JP2540571B2 - Polyimide resin composition - Google Patents

Description

The present invention relates to a resin composition for molding. For more details,
The present invention relates to a polyimide-based molding resin composition having excellent heat resistance, chemical resistance, mechanical strength, and the like, and excellent molding processability.

[Conventional technology]

Conventionally, polyimide obtained by the reaction of tetracarboxylic dianhydride and diamine has high mechanical strength, dimensional stability, flame retardancy, and electrical insulation in addition to its high heat resistance. , Aerospace equipment, transportation equipment, etc., and is expected to be widely used in the fields where heat resistance is required in the future.

Various polyimides having excellent characteristics have been developed so far.

However, even if it is excellent in heat resistance, it does not have a clear glass transition temperature, so when it is used as a molding material, it must be processed using a method such as sintering molding. In addition, it has a low glass transition temperature, is soluble in halogenated hydrocarbons, is not satisfactory in terms of heat resistance and solvent resistance, and has advantages and disadvantages in performance.

[Problems to be solved by the invention]

An object of the present invention is to obtain a polyimide-based resin composition having good molding processability in addition to the excellent properties inherent to polyimide.

[Means for solving problems]

As a result of intensive studies to solve the above problems, the present inventors have found that a polyimide resin composition composed of a thermoplastic polyimide and a specific amount of aromatic polyetherimide is particularly effective for the above purpose. Heading, completed the present invention.

The present inventor has previously described a thermoplastic polyimide having excellent mechanical properties, thermal properties, electrical properties, solvent resistance, and the like and having heat resistance. (In the formula, X represents a carbonyl group or a sulfonyl group,
R is an aliphatic group having 2 or more carbon atoms, a cycloaliphatic group, a monocyclic aromatic group, a condensed polycyclic aromatic group, or a non-condensed polycyclic group in which aromatic groups are directly or crosslinked with each other. Represents a tetravalent group selected from the group consisting of formula aromatic groups. The present invention has found a thermoplastic polyimide having a repeating unit represented by the formula (JP-A-62-53388).

The above thermoplastic polyimide is a novel heat resistant resin having many good physical properties peculiar to polyimide. However, polyethylene terephthalate, polybutylene terephthalate, polyether sulfone, polysulfone,
Compared with ordinary engineering plastics such as polyphenylene sulfide, the above polyimides are far superior in heat resistance and other mechanical properties, but melt flowability decreases as the molecular weight of the polyimide increases, and molding processing The sex becomes worse.

An object of the present invention is to provide a polyimide resin composition for molding which has excellent melt fluidity without deteriorating the inherent properties of thermoplastic polyimide.

That is, the present invention provides the following formula (A) (In the formula, X represents a carbonyl group or a sulfonyl group,
R is the following formula C = C, Represents at least one tetravalent group selected from the group consisting of ) Polyimide having repeating unit represented by
It is a resin composition comprising 0.1% by weight and 0.1 to 50% by weight of aromatic polyetherimide.

The polyimide used in the present invention has the formula (Wherein X represents a carbonyl group or a sulfonyl group), that is, 4,4'-bis [4
-(4-Amino-α, α-dimethylbenzyl) phenoxy] benzophenone or bis [4- {4- (4-amino-α, α-dimethylbenzyl) phenoxy} phenyl] sulfone and one or more tetracarboxylic acid dianhydrides It is obtained by imidizing a polyamic acid obtained by reacting a product with a product.

The tetracarboxylic dianhydride used at this time has the formula (Wherein R is the same as R in formula (A)) is a tetracarboxylic dianhydride.

