JPH01279965A - Polyimide resin composition - Google Patents

Abstract

PURPOSE:To improve the moldability without impairing the excellent heat resistance, mechanical strength, etc., inherent in polyimide by incorporating a specified amount of an aromatic polysulfone into a polyimide having specified repeating units. CONSTITUTION:The title composition is prepared by incorporating 0.1-50wt.% aromatic polysulfone (e.g., of formula II) into 99.9-50wt.% polyimide having repeating units of formula I (wherein R is a tetravalent group selected from among a 2C or higher aliphatic group, an alicyclic group, a monocyclic aromatic group, a condensed polycyclic aromatic group, and a noncondensed polycyclic aromatic group wherein the aromatic groups are bound to one another directly or through a crosslinking member). Said polyimide can be obtained by reacting an etherdiamine of formula III with a tetracarboxylic acid dianhydride to give a polyamic acid and imidating this acid.

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 be widely used in fields where heat resistance is required in the future.

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 when it is used as a molding material, it must be processed using methods such as sintering. However, it had advantages and disadvantages in terms of performance, such as having a low glass transition temperature, being soluble in halogenated hydrocarbons, and being unsatisfactory in terms of 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 which not only has the excellent properties inherently possessed by polyimide but also has extremely good moldability.

[Means for solving problems]

The present inventors conducted intensive research to solve the above-mentioned problems, and found that a polyimide-based resin composition comprising a new polyimide and a specific amount of aromatic polysulfone is particularly effective for the above-mentioned purpose. Completed the invention.

The inventor first described mechanical properties, thermal properties, electrical properties,
As a polyimide having excellent solvent resistance and heat resistance, the formula (wherein R is an aliphatic group having 2 or more carbon atoms, a cycloaliphatic group,
Represents a tetravalent group selected from the group consisting of a monocyclic aromatic group, a fused polycyclic aromatic group, and a non-fused polycyclic aromatic group in which aromatic groups are interconnected directly or through a bridge member. , ) We have discovered a resin that grows repeating units represented by (
(Patent Application No. 1982-076095).

The above-mentioned polyimide is a new heat-resistant resin having good physical properties unique to polyimide.

However, compared to ordinary engineering plastics such as polyethylene terephthalate, polybutylene terephthalate, polyether sulfone, polysulfone, and polyphenylene sulfide, the above polyimide has much superior heat resistance and other properties, but has a large molecular weight. In this case, the melt fluidity decreases, and the moldability is still inferior to those resins.

An object of the present invention is to provide a polyimide resin composition for molding that has excellent fluidity during melting without impairing the inherent properties of polyimide.

That is, the present invention provides polyimide 99.9 having a repeating unit represented by the formula (wherein R is the same as before)
~50% by weight and aromatic polysulfone 0.1-50% by weight
It is a resin composition consisting of.

The polyimide used in the present invention is an ether diamine represented by the formula as a diamine component, that is, bis[4-(3-
(4-Aminophenoxy)benzoyl)phenyl]ether is used, and is obtained by imidizing a polyamic acid obtained by reacting this with one or more types of tetracarboxylic dianhydride. Preferably it is carried out in an organic solvent.

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 dianhydride, cyclopentanetetracarboxylic dianhydride, pyromeria dianhydride, 3.3', 4.4'
-benzophenonetetracarboxylic dianhydride, 2,2
°, 3.3'-benzophenonetetracarboxylic dianhydride, 3.3', 4.4''-biphenyltetracarboxylic dianhydride, 2.2°, 3,3°-biphenyltetracarboxylic dianhydride , 2.2-bis(3,4-dicarboxyphenyl)propanihydride, 2.2-bis(2,3-
dicarboxyphenyl)propanihydride, bis(3,
4-dicarboxyphenyl)ether diamine, 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, 4,4°-( p-)unilenedioxy)cyphthalic dianhydride, 4.4°-(m-phenylenedioxy)cyphthalic dianhydride, 2.3.6.7-naphthalenetetracarboxylic dianhydride, 1.4 .5.8-Naphthalenetetracarboxylic dianhydride, 1.2,5.6-naphthalenetetracarboxylic dianhydride, 1.2,3.4-Hensenetetracarboxylic dianhydride, 3°4. 9.10-perylenetetracarboxylic dianhydride, 2゜3.6.7-anthracenetetracarboxylic dianhydride, 1.2,7.8
-phenanthrenetetracarboxylic dianhydride, etc., and these tetracarboxylic dianhydrides may be used alone or in combination of two or more.

