JPS63289066A - Polyimide resin composition - Google Patents

Abstract

PURPOSE:To obtain a polyimide resin composition which is excellent in heat resistance, dimensional stability, strength, etc., can be melt-molded and is suitable for, e.g., electronic devices, by mixing a polyimide resin produced from a specified ether diamine with a specified amount of glass fiber. CONSTITUTION:A polyimide resin having repeating units each represented by formula I (wherein X is carbonyl or sulfone, Y is formula II and R is a tetravalent group selected from among a 2C or higher aliphatic group, a cycloaliphatic group, a monocyclic aromatic group, a condensed polycyclic aromatic group and a noncondensed polycyclic aromatic group) is prepared. 100pts.wt. this polyimide resin is mixed with 5-100pts.wt. glass fiber to obtain the purpose polyimide resin composition. Said polyimide resin can be obtained by reacting an ether diamine of formula III as a diamine component with a tetracarboxylic dianhydride of formula IV.

Description

DETAILED DESCRIPTION OF THE INVENTION [Field of Industrial Application] The present invention relates to a novel polyimide resin composition having excellent heat resistance, dimensional stability, mechanical strength, etc.

[Conventional technology]

Traditionally, polyimide resins obtained by the reaction of tetracarboxylic dianhydride and diamines have high heat resistance,
Due to its excellent mechanical strength, dimensional stability, flame retardancy, and electrical insulation properties, it is widely used in fields such as electrical and electronic equipment, aerospace equipment, and transportation equipment, and will continue to improve its heat resistance. It is expected that it will be used in required fields.

Many conventionally developed polyimides exhibit excellent properties, but some have excellent heat resistance but poor processability, and resins developed with the aim of improving processability have poor heat resistance and solvent resistance. There were advantages and disadvantages in performance, such as being inferior to .

The present inventors first developed a polyimide resin of the general formula (I) (wherein X is a carbonyl group or a sulfone Y represents a group, 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 polyimide resin having repeating units represented by the following formulas (Japanese Patent Application No. 60-193020).

The above polyimide resin is a new heat-resistant resin that has good physical properties unique to polyimide resins, and is superior to ordinary engineering plastics such as polyethylene terephthalate, polybutylene terephthalate, polyether sulfone, polysulfone, and polyphenylene sulfide. Although the heat resistance is much better, the glass transition temperature is 220-290℃ and the heat distortion temperature is 200-200℃.
There were some problems in terms of heat resistance, which was around 270°C.

[Problems to be Solved by the Invention] The purpose of the present invention is to obtain a polyimide resin composition with further improved heat resistance, dimensional stability, mechanical strength, etc., without impairing the moldability of the polyimide resin. It is in.

[Means for Solving the Problems] The present inventors have conducted extensive research to achieve the above object, and have found that a polyimide resin composition comprising the polyimide resin and a specific amount of glass fiber is effective. They discovered this and completed the present invention.

That is, the present invention provides polyimide resin 10 represented by formula (I).
This is a polyimide resin composition consisting of 0 parts by weight and 5 to 100 parts by weight of glass fibers.

The polyimide resin used in the present invention has the formula (I1) as a diamine component (wherein, X represents a carbonyl group or a sulfone group,
), i.e., 4.4°-bis(
4-(4-amino-α,α-dimethylbenzyl)phenoxifbenzophenone or 4.4°-bis(4-(4
-amino-α,α-dimethylbenzyl)phenoxyfudiphenyl sulfone, and is a polyimide obtained by further cyclodehydration of polyamic acid obtained by reacting these with one or more tetracarboxylic dianhydrides. It is.

Further, other diamines may be mixed and used within a range that does not impair the various good physical properties of the polyimide resin used in the present invention. Examples of diamines that can be used in combination include mekphenylenediamine, paraphenylenediamine, orthophenylenediamine, aminobenzylamine, p-aminobenzylamine, 313°-diaminodiphenyl ether, 3.4'-diaminodiphenyl ether, 4. 4°-diaminodiphenyl ether, 3.3°-diaminodiphenyl sulfide, 3,4°-diaminodiphenylsulfide, 4,4°-diaminodiphenylsulfide, 3.3°-diaminodiphenylsulfoxide, 3,4°-diaminodiphenylsulfoxide , 4,4°-diaminodiphenylsulfoxide, 3
゜3゜-diaminodiphenylsulfone, 3,4'-diaminodiphenylsulfone, 4,4゛-diaminodiphenylsulfone, 313゜-diaminobenzophenone, 3゜4゜-diaminobenzophenone, 4,4゜-diaminobenzophenone, bis( 4-(3-aminophenoxy)phenylcomethane, bis(4-(4-aminophenoxy)
Phenylcomethane, 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, 2I2-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, 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,
Examples include 1.4-bis(4-(3-aminophenoxy)benzoyl)benzene and 1.3bis(4-(3-aminophenoxy)benzoyl)benzene.