That is, as the tetracarboxylic dianhydride used, ethylene tetracarboxylic dianhydride, cyclopentane tetracarboxylic dianhydride, pyromellitic dianhydride, 3,3 ', 4,4'-benzophenone tetra Carboxylic dianhydride, 2,2 ', 3,3'-benzophenone tetracarboxylic dianhydride, 3,3', 4,4'-biphenyltetracarboxylic dianhydride, 2,2 ', 3,3 ′ -Biphenyltetracarboxylic dianhydride, 2,2-bis (3,4-dicarboxyphenyl)
Propane dianhydride, 2,2-bis (2,3-dicarboxyphenyl) propane dianhydride, bis (3,4-dicarboxyphenyl) ether dianhydride, bis (3,4-dicarboxyphenyl) sulfone Dianhydride, 1,1-bis (2,3-dicarboxyphenyl) ethane dianhydride, bis (2,3-dicarboxyphenyl) methane dianhydride, bis (3,4-dicarboxyphenyl) methane dianhydride Anhydride, 4,4 '-(p-phenylenedioxy) diphthalic acid dianhydride, 4,4'-(m-
(Phenylenedioxy) diphthalic acid dianhydride, 2,3,6,7-
Naphthalene tetracarboxylic dianhydride, 1,4,5,8-naphthalene tetracarboxylic dianhydride, 1,2,5,6-naphthalene tetracarboxylic dianhydride, 1,2,3,4-benzenetetra Carboxylic dianhydride, 3,4,9,10-berylenetetracarboxylic dianhydride, 2,3,6,7-anthracene tetracarboxylic dianhydride, 1,2,7,8-phenanthrene tetracarboxylic acid An acid dianhydride, and these tetracarboxylic acid dianhydrides may be used alone or in combination of two or more.

In addition, the thermoplastic polyimide used in the composition of the present invention is a polyimide used as a raw material of the above-mentioned ether diamine, but is obtained by mixing and using other diamines within a range not to impair the good physical properties of this polyimide. The resulting polyimide can also be used in the composition of the present invention.

Examples of the diamine that can be used as a mixture include m-phenylenediamine, o-phenylenediamine,
p-phenylenediamine, m-aminobenzylamine,
p-aminobenzenamine, bis (3-aminophenyl) ether, (3-aminophenyl) (4-aminophenyl) ether, bis (4-aminophenyl) ether, bis (3-aminophenyl) sulfide, (3- Aminophenyl) (4-aminophenyl) sulfide, bis (4-aminophenyl) sulfide, bis (3-aminophenyl) sulfoxide, (3-aminophenyl)
(4-aminophenyl) sulfoxide, bis (4-aminophenyl) sulfoxide, bis (3-aminophenyl) sulfone, (3-aminophenyl) (4-aminophenyl) sulfone, bis (4-aminophenyl) sulfone, 3 , 3'-diaminobenzophenone, 3,4'-diaminobenzophenone, 4,4'-diaminobenzophenone, bis [4- (3-aminophenoxy) phenyl] methane,
Bis [4- (4-aminophenoxy) phenyl] methane, 1,1-bis [4- (3-aminophenoxy) phenyl] ethane, 1,1-bis [4- (4-aminophenoxy) phenyl] ethane, 1,2-bis [4- (3-aminophenoxy) phenyl] ethane, 1,2-bis [4- (4
-Aminophenoxy) phenyl] ethane, 2,2-bis [4- (3-aminophenoxy) phenyl] propane,
2,2-bis [4- (4-aminophenoxy) phenyl]
Propane, 2,2- [4- (3-aminophenoxy) phenyl] butane, 2,2-bis [4- (4-aminophenoxy) phenyl] butane, 2,2-bis [4- (3-aminophenoxy) ) Phenyl] -1,1,1,3,3,3-hexafluoropropane, 2,2-bis [4- (4-aminophenoxy) phenyl] -1,1,1,3,3,3-hexa Fluoropropane, 1,3-bis (3-aminophenoxy) benzene, 1,3
-Bis (4-aminophenoxy) benzene, 1,4-bis (3-aminophenoxy) benzene, 1,4-bis (4-
Aminophenoxy) benzene, 4,4'-bis (3-aminophenoxy) biphenyl, 4,4'-bis (4-aminophenoxy) biphenyl, bis [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] sulfoxide, bis [4- (4-aminophenoxy) phenyl] sulfoxide, bis [4- (3-aminophenoxy) phenyl]
Sulfone, bis [4- (4-aminophenoxy) phenyl] sulfone, bis [4- (3-aminophenoxy) phenyl] ether, bis [4- (4-aminophenoxy) phenyl] ether, 1,4-bis [ 4- (3-aminophenoxy) benzoyl] benzene, 1,3-bis [4- (3-aminophenoxy) benzoyl] benzene and the like can be mentioned.

