
Measured at 20 ° C. Thermal stability: As an index of the thermal stability of the resin at the time of melting, 42
The amount of change in the melt viscosity when held at 0 ° C. for 5 minutes and 30 minutes was determined. Change in melt viscosity (%) = (melt viscosity when held at 420 ° C for 30 minutes-melt viscosity when held at 420 ° C for 5 minutes and melted) / (when melted while held at 420 ° C for 5 minutes) Holding at 420 ° C. for 5 minutes and 420 ° C. for 30 minutes means that a sample is filled in a cylinder of a flow tester at 420 ° C. and held for 5 minutes and 30 minutes. Crystallization behavior: DSC (Seiko Electronics Corporation EXSTAR)
6200), the crystallization temperature during cooling (Tc), the crystallization energy (ΔHc), the crystallization temperature during the second heating (Tc), the crystallization energy (ΔHc), the melting point (Tm), and the melting point Measure energy (ΔHm). The heating / cooling pattern at the time of the DSC measurement is based on the following three steps.

Room temperature → (heating rate 10 ° C./mi
n) → 430 ° C 430 ° C → (Cooling rate 50 ° C / min) →
50 ℃ 50 ℃ → (heating rate 10 ℃ / min) → 4
30 ° C. The larger the crystallization energy (ΔHc) during cooling, the higher the crystallinity of the polyimide after cooling.

Synthesis Example 1 1,3-bis (4-aminophenoxy) benzene purchased from Wakayama Seika was converted to a Smith-type thin-film evaporator (2-03 type thin-film distillation apparatus manufactured by Shinko Pantech Co., Ltd., heating heat transfer area: 0). .0
34m2, single-evaporation distillation at a rotor rotation speed of 450 rpm, and 1,3-bis (4-
9700 g of (aminophenoxy) benzene were obtained. In addition,
The distillation was performed at a heat transfer surface temperature of 270 ° C. and a degree of vacuum of 17.3 Pa.
(0.13 Torr) and 1,3-bis (4-aminophenoxy) benzene feed rate of 4.2 g / min. 1,3-bis (4) containing no high molecular weight impurities as distillate
-Aminophenoxy) benzene was pale yellow and transparent when melted, and was pale orangeish white after cooling and solidifying. 426 g of the distillation residue was a black-brown tar and had almost no fluidity. The apparent purity of the obtained 1,3-bis (4-aminophenoxy) benzene containing no high molecular weight impurities was 99.2%, and no high molecular weight impurities were confirmed. The light transmittance (T%) was 69.3% (see FIG. 2). FIG. 1 shows a GPC chart. (Note that
In FIG. 1, some measurement times are different, and thus the retention times are different. 0.1) with a stirrer, reflux condenser and nitrogen inlet
In a reactor of m3, 1,3 containing no high molecular weight impurities
-Bis (4-aminophenoxy) benzene 877.1 g
(3.0 mol), 857.9 g of 3,3 ′, 4,4′-biphenyltetracarboxylic dianhydride (2.916 mo)
l), 24.88 g of phthalic anhydride (0.168 mol)
l), 15.0 kg of m-cresol was charged, and heated to 200 ° C. while stirring under a nitrogen atmosphere.
Thereafter, the reaction was carried out at 200 ° C. for 8 hours.
4.88 g (0.168 mol) was added, and the reaction was further performed for 4 hours. During that time, distillation of about 110 ml of water was confirmed. During the reaction, the mass was light yellow and transparent.

After the completion of the reaction, the mixture is cooled to room temperature, and toluene 3
7.5 kg was dropped over about 2 hours to precipitate polyimide. The slurry liquid was filtered, and the obtained polyimide cake was washed with toluene and dried in nitrogen at 300 ° C. for 4 hours to obtain 1580 g of yellow polyimide powder (yield 95.6).
%).

The logarithmic viscosity of the obtained polyimide powder is 1.0
It was 0 dl / g. The melting point of this polyimide powder was 398 ° C, and the 5% weight loss temperature was 571 ° C.

When this polyimide powder was melted by holding it at 420 ° C. for 5 minutes and 30 minutes in a cylinder of a flow tester, the melt viscosity was 960 and 1120 Pa · sec.
c, indicating a good change in the melt viscosity of 16% and good thermal stability.

