JPH01161055A - Polyimide resin composition - Google Patents

Abstract

(57) [Summary] This bulletin contains application data before electronic filing, so abstract data is not recorded.

Description

DETAILED DESCRIPTION OF THE INVENTION [Field of Industrial Application] The present invention relates to a molding resin composition. More specifically, the present invention relates to a polyimide-based molding resin composition that has excellent heat resistance, chemical resistance, mechanical strength, etc., and excellent moldability.

[Conventional technology]

Polyimide, which is obtained by the reaction of tetracarboxylic dianhydride and diamine, has traditionally been used in electrical and electronic equipment due to its high heat resistance, excellent mechanical strength, dimensional stability, flame retardancy, and electrical insulation properties. It is used in fields such as , aerospace equipment, and transportation equipment, and is expected to continue to be widely used in fields that require heat resistance.

Various polyimides have been developed that exhibit superior properties.

However, even if it has excellent heat resistance, it does not have a clear glass transition temperature, so it must be processed using methods such as sintering when used as a molding material, and although it has excellent processability, it does not have a clear glass transition temperature. , low glass transition temperature,
Moreover, it is soluble in halogenated hydrocarbons, and its performance has both advantages and disadvantages, such as unsatisfactory heat resistance and solvent resistance.

[Problem that the invention seeks to solve]

An object of the present invention is to obtain a polyimide resin composition that has good moldability in addition to the excellent properties inherent to polyimide.

[Means for solving problems]

The present inventors have conducted extensive research to solve the above problems, and have found that a polyimide resin composition comprising a thermoplastic polyimide and a specific amount of aromatic polyetherimide is particularly effective for the above purpose. The present invention has been completed.

The inventor first described mechanical properties, thermal properties, electrical properties,
As a thermoplastic polyimide with excellent solvent resistance and heat resistance (wherein 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 fused polycyclic aromatic group, or a non-fused polycyclic group in which aromatic groups are interconnected directly or through a bridge member. We have discovered a thermoplastic polyimide containing a repeating unit represented by the following formula, which represents a tetravalent group selected from the group consisting of aromatic groups (Japanese Patent Application Laid-open No. 193020/1982).

The above-mentioned thermoplastic polyimide is a novel heat-resistant resin that has many good physical properties unique to polyimide. However, although the above polyimides are far superior in heat resistance and low mechanical properties compared to ordinary engineering plastics such as polyethylene terephthalate, polybutylene terephthalate, polyether sulfone, polysulfone, and polyphenylene sulfide, As the molecular weight of polyimide increases, melt fluidity decreases and moldability deteriorates.

An object of the present invention is to provide a polyimide resin composition for molding that has excellent melt flowability without impairing the inherent properties of thermoplastic polyimide.

That is, the present invention provides a polyimide 99.9 having a steering unit represented by (wherein X and R are the same as before)
~50 weight% double aromatic polyetherimide 0.1~50
% by weight.

The polyimide used in the present invention is of the formula) phenoxylabenzophenone or bis[4-(4-
It is obtained by imidizing a polyamic acid obtained by reacting (4-amino-α,α-dimethylbenzyl)phenoxy)phenyl]sulfone with one or more tetracarboxylic dianhydrides.

The tetracarboxylic dianhydride used at this time has the formula (R in the formula is the same as before) It is a tetracarboxylic dianhydride represented by

That is, the tetracarboxylic dianhydride used is:
Ethylenetetracarboxylic dianhydride, butanetetracarboxylic anhydride, cyclobenkunetetracarboxylic dianhydride, pyromellitic dianhydride, 3.3', 4.4'
-benzophenone tetracarboxylic dianhydride, 2,2°
, 3.3''-benzophenonetetracarboxylic dianhydride, 3.3', 4.4'-biphenyltetracarboxylic dianhydride, 2,2°73,3''-biphenyltetracarboxylic dianhydride, 2 .2-bis(3,4-dicarboxyphenyl)propanihydride, 2,2-bis(2,3-
dicarboxyphenyl)propanihydride, bis(3,
4-dicarboxyphenyl)ether dianhydride Th, bis(3,4-dicarboxyphenyl)sulfone dianhydride,
1.1-bis(2,3-dicarboxyphenyl)ethanihydride, bis(2,3-dicarboxyphenyl)methanidianhydride, bis(3,4-dicarboxyphenyl)methanidianhydride, 4.4' -(p-phenylenedioxy)
Cyphthalic dianhydride, 4.4'-(m-phenylenedioxy)cyphthalic dianhydride, 2.3,6.7-naphthalenetetracarboxylic dianhydride, L4,5.8-naphthalenetetracarboxylic acid Dianhydride, 1.2,5.6-naphthalenetetracarboxylic dianhydride, 1.2,3.4-benzenetetracarboxylic dianhydride, 3゜4.9.10-perylenetetracarboxylic dianhydride 2゜3.6.7-anthracentetracarboxylic dianhydride, 1.2,7.8
-phenanthrenetetracarboxylic dianhydride, etc., and these tetracarboxylic dianhydrides may be used alone or in combination of two or more.