The aromatic polyetherimide used as a fluidization accelerator in the present invention is a polymer composed of an ether bond and an imide bond as essential bond units. Is the main unit.

Here, Z is a trifunctional aromatic in which a bifunctional group among the trifunctional groups is bonded to adjacent carbons, and Ar is a divalent aromatic residue. Then, specifically, the aromatic polyetherimide used in the present invention is an aromatic polyetherimide having at least one repeating unit selected from the group consisting of the following formulas (1) to (8). . That is, These aromatic polyetherimides are commercially available from G.E., Ltd. under the names Ultem-100, Ultem-4000, Ultem-6000 and the like.

These aromatics can be freely produced with various degrees of polymerization, and those having appropriate melt viscosity characteristics for the intended blend can be arbitrarily selected.

The mixture of the thermoplastic polyimide of the present invention and the aromatic polyetherimide has a remarkably low melt viscosity in a high temperature range, particularly at 350 ° C. or higher, as compared with the case of using the thermoplastic polyimide alone. This effect is recognized even with a small amount of aromatic polyetherimide, and the lower limit of the effect is 0.1% by weight, but preferably 0.5% by weight or more.

Further, the mechanical strength of the aromatic polyetherimide at high temperature belongs to the excellent class among heat-resistant resins, but the mechanical strength, especially Izod impact strength, is inferior to that of the thermoplastic polyimide. If the amount of the aromatic polyetherimide is too large, the mechanical strength inherent to the thermoplastic polyimide cannot be maintained, which is not preferable.

Further, since aromatic polyether imides are easily dissolved in halogenated hydrocarbons such as methylene chloride and chloroform, amide solvents such as dimethylacetamide and N-methyl-2-pyrrolidone, aromatic polyether imides in the composition If the amount of the imide is too large, the chemical resistance inherent in the thermoplastic polyimide cannot be maintained, which is not preferable.

For the above reasons, the composition ratio of the aromatic polyetherimide has an upper limit, and is preferably 50% by weight or less.

In mixing and preparing the composition according to the present invention, the composition can be produced by a generally known method. For example, the following method is a preferable method.

(1) The thermoplastic polyimide powder and the aromatic polyetherimide powder are pre-kneaded into a powder using a mortar, a Henschel mixer, a drum blender, a tumbler blender, a ball mill ribbon blender and the like.

(2) A thermoplastic polyimide powder is dissolved or suspended in an organic solvent in advance, and an aromatic polyetherimide is added to the solution or suspension to be uniformly dispersed or dissolved. And

(3) An aromatic polyetherimide is dissolved or suspended in an organic solution of a polyamic acid that is a precursor of a thermoplastic polyimide, and then heat treated at 100 to 400 ° C, or a commonly used imidizing agent. After chemical imidization using, the solvent is removed to obtain a powder.

The powdery polyimide resin composition thus obtained is directly used for various molding applications, that is, injection molding, compression molding, transfer molding, extrusion molding, etc., but it is more preferable to use it after melt blending. Is. In particular, in mixing and preparing the above-mentioned composition, it is also a simple and effective method to mix and melt powders and pellets or powder and pellets.

For the melt blending, devices used for melt-blending ordinary rubber or plastics, for example, a hot roll, a Banbury mixer, a Brabender, an extruder and the like can be used. The melting temperature is set to a temperature higher than the melting temperature of the blending system and lower than the temperature at which the blending system starts to thermally decompose, and the temperature is usually 280 to 420 ° C., preferably 30 ° C.
0-400 ° C.

As the molding method of the resin composition of the present invention, injection molding or extrusion molding, which is a molding method of molding a homogeneous melt blend and having high productivity, is preferable, but other transfer molding, compression molding, or sintering molding is performed. Shape, extrusion film molding, etc. can be applied without any problem.