Synthesis Example 2 1,3 containing no high molecular weight impurities obtained in Synthesis Example 1
833.2 g of bis (4-aminophenoxy) benzene
(2.85 mol), 55.3 g (0.15 mol) of 4,4′-bis (3-aminophenoxy) biphenyl,
856.2 g (2.91 mol) of 3,3 ′, 4,4′-biphenyltetracarboxylic dianhydride and phthalic anhydride 2
Using 6.7 g (0.18 mol), 1589 g of yellow polyimide powder (yield 95.5%) in the same manner as in Synthesis Example 1.
I got

The logarithmic viscosity of the obtained polyimide powder was 0.9.
It was 8 dl / g. The melting point of this polyimide powder was 386 ° C, and the 5% weight loss temperature was 570 ° C.

When the polyimide powder was melted by holding it at 420 ° C. for 5 minutes and 30 minutes in a cylinder of a flow tester, the melt viscosity was 1220 and 1400 Pa · s.
ec, and a good change in the melt viscosity of 15%, indicating good thermal stability.

Examples 1 to 8 The polyimide powder obtained in Synthesis Example 1 or 2 and a polyamide-imide resin (Toron 4203L, manufactured by Teijin Amoco Engineering Plastics), a polyether resin (PEEK450G, manufactured by Victrex), a liquid crystal polymer (Polyplastics: Vectra A950) or polyethersulfone resin (Mitsui Chemicals: Ultrazone E2010) was mixed at the ratio shown in Table 1 and melted at 420 ° C. by a 25 mm diameter single screw extruder. Extruded to obtain pellets.

Using the obtained pellets, the spiral flow length was measured at a cylinder temperature of 420 ° C., a mold temperature of 200 ° C., an injection pressure of 147 MPa, a flow thickness of 1 mm, and a molding cycle of 120 seconds. The ratio of the flow length of the first shot to the flow length of the tenth shot was defined as the fluidity retention during melting, and was used as an index of the flow stability. Table 1 shows the results.

Using the obtained pellets, a cylinder temperature of 420 ° C., a mold temperature of 210 ° C., and an injection pressure of 147 MPa
Various test pieces were molded in a, and tensile strength (ASTM D-6)
38) and deflection temperature under load (ASTM D-648,
The pressure was 1.82 MPa). Table 2 shows the results.

[0069]

[Table 1]

[0070]

[Table 2] As is clear from Tables 1 and 2, the melt molding polyimide resin composition of the present invention has a small decrease in fluidity during melting,
It has excellent heat resistance and high strength.

Reference Example 1 The polyimide powder obtained in Synthesis Example 1 was melt-extruded at 420 ° C. using a single-screw extruder having a diameter of 25 mm to obtain yellow opaque pellets. The transparent resin extruded in the molten state crystallized immediately after leaving the die and became opaque.

Using the obtained pellets, the spiral flow length was measured at a cylinder temperature of 420 ° C., a mold temperature of 200 ° C., an injection pressure of 147 MPa, a flow thickness of 1 mm, and a molding cycle of 120 seconds. The ratio of the flow length of the first shot to the flow length of the tenth shot was defined as the fluidity retention during melting, and was used as an index of the flow stability. The results are shown below.

Spiral flow length (first shot): 390 mm Spiral flow length (10th shot): 380 mm Fluidity retention: 97% Further, the obtained pellets were subjected to cylinder temperature of 420 ° C. and mold temperature using a usual injection molding machine. 200 ° C, injection pressure 14
Various test pieces were molded at 7 MPa. The obtained test piece was crystallized in the mold.

Using the test pieces obtained at the 1st to 5th shots and the test pieces obtained at the 20th to 25th shots,
The tensile strength was measured according to MD-638, the bending strength was measured according to D-790, and the Izod impact strength (notched) was measured according to D-256. The results are shown below.

1-5 shot average tensile strength 148 MPa Tensile elongation 7% Bending strength 310 MPa Flexural modulus 6420 MPa Izod impact strength 70 N · cm / cm 20-25 shot average tensile strength 148 MPa Tensile elongation 7% bending Strength 310 MPa Flexural Modulus 6420 MPa Izod Impact Strength 70 N · cm / cm As is clear from the above results, the polyimide used in the present invention has no change in resin fluidity or physical properties at the time of molding. Products with stable physical properties can be manufactured.

Reference Example 2 Using the polyimide powder obtained in Synthesis Example 2, pellets were obtained in the same manner as in Reference Example 1, and flow stability and various mechanical properties were measured. The results are shown below.

Spiral flow length (1st shot) 280 mm Spiral flow length (10th shot) 280 mm Fluidity retention 100% 1-5 shots average Tensile strength 140 MPa Tensile elongation 7% Flexural strength 290 MPa Flexural modulus 6040 MPa Izod impact strength 70 N · cm / cm 20-25 shot average Tensile strength 140 MPa Tensile elongation 7% Flexural strength 290 MPa Flexural modulus 6020 MPa Izod impact strength 70 N · cm / cm The polyimide used in the present invention has no change in resin fluidity or physical properties at the time of molding, and can produce a product with stable molding and stable physical properties.

Reference Comparative Example 1 1556 g (yield) of polyimide powder according to Synthesis Example 1 except that 1,3-bis (4-aminophenoxy) benzene (see FIGS. 1 and 2) purchased from Wakayama Seika was used. 9
4.2%). Here, the 1,3-bis (4-
Aminophenoxy) benzene was light brown and had an apparent purity of 99.7%, but GPC confirmed the presence of high molecular weight impurities. Further, its T% was 24.9%.

The logarithmic viscosity of the obtained polyimide powder is 1.1.
1 dl / g, melting point 397 ° C., 5% weight loss temperature 56
8 ° C.

When this polyimide powder was melted by holding it at 420 ° C. for 5 minutes and 30 minutes in a cylinder of a flow tester, the melt viscosity was 1820 and 3240 Pa · s.
ec, the change in the melt viscosity was 78%.
The thermal stability was clearly inferior to that of.

Pellets were obtained in the same manner as in Synthesis Example 1, and flow stability and various mechanical properties were measured. The test pieces obtained at the 20th to 25th shots were greenish in comparison with the test pieces obtained at the 1st to 5th shots. The results are shown below.

Spiral flow length (1st shot) 290 mm Spiral flow length (10th shot) 160 mm Flowability retention 55% 1-5 shots average Tensile strength 125 MPa Tensile elongation 5% Flexural strength 260 MPa Flexural modulus 9280 MPa Izod impact strength 50 N · cm / cm 20-25 shot average Tensile strength 130 MPa Tensile elongation 4% Bending strength 270 MPa Flexural modulus 12060 MPa Izod impact strength 30 N · cm / cm The polyimide of the example decreased the fluidity of the resin with the passage of time at the time of molding, and also changed the color tone and physical properties of the obtained test piece, making it difficult to produce a product with stable molding and stable physical properties. .

REFERENCE EXAMPLE 3 130.2 g of 1,3-bis (4-aminophenoxy) benzene purchased from Wakayama Seika was placed at 270 ° C. in a eggplant-shaped flask into which nitrogen gas had been introduced through a glass capillary.
And melted, and the internal pressure was increased to 13.3 by an oil diffusion pump.
By evaporating the content by simple evaporation to Pa, 100.9 g of 1,3-bis (4-aminophenoxy) benzene containing no high molecular weight impurities was obtained as a distillate (see FIGS. 1 and 2). . The temperature of the distilled steam was 240 ° C., and the distilled 1,3-bis (4-aminophenoxy) benzene was colorless and transparent when molten, and white after coagulation. The apparent purity of the obtained 1,3-bis (4-aminophenoxy) benzene containing no high molecular weight impurities was 99.2%, and no high molecular weight impurities were confirmed. The T% is 9
3.7%.

In a flask equipped with a stirrer, a reflux condenser, and a nitrogen inlet tube, 1
8.595 3-bis (4-aminophenoxy) benzene
g (29.4 mmol), 0.221 g of 4,4′-bis (3-aminophenoxy) biphenyl (0.6 mmol)
l), 8.606 g (29.25 mmol) of 3,3 ′, 4,4′-biphenyltetracarboxylic dianhydride, 0.222 g (1.5 mmol) of phthalic anhydride, and 158.8 g of m-cresol Then, the mixture was heated to 200 ° C. while stirring under a nitrogen atmosphere. Thereafter, the reaction was carried out at 200 ° C. for 8 hours, and phthalic anhydride 0.222 g (1.5
(mmol) was added and the reaction was continued for another 4 hours. Meanwhile, distillation of about 1.1 ml of water was confirmed. During the reaction, the mass was light yellow and transparent.

After the completion of the reaction, the mixture was cooled to room temperature, and toluene 33
0 g was dropped over about 1 hour to precipitate polyimide. The slurry liquid was filtered, and the obtained polyimide cake was washed with toluene, and then dried in nitrogen at 300 ° C. for 4 hours to obtain 15.77 g (yield 95.2%) of yellow polyimide powder.
I got

The logarithmic viscosity of the obtained polyimide powder was 1.0.
It was 4 dl / g. The melting point of this polyimide powder was 390 ° C., and the 5% weight loss temperature was 570 ° C. Table 3 shows the crystallization behavior of this polyimide powder.

When this polyimide powder was melted by holding it at 420 ° C. for 5 minutes and 30 minutes in a cylinder of a flow tester, the melt viscosity was 1460 and 1750 Pa · s.
ec, and showed a good thermal stability with a change in melt viscosity of 20%. The obtained strand was crystallized and was yellow and opaque.