The thermoplastic polyimide used in the composition of the present invention is a polyimide using the above-mentioned ether diamine as a raw material, but it may be obtained by mixing other diamines within a range that does not impair the good physical properties of this polyimide. Polyimides that can be used in the compositions of the present invention can also be used.

Examples of diamines that can be used in combination include m-phenylenediamine, 0-phenylenediamine, and p-phenylenediamine.
-phenylenediamine, m-aminobenzylamine, p
-aminobenzylamine, 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)phenylcomethane,
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-bis(4-(3-aminophenoxy)phenylcobutane), 2.2-bis(4-(4-
aminophenoxy)phenylcobutane, 2,2-bis(
4-(3-aminophenoxy)phenyl) -11,1
,3,3,3-hexafluoropropane, 2,2-bis(4-(4-aminophenoxy)phenyl) -1,1
, 1,3,3,3-hexafluoropropane, 1.3-
Bis(3-aminophenoxy)benzene, 1.3-bis(4-aminophenoxy)benzene, 1.4-bis(3
-aminophenoxy)benzene, 1,4-bis(4-aminophenoxy)benzene, 4,4°-bis(3-aminophenoxy)biphenyl, 4,4′-bis(4-aminophenoxy)biphenyl, bis(4-aminophenoxy)benzene, -(3-aminophenoxy)phenyl]ketone, bis(4-(4-aminophenoxy)phenyl)ketone, bis[4-(3-aminophenoxy)phenyl]sulfide, bis(4-(4-aminophenoxy)phenyl)ketone,
-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-amino) phenoxy)
Phenyl phether, bis(4-(4-aminophenoxy)phenyl phether, 1.4-bisC4-(3-aminophenoxy)benzoyl)benzene, 1.3-bis(4-(3-aminophenoxy)benzoyl) ] Examples include benzene.

The aromatic polyetherimide used as a fluidization promoter in the present invention is a polymer composed of both an ether bond and an imide bond as essential bonding units, and the repeating unit represented by the general formula is the main unit. ing.

Here, Z is a trifunctional aromatic group in which three of the three functional groups is bonded to an adjacent carbon, and Ar is a divalent aromatic residue. The following can be cited as specific examples. That is, these aromatic polyetherimides are available from GE Corporation in the United States as Ultem-1000,
It is commercially available under names such as Ultem-4000 and Ultem-6000.

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

The mixture of thermoplastic polyimide and aromatic polyetherimide of the present invention has a significantly lower melt viscosity in a high temperature range, particularly at 350'C or higher, compared to the case of thermoplastic polyimide alone. This effect is observed even when the amount of aromatic polyetherimide is small, and the lower limit of this effect is 0.1% by weight, but preferably 0.5% by weight or more.

In addition, the mechanical strength of aromatic polyetherimide at high temperatures is among the best among heat-resistant resins, but the mechanical strength, especially the Izot impact strength, is inferior to that of thermoplastic polyimide. If the amount of aromatic polyetherimide is too large, the inherent mechanical strength of the thermoplastic polyimide cannot be maintained, which is not preferable.

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

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

The composition according to the present invention can be mixed and prepared by commonly known methods, but the following methods are preferred, for example.

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

(2) Thermoplastic polyimide powder is dissolved or suspended in an organic solvent in advance, aromatic polyetherimide is added to this solution or suspension, and after uniformly dispersing or dissolving, the solvent is removed and powdered shall be.

(3) After dissolving or suspending aromatic polyetherimide in an organic solution of polyamic acid, which is a precursor of thermoplastic polyimide, heat treatment is performed at 100 to 400°C, or normally used imidization After chemical imidization using a solvent, the solvent is removed to form a powder.

The powdered polyimide resin composition thus obtained can be used as it is for various molding purposes, such as injection molding, compression molding, transfer molding, and extrusion molding.
A more preferred method is to use the mixture after melt blending. In particular, when preparing the composition by mixing, it is a simple and effective method to mix and melt powders, pellets, or powders and pellets.

Melt blending involves equipment used to melt blend conventional rubbers or plastics, such as hot rolls,
A Banbury mixer, a plastic bender, an extruder, etc. can be used. The melting temperature is set above the temperature at which the blended system can be melted and below the temperature at which the blended system begins to thermally decompose, and the temperature is usually 280 to 420°C, preferably 300 to 400°C.