One or more solid lubricants such as molybdenum dioxide, graphite, boric acid nitride, lead monoxide, and lead powder can be added to the resin composition of the present invention. It is also possible to add one or more reinforcing agents such as glass fiber, carbon fiber, aromatic polyimide fiber, silicon carbide fiber, potassium titanate fiber and glass beads. In addition, with respect to the resin composition of the present invention, an antioxidant, a heat stabilizer, an ultraviolet absorber, a flame retardant, a flame retardant auxiliary, an antistatic agent, a lubricant, and a coloring material, as long as the object of the present invention is not impaired. One or more ordinary additives such as, can be added.

〔Example〕

Hereinafter, the present invention will be described in more detail with reference to Synthesis Examples, Examples and Comparative Examples.

Synthesis Example-1 A reaction vessel equipped with a stirrer, a reflux condenser and a nitrogen inlet tube was charged with 6.68 kg of bis [4- {4- (4-amino-α, α-dimethylbenzyl) phenoxy} phenyl] sulfone.
(10 mol) and 50.0 kg of N, N, -dimethylacetamide were charged, and pyromellitic dianhydride under a nitrogen atmosphere at room temperature 2.
14 kg (9.8 mol) was added while paying attention to the rise in solution temperature, and the mixture was stirred at room temperature for about 20 hours.

2.02 kg (20 mol) of triethylamine and 2.55 kg (25 mol) of acetic anhydride were added dropwise to this solution at room temperature under a nitrogen atmosphere. The mixture was stirred at room temperature for about 20 hours to obtain a pale yellow slurry. This slurry was separated by filtration, washed with methanol, separated by filtration, and dried under reduced pressure at 180 ° C. for 8 hours to obtain 8.26 kg (yield 9
7.6%) of pale yellow polyimide powder was obtained. The polyimide powder had an inherent viscosity of 0.83 dl / g. Here, the logarithmic viscosity is a value obtained by dissolving 0.5 g of polyimide powder in 100 ml of a solvent (p-chlorophenol: phenol = 90: 10 weight ratio) by heating, cooling, and measuring at 35 ° C. The glass transition temperature of this polyimide powder was 280 ° C. (measured by the DSC method, the same applies hereinafter), and the 5% weight loss temperature was 545 ° C. (measured by the DTA-TG method).

Synthesis examples-2 to 6 Various diamines and various tetracarboxylic dianhydrides In the same manner as in Synthesis Example-1, various polyimide powders were obtained.

Table 1 shows the polyimide synthesis conditions and the logarithmic viscosity of the produced polyimide powder.

Examples-1 to 14 The thermoplastic polyimide powders obtained in Synthesis Examples-1 to 6 and an aromatic polyetherimide, commercially available Ultem 1000 (trademark of GEE Co., USA) are shown in Table 2. As described above, after dry blending with various compositions, it was extruded at 330 to 350 ° C. using a twin-screw melt extruder and granulated.

The pellets thus obtained are subjected to an injection molding machine at a molding temperature of 36
Injection molding was carried out at 0 to 380 ° C and a mold temperature of 150 ° C, and the physical and thermal properties of the molded product were measured.

 The results are shown in Table 2 as Examples 1-14.

In the table, tensile strength and elongation at break are ASTM D-638, bending strength and flexural modulus are ASTM D-790, and Izod impact value is AST.
MD-256, glass transition temperature is TMA penetration method, heat distortion temperature is A
Based on STM D-648.

The table also shows the minimum injection pressure, which is a measure of melt fluidity.

Comparative Examples-1 to 6 Using the compositions outside the scope of the present invention, the physical and thermal properties of the molded articles obtained by the same operation as in Examples 1 to 14 were measured and the results are shown in Table-2. This is shown as a comparative example.

〔The invention's effect〕

The method of the present invention provides a polyimide resin composition having excellent melt flowability in addition to the excellent properties inherent in thermoplastic polyimide.

Claims (1)

(57) [Claims] 1. A formula (In the formula, X represents a carbonyl group or a sulfonyl group,
R is the following formula C = C, Represents at least one tetravalent group selected from the group consisting of 99.9 to 50% by weight of a thermoplastic polyimide having a repeating unit represented by the formula (1) and at least one aromatic selected from the group consisting of those having a repeating structural unit represented by the following formulas (1) to (8) Polyetherimide 0.1-50
A resin composition comprising 100% by weight.