Reference Example 4 1,3 containing no high molecular weight impurities obtained in Reference Example 3
-Bis (4-aminophenoxy) benzene 7.894 g
(27.0 mmol) and 1.105 g of 4,4′-bis (3-aminophenoxy) biphenyl (3.0 mmol)
1) Polyimide powder 15.
90 g (94.9% yield) was obtained.

The logarithmic viscosity of the obtained polyimide powder is 1.0.
5 dl / g, melting point 382 ° C., 5% weight loss temperature 56
9 ° C. Table 3 shows the crystallization behavior of this polyimide powder. When this polyimide powder was melted while held at 420 ° C. for 5 minutes and 30 minutes in a cylinder of a flow tester, the melt viscosity was 1850 and 2260 Pa · sec.
And a good thermal stability with a change in the melt viscosity of 22%. The obtained strand was crystallized and was yellow and opaque.

REFERENCE COMPARATIVE EXAMPLE 2 1,3 containing no high molecular weight impurities obtained in Reference Example 3
-Bis (4-aminophenoxy) benzene 7.017 g
(24.0 mmol) and 2.211 g of 4,4′-bis (3-aminophenoxy) biphenyl (6.0 mmol)
Except for using l), according to Reference Example 3, polyimide powder 16.
06 g (94.6% yield) was obtained.

The logarithmic viscosity of the obtained polyimide powder is 1.0.
5 dl / g, melting point: 360 ° C., 5% weight loss temperature: 56
5 ° C. Table 3 shows the crystallization behavior of this polyimide powder. As shown in Table 2, this polyimide was obtained in Reference Example 3,
Crystallization was slower than that of Sample No. 4. When this polyimide powder was melted while being held at 420 ° C. for 5 minutes and 30 minutes in a cylinder of a flow tester, the melt viscosity was 2900 and 3490 Pa · sec, and the change in melt viscosity was 20%.
%, But the resulting strand was transparent due to insufficient crystallization.

[0092]

[Table 3]

[0093]

According to the present invention, stable melt molding is possible.
A product with stable color tone and physical properties can be manufactured, and the product obtained by molding is sufficiently crystallized without heat treatment, and has high heat resistance, that is, a sufficient machine even at a temperature higher than the glass transition temperature. An object of the present invention is to provide a polyimide resin composition for melt molding having high strength and high thermal stability.

[Brief description of the drawings]

FIG. 1: 1,3-bis (4-aminophenoxy) used
It is a GPC chart of benzene.

FIG. 2: 1,3-bis (4-aminophenoxy) used
It is a light transmittance chart of benzene.

Continued on the front page (51) Int.Cl. ⁷ Identification code FI Theme coat II (Reference) C08L 77/00 C08L 77/00 81/00 81/00 (72) Inventor Shoji Tamai 1190 Kasama-cho, Sakae-ku, Yokohama-shi, Kanagawa F-term (reference) in Mitsui Chemicals Co., Ltd.

Claims (5)

[Claims] 1. A repeating unit 9 represented by the following formula (1):
0 to 100% by mole and 10 to 0% by mole of a repeating unit represented by the following formula (2) or (3), the molecular terminal of which is represented by formula (4) and / or (5):
50% to 95% by weight of a crystalline polyimide whose change in melt viscosity when held at 420 ° C. for 30 minutes is within 50% compared to the melt viscosity when melted while held at 20 ° C. for 5 minutes
And polyphenylene sulfide resin, liquid crystal polymer resin, polyether sulfone resin, polysulfone resin, polyarylate resin, polyamide resin, polyether resin, polyetherimide resin, polyamideimide resin,
One or two selected from fluorine resin and polyimide resin
A polyimide resin composition for melt molding, comprising 50 to 5% by weight of at least one kind of resin. Embedded image (In the formula, R1 is a divalent aromatic group, R2 is a tetravalent aromatic group, R3 is a monovalent aromatic group, and R4 is a divalent aromatic group.) 2. The polyimide resin composition for melt molding according to claim 1, wherein the crystalline polyimide is a polyimide that develops crystallization when cooled from a molten state at a cooling rate of 50 ° C./min. 3. In the formula (2), R1 is the same as the formula (6). The crystalline polyimide for melt molding according to claim 1 or 2, wherein 4. In the formula (3), R2 is represented by the formula (7). The crystalline polyimide for melt molding according to claim 1 or 2, wherein 5. An injection molded product obtained from the polyimide resin composition for melt molding according to claim 1.