The tetracarboxylic dianhydride used in this method has the formula (Iff) (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. , ) is a tetracarboxylic dianhydride represented by

That is, the tetracarboxylic dianhydride used is:
For example, ethylenetetracarboxylic dianhydride, cyclopencune carboxylic dianhydride, and lomelift dianhydride,
3,3°14,4° -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)
Propane dianhydride, bis(3,4-dicarboxyphenyl)ethane dianhydride, bis(3゜4-dicarboxyphenylsulfone dianhydride, 1,1-bis(2,3-dicarboxyphenyl)ethane dianhydride) compound, bis(2,3-dicarboxyphenyl)ethane dianhydride, bis(3,4-dicarboxyphenyl)ethane dianhydride, 2.3.6.7
-Naphthalenetetracarboxylic dianhydride, 1,4,5.
8-Naphthalenetetracarboxylic 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-phenantetracarboxylic dianhydride, 4
．． Examples thereof include 4°-<p-phenylenedioxy)cyphthalic dianhydride and 4.4°-(m-phenylenedioxy)cyphthalic dianhydride.

These tetracarboxylic dianhydrides may be used alone or in combination of two or more.

Glass fiber is made by rapidly cooling molten glass while drawing it using various methods to form thin fibers with a predetermined diameter. This means bundled roving, etc., and any of them can be used in the present invention. In order to make the glass fibers compatible with the base resin of the present invention, silane coupling agents such as aminosilane and epoxysilane, chromic chloride, and other surface treatment agents depending on the purpose can be used.

The length of the glass fiber in the present invention greatly affects the physical properties of the molded product obtained and the workability during production of the molded product. Generally, as the length of the glass fiber increases, the physical properties of the molded article improve, but on the contrary, the workability during production of the molded article deteriorates. For this reason,
In the present invention, the length of the glass fiber is 0.1 to 5 mm.
s is preferably in the range of 063 to 4 m-, since both the physical properties and workability of the molded product are well-balanced.

The glass fiber in the present invention is 5 to 100 parts by weight, preferably 10 to 50 parts by weight, based on 100 parts by weight of the polyimide resin.
Weight parts can be used. If it is less than 5 parts by weight, the reinforcing effect peculiar to glass fiber, which is a feature of the present invention, cannot be obtained, and conversely, if it is used more than 100 parts by weight, the fluidity of the composition during molding will deteriorate, making it difficult to obtain a satisfactory molded product. It becomes difficult.

The composition for polyimide resin according to the present invention can be produced by a generally known method, but the following method is particularly preferred.

(I1 polyimide powder, glass fiber in mortar, Henschel mixer, drum blender, tumbler blender,
After preliminary mixing using a ball mill, ribbon blender, etc., the mixture is kneaded using a commonly known melt mixer, hot roll, etc., and then made into pellets or powder.

(2) Polyimide powder is dissolved or suspended in an organic solvent in advance, glass fibers are impregnated with this solution or suspension, and then the solvent is removed in a hot air oven and then made into pellets or powder. In this case, examples of the solvent include N,N-dimethylformamide, N,N-dimethylmethoxyacetamide, 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, pyridine, picoline, dimethyl sulfoxide, dimethyl sulfone, tetramethylurea, hexamethylphosphoramide, phenol,
Examples include m-cresol, p-cresol, 0-cresol, anisole, and p-chlorophenol. Further, these organic solvents may be used alone or in combination of two or more.

(3) After impregnating glass fibers in a solution of polyamic acid, which is a precursor of the polyimide of the present invention, dissolved in the organic solvent, heat treatment is performed at 100 to 400°C, or a commonly used imidizing agent is used. After chemical imidization, the solvent is removed and the product is made into pellets or powder.

The composition of the present invention may contain conventional additives such as antioxidants, heat stabilizers, ultraviolet absorbers, flame retardant aids, antistatic agents, lubricants, colorants, etc., to the extent that the purpose of the present invention is not impaired. One or more kinds of additives can be added.