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

Examples of diamines that can be used in combination include m-phenylenediamine, O-phenylenediamine, and p-phenylenediamine.
-phenylenediamine, m-aminobenzylamine, p
-aminobenzylamine, bis(3-aminophenyl)
ether, (3-aminophenyl)(4-7minophenyl) 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)phenylcomethane, 1.L-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) -1,1
, 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-(3-aminophenoxy)phenylkoketone, bis(4-(4-aminophenoxy)phenylkoketone, 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), and the like.

The aromatic polysulfone used as a fluidization promoter in the present invention is a polysulfone having a repeating unit such as (. VICTREX from I.C.I.
Polyether sulfone, commercially available under the trademark ``PES'' and/or represented by the formula -S, U.S. Union Carbide Lk#l) ``UD
Examples include polysulfones sold under the trademark ELPOLYSULFONE.

These aromatic polysulfones 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 molding resin composition of the present invention comprises the polyimide 99.9 to 99.9.
511%, and the aromatic polysulfone is adjusted to be in the range of 0.1 to 50% by weight.

The polyimide/aromatic polysulfone composite resin system of the present invention exhibits a significantly low melt viscosity in a high temperature range such as 350°C or higher.The good fluidizing effect of aromatic polysulfone is observed even in small amounts, and the lower limit of its composition ratio is 0.1% by weight
However, it is preferably 0.5% by weight or more.

In addition, although the mechanical strength of aromatic polysulfone at high temperatures is among the best among heat-resistant resins, its mechanical strength is inferior to that of polyimide, so if the amount of aromatic polysulfone in the composition is too large, However, the inherent mechanical strength of the polyimide cannot be maintained, which is undesirable.Therefore, there is an upper limit to the composition ratio of the aromatic polysulfone, which 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) Preliminarily kneading polyimide powder and aromatic polysulfone powder using a mortar, Henschel mixer, drum blender, tumbler blender, ball mill ribbon blender, etc. to form a powder.

(2) Polyimide powder is dissolved or suspended in an organic solvent in advance, aromatic polysulfone is added to this solution or suspension, and after uniformly dispersing or dissolving, the solvent is removed to form a powder.

(3) Dissolve aromatic polysulfone in an organic solvent solution of polyamic acid, which is a precursor of the polyimide of the present invention. After making it cloudy, it is heated to 100 to 400°C or chemically imidized using a commonly used imidizing agent, and then 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. Especially when mixing the said composition! When producing Il, 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 280-420°C, preferably 300-400°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 using shapes, extrusion film molding, etc.

In addition, one or more solid lubricants such as molybdenum disulfide, graphite, boric acid nitride, lead oxide, lead powder, etc. 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 with reference to Synthesis Examples, Examples, and Comparative Examples.

Synthesis Example-1 In a reaction vessel equipped with a stirrer, a reflux condenser, and a nitrogen inlet tube, 5°92 kg (10 moles) of bis(4-(3-(4-aminophenoxy)benzoyl)phenyl ether, N, N,-dimethylacetamide 18.8kg
2.14 kg (9.8 mol) of lomelift dianhydride was added under a nitrogen atmosphere at room temperature, being careful not to increase the solution temperature, and stirred at room temperature for about 24 hours to obtain a polyamic acid solution. Ta.

5.37 kg of N,N,-dimethylacetamide was added to this polyamic acid solution, and while stirring at room temperature under a nitrogen atmosphere, 4.08 kg (40 mol) of triethylamine and 6.03 kg (60 mol) of acetic anhydride were added dropwise. .

After approximately 24 hours of additional stirring at room temperature, the solution was drained into 2501 of vigorously stirred water. The obtained precipitate was filtered, washed with methanol, and dried under reduced pressure at 150°C for 24 hours to obtain 7.47 kg (yield: 97.0
%) of pale yellow polyimide powder was obtained.

The logarithmic viscosity of this polyimide powder was 0.83 dl/g. Here, the logarithmic viscosity is 0.5g of polyimide powder.
-Mixed solvent of chlorophenol and phenol (p-chlorophenol:phenol = 90:10 weight ratio)
This value was measured after heating and dissolving 100 g of the sample and cooling it to 35°C.

Furthermore, the glass transition temperature of this powder according to DSC measurement is 23
The temperature was 5°C.

Examples-1 to 3 Polyimide powder obtained in Synthesis Example-1 and aromatic polysulfone powder, commercially available tlDEL P
After tri-blending OLYSIILFONE P-1700 (trademark of Union Carbide Company, USA) with various compositions as shown in Table 1, it was mixed with 360 to 39
It was extruded and granulated at 0°C.

The obtained pellets were put into an injection molding machine and injection molded at a cylinder temperature of 360 to 390°C and a mold temperature of 170°C, and the physical and thermal properties of the molded product were measured.

The results are shown in Table 1 as Examples 1 to 3. In the table, the minimum injection molding pressure, which is a measure of moldability, is also listed.

The tensile strength and elongation at break in the table are ASTl'l D-638
, bending strength and flexural modulus are ASTM D-790, Izod impact value is ASTM [1-256, glass transition temperature is TMA needle corporation method deformation temperature is ASTM D-64
Based on 8.

Comparative Example-1 The results of measuring the physical and thermal properties of molded products obtained by the same operations as Examples 1 to 3 using a composition outside the scope of the present invention are also compared in Table-1. This is shown as Example-1.

Synthesis Examples 2 to 5 Various polyimide powders were obtained by combining various diamines and various tetracarboxylic dianhydrides in the same manner as in Synthesis Example 1.

Table 2 shows the polyimide resin synthesis conditions, logarithmic viscosity, and glass transition temperature of the resulting polyimide powder.

Examples 4 to 11, Comparative Examples 2 to 5 Polyimide powder obtained in Synthesis Examples 2 to 5 and aromatic polysulfone, commercially available tlDELPOLY
SULFONE P-1700 (U.S. Union Carbide Company trademark) or VICTREX PES 3600
P (trademark of ICI Corporation) having the composition shown in Tables 3 and 4 was extruded while being melt-kneaded using an extruder to obtain uniformly blended pellets.

Next, the uniformly blended pellets obtained above were used in Examples-1 to
Injection molding was carried out under the same conditions as in Example 3, and the physical and thermal properties were measured.

The results of compositions within the scope of the present invention are shown in Examples 4 to 11.
Compositions outside the range are shown in Table 3 as Comparative Examples 2 to 5.
- Shown in 4.

〔Effect of the invention〕

According to the method of the present invention, a polyimide resin composition which not only has the excellent properties inherently possessed by polyimide but also has extremely good moldability is provided.

Patent Applicant: Mitsui Toatsu Chemical Co., Ltd. Proceeding Officer Bo Jeong-hui (Volunteer) January 1, 1999 Director General of the Patent Office Yoshi 1) Moon Takeshi 1, Indication of Case 1986 Patent Application No. 109081 2 , Title of the invention: Polyimide resin composition 3, Relationship with the case of the person making the amendment Patent applicant's address: 3-2-5-4 Kasumigaseki, Chiyoda-ku, Tokyo Number of inventions increased by the amendment: Produced in an organic solvent. Delete that.

(2) The statement "mechanical strength is" on page 15, line 12 of the specification is corrected to "mechanical strength is".

(3) In the column of bending strength of Example 6 in Table 3 on page 24 of the specification, the number rl150J is corrected to r1200J.

Claims (1)

[Claims] 1) Formula ▲ Numerical formula, chemical formula, table, etc. ▼ (In the formula, R is an aliphatic group having 2 or more carbon atoms, a cycloaliphatic group,
Represents a tetravalent group selected from the group consisting of a monocyclic aromatic group, a fused polycyclic aromatic group, and a non-fused polycyclic aromatic group in which aromatic groups are interconnected directly or through a bridge member. . ) Polyimide 99.9 having a repeating unit represented by
~50% by weight and aromatic polysulfone 0.1-50% by weight
A resin composition consisting of. 2) The resin composition according to claim 1, wherein the aromatic polysulfone is a polysulfone consisting of a repeating unit represented by the following formula (numerical formula, chemical formula, table, etc.). 3) The resin composition according to claim 1, wherein the aromatic polysulfone is a polysulfone consisting of a repeating unit represented by the following formula (numerical formula, chemical formula, table, etc.).