As a method for molding the resin composition of the present invention, injection molding or extrusion molding, which is a molding method that molds a homogeneous molten blend and has high productivity, is suitable, but other methods such as transfer molding, compression molding, and sinter molding are suitable. There is no problem in applying shapes, extrusion film molding, etc.

Note that one or more solid lubricants such as molybdenum dioxide, graphite, boric acid nitride, lead oxide, and lead powder can be added to the resin composition of the present invention. It is also possible to add one or more types of reinforcing agents, such as glass fibers, carbon fibers, aromatic polyamide fibers, silicon carbide fibers, potassium titanate fibers, and glass peas. In addition, antioxidants, heat stabilizers, ultraviolet absorbers, flame retardants, flame retardant aids, antistatic agents, lubricants, and colorants may be added to the resin composition of the present invention within a range that does not impair the purpose of the present invention. One or more conventional additives such as , etc. can be added.

[Example] The present invention will be explained in more detail below using Synthesis Examples, Examples, and Comparative Examples.

Synthesis Example-1 Bis(4-(4-(4-amino-α,α-dimethylbenzyl)phenoxy)phenyl)sulfone 6.6
8 kg (10 mol) and 50.0 kg of N,N,-dimethylacetamide were charged, and 2.14 kg (9.8 mol) of pyromellitic dianhydride was added under nitrogen atmosphere at room temperature.
The solution was added while being careful not to increase the temperature of the solution, and the mixture was stirred at room temperature for about 20 hours.

To this solution was added 2.02 kg (20
mol) of triethylamine and 2.55 kg (25
mol) of acetic anhydride was added dropwise. After stirring at room temperature for about 20 hours, a pale yellow slurry was obtained. Filter this slurry and
After washing with methanol, the mixture was separated and dried under reduced pressure at 180°C for 8 hours to obtain 8.26 kg (yield: about 97.6%) of pale yellow polyimide powder. The logarithmic viscosity of this polyimide powder was Q, 83 dfl/g. Here, the logarithmic viscosity is calculated by adding 0.5 g of polyimide powder to 100 ml of solvent (p-chlorophenol:phenol = 90:10 weight ratio).
This is the value measured at 35°C after heating and dissolving the material and cooling it. In addition, the glass transition temperature of this polyimide powder is 280°
C (measured by the DSC method, the same applies hereinafter), and the 5% weight loss hot water temperature was 545° C. (measured by the DTA-TO method).

Synthesis Examples 2 to 6 Various diamines and various tetracarboxylic dianhydrides were combined and the same procedure as in Synthesis Example 1 was carried out to obtain various polyimide powders.

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

Examples-1 to 14 Thermoplastic polyimide powder obtained in Synthesis Examples-1 to 6,
Aromatic polyetherimide, commercially available Ultem 1000 (trademark of GE Corporation, USA), was triblended with various compositions as shown in Table 2, and then heated at 330 to 350°C using a two-wheel melt extruder. It was extruded and granulated.

The obtained pellet was put into an injection molding machine at a molding temperature of 36
Injection molding was performed at a mold temperature of 150°C from 0 to 380°C, and the physical and thermal properties of the molded product were measured.

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

In the table, tensile strength and elongation at break are ASTM D-638, bending strength and flexural modulus are ASTM D-790, Izod impact value is ASTM D-256, glass transition temperature is TMA needle corporation deformation temperature is ASTM D- According to 648.

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

Comparative Examples 1 to 6 Table 2 shows the results of measuring the physical and thermal properties of molded products obtained by the same operations as Examples 1 to 14 using compositions outside the scope of the present invention. Shown as a comparative example.

〔Effect of the invention〕

The method of the present invention provides a polyimide resin composition that has excellent melt flowability in addition to the excellent properties inherently possessed by thermoplastic polyimide.

Patent applicant Kunio Ogawa, Commissioner of the Patent Office, Mitsui Toatsu Chemical Co., Ltd.3. Relationship with the person making the amendment Patent applicant address 3-2-5 Kasumigaseki, Chiyoda-ku, Tokyo Name (31
2) Mitsui Toatsu Chemical Co., Ltd. 4. The number of inventions that will increase due to the amendment will be zeroed out.

Claims (1)

[Claims] 1) Formula ▲ Numerical formula, chemical formula, table, etc. ▼ (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 fused polycyclic aromatic group, or a non-fused polycyclic group in which aromatic groups are interconnected directly or through a bridge member. represents a tetravalent group selected from the group consisting of aromatic groups. 99.9 to 50% by weight of thermoplastic polyimide having repeating units represented by ) and 0.9% by weight of aromatic polyetherimide.
A resin composition consisting of 1 to 50% by weight.