JPS63301253A - Polyimide resin composition - Google Patents

Abstract

PURPOSE:To obtain a polyimide resin composition which is melt-moldable, excellent in heat resistance, dimensional stability, mechanical strengths, etc. and suitable for electronic devices, etc., by mixing a polyimide resin having specified repeating units with a specified amount of a reinforcing fiber. CONSTITUTION:The purpose polyimide resin composition is formed by mixing 100pts.wt. polyimide resin (A) having repeating units each represented by formula I (wherein 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 composed of aromatic groups bonded directly or through bridging members) with 5-100pts.wt. reinforcing fiber (B) (e.g. carbon fiber or glass fiber). Component A can be obtained by reacting an ether-diamine of formula II with a tetracarboxylic acid dianhydride and dehydrating the formed polyamic acid to effect ring closure.

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 terms of performance.

The present inventors first developed a polyimide resin having the general formula (1) (wherein R is 2 or more carbon atoms) as a polyimide resin that can be melt-molded and has excellent mechanical strength, thermal properties, electrical properties, solvent resistance, etc. consisting of an aliphatic group, a cycloaliphatic group, a monocyclic aromatic group, a fused polycyclic aromatic group, or a non-fused polycyclic aromatic group in which aromatic groups are interconnected directly or through a bridge member. 4 selected from the group
We have discovered a polyimide resin having a repeating unit represented by ), which represents a valence group (Japanese Patent Application No. 61-297641).

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 Problem C] The present inventors have conducted intensive research to achieve the above object, and as a result, it has been found that a polyimide resin composition comprising the polyimide resin and a specific amount of reinforcing 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 reinforcing fibers.

The polyimide resin used in the present invention has the formula (n) (n) (wherein, X represents a carbonyl group or a sulfone group) as a diamine component.

) is a polyimide obtained by further cyclodehydration of a polyamic acid obtained by reacting an ether diamine represented by the following formula with one or more types of tetracarboxylic dianhydride.

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, 3,3'-diaminodiphenyl ether, 3,4'-diaminodiphenyl ether, 4.4'-diaminodiphenyl ether, 3.3'-diaminodiphenylsulfide, 3,4'-diaminodiphenylsulfide, 4,4'-diaminodiphenyl sulfide, 3,3'-diaminodiphenylsulfoxide, 3.4''-diamino diphenyl sulfoxide, 4,4°-diaminodiphenylsulfoxide, 3
゜3゛-diaminodiphenylsulfone, 3,4゛-diaminodiphenylsulfone, 4,4'-diaminodiphenylsulfone, 3,3゛-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, 212-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, 113-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 fusulfide, bis(4-(4-aminophenoxy) phenyl fusulfide, 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, 1,3bis(4 -(3-aminophenoxy)benzoyl]benzene and the like.

The tetracarboxylic dianhydride used in this method has the formula (I[[) (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, cyclobencunecarboxylic dianhydride, pyromellitic dianhydride,
3.3', 4.4' -benzophenone, tetracarboxylic 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)propanihydride, 2.2-bis(2,3-dicarboxyphenyl)propanihydride, bis(3 ,4-dicarboxyphenyl)ether dianhydride, bis(3,4-dicarboxyphenylsulfone dianhydride, 1.1-bis(2,3-dicarboxyphenyl)ethane dianhydride, bis(2,3-
dicarboxyphenyl)methanihydride, bis(3,4
-dicarboxyphenyl) mecunni anhydride, 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-anthracenetetracarboxylic dianhydride, 1,2,7.8-phenantetracarboxylic dianhydride, 4,4°-<p-phenylenedioxy)cyphthalic dianhydride , 4.4'-(m-7 22-dioxy)cyphthalic dianhydride, and the like.

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

The reinforcing fibers used in the present invention are carbon fibers, glass fibers,
Indicates commonly known inorganic or organic fibers such as potassium titanate fibers, aromatic polyamide fibers, ceramic fibers, and silicon carbide fibers.

As carbon fibers, high elasticity and high strength fibers obtained by carbonizing polyacrylonitrile, petroleum pitch, etc. as main raw materials can be used. Furthermore, due to the reinforcing effect and mixability of carbon fibers, carbon fibers with an appropriate diameter and appropriate aspect ratio (length/diameter ratio) are used, and the diameter of carbon fibers is usually 5 to 20μ, particularly 8 to 15μ. The aspect ratio is preferably about 1 to 600, and particularly preferably about 100 to 350 from the viewpoint of mixability and reinforcing effect. If the aspect ratio is small, there will be no reinforcing effect, and if the aspect ratio is large, the mixing property will be poor and a good molded product will not be obtained. Those treated with polyamide resin, polycarbonate resin, polyacecool resin, etc., and those treated with other known surface treatment agents depending on the purpose are also used.

Glass fibers are made by rapidly cooling molten glass while drawing it using various methods to form thin fibers with a predetermined diameter, and by using a binding agent to bundle single fibers together into strands, and by uniformly aligning the strands to form a bundle. Roving etc. can be used. Furthermore, the glass fibers may be treated with a silane coupling agent such as aminosilane or epoxysilane, chromic chloride, or other surface treatment agent depending on the purpose in order to have affinity with the base resin of the present invention. .

The length of the glass fiber 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. Therefore, in the present invention, it is preferable that the length of the glass fiber be in the range of 0.1 to 6ffi+++, preferably 0.3 to 4 mm, since the physical properties and workability of the molded product are well-balanced. .

Potassium titanate fiber is a type of high-strength fiber (whisker), and its chemical composition is 0.6TiOt.
, 6T+Oz .18H,O, and those having a typical melting point of 1300 to 1350°C can be used. Average fiber length is 5 to 50 μm, average fiber diameter is 0
．． Potassium titanate fibers with a surface of 0.05 to 1.0 μm are applicable, but those with an average fiber length of 20 to 30 μm and an average fiber diameter of 0.1 to 0.3 μm are preferred. The potassium titanate fibers are usually used without treatment. However, in order to have affinity with the base resin of the present invention, those treated with a silane coupling agent such as aminosilane or epoxysilane, chromic chloride, or other surface treatment agent depending on the purpose can also be used.

Aromatic polyamide fibers include, for example, those having the following structural formula, at least one of them.
Species or mixtures of two or more species may be used.

Example) DuPont product name 1 (evlar) Example) DuPont product name Homex Music University Product name Comex Other aromatic polyamide fibers with various skeletons depending on the isomeric structure at the ortho, meta, and para positions can also be used, but among them (1) Those with a bond in the b-para position have high softening and melting points, and are the most preferable examples of heat-resistant organic fibers in the present invention.

Carbon fiber, glass fiber, potassium titanate fiber,
and reinforcing fibers such as aromatic polyamide fibers in an amount of 5 to 100 parts by weight, preferably 10 parts by weight per 10 parts of polyimide resin.