Also, other thermoplastic resins (e.g., polyethylene, polypropylene, polyamide, polycarbonate, polyarylate, polysulfone, polyethersulfone, polyetherketone, modified polyphenylene oxide, polyphenylene sulfide, polyamideimide, polyetherimide, etc.), thermosetting resins (e.g. phenolic resins,
The polyimide resin composition of the present invention can also contain fillers such as clay, mica, silica, graphite, glass beads, alumina, and calcium carbonate in appropriate amounts depending on the purpose. It is molded by a known molding method such as a molding method, an extrusion molding method, a compression molding method, or a rotary molding method, and then put into practical use.

〔Example〕

Hereinafter, the present invention will be further explained in detail by giving production examples, examples, and comparative examples.

In addition, unless otherwise specified, the values of % and parts shown in the following examples mean % by weight and parts by weight, respectively.

Production Example 1 4,4゛-bis(4-(4-amino-α).

α-dimethylbenzyl)phenoxyfudiphenylsulfone 6.68Kg (I0 mol) and N,N-dimethylace[
50.0 g of amide was charged, and 2.14 kg (9.8 mol) of pyromellitic dianhydride was added under a nitrogen atmosphere at room temperature while being careful not to increase the solution temperature, and the mixture was stirred at room temperature for about 20 hours. .

To this solution, 2.02Kg (20
mol) of triethylamine and 2.55 Kg (25 mol) of acetic anhydride were added dropwise. Stir at room temperature for about 20 hours,
A pale yellow slurry was obtained. This slurry was filtered, washed with methanol, filtered, 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 is 0.65
It was dl/g. Here, the logarithmic viscosity is 0 for polyimide powder.
．． This is the value measured at 35° C. after dissolving 5 g of the solution by heating in 100 ml of a solvent (p-chlorophenol; phenol-90/10 weight ratio).

Additionally, the glass transition temperature of this polyimide powder is 278°C.
(Measured by DSC method) and 5% weight! The decreasing temperature is 5
The temperature was 47°C (measured by the DTA-TG method).

Figure 1 shows an infrared absorption spectrum diagram of the obtained polyimide powder. In this spectrum diagram, the characteristic absorption band of imide is 1720 (around J-' and 1780el11
-', and 12, which is the characteristic absorption band of the ether bond.
Around 403-', 133 is the characteristic absorption band of the sulfone group.
Absorption near 0(J-' and 1150 cm-' was clearly observed.

Production Examples 2 to 5 The same procedure as Production Example 1 was carried out using a combination of the diamine used in the present invention and various tetracarboxylic dianhydrides.
Various polyimide powders were obtained. Table 1 shows the polyimide synthesis conditions, logarithmic viscosity and glass transition temperature of the produced polyimide powder. Table 1 also shows the production conditions of Production Example 1 and the physical properties of the produced polyimide powder. I wrote it down.

Examples 1 to 22, Comparative Examples 1 to 10 Silane-treated glass fibers (Nitto Boseki Co., Ltd. Manufactured by C5-3P
E-4765) in the amounts shown in Tables 2 to 6 and mixed with a drum blender mixer (manufactured by Yoda Seisakusho).
After melt-kneading in a 1gl11 single-screw extruder at a temperature of 310 to 350°C, the strands were air-cooled and cut to obtain pellets.

The obtained pellet was injection molded using an injection molding machine (Arburg Allround A-220, manufactured by Arburg, West Germany) at an injection pressure of 500 kg/ci and a cylinder temperature of 340~
(380° C., mold temperature 180° C.) Tensile test pieces, bending test pieces, Izot impact strength test pieces, and mold shrinkage rate measurement test pieces were obtained.

Tensile test follows ASTM D-638, bending test follows AST
MD-790, Izotsu impact strength test is ASTM
D-256, heat distortion temperature was determined according to ASTM D-684, and molding shrinkage rate was determined according to ASTM D-955. The results are shown in Tables 2-G.

〔Effect of the invention〕

The heat-resistant resin composition of the present invention has excellent heat resistance, dimensional stability, mechanical strength, etc., and can be melt-molded, and is used for electrical and electronic equipment, aerospace equipment, transportation equipment, and office equipment. It can also be used in a wide range of industrial fields as general industrial equipment.

[Brief explanation of drawings]

FIG. 1 is an example of an infrared absorption spectrum diagram of the polyimide powder of the present invention.

Claims (1)

[Claims] Formula (I) ▲There are mathematical formulas, chemical formulas, tables, etc.▼(I) (In the formula, X represents a carbonyl group or sulfone group, and Y represents ▲There are mathematical formulas, chemical formulas, tables, etc.), 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 resin 100 having a repeating unit represented by
A polyimide resin composition comprising 5 parts by weight and 5 to 100 parts by weight of glass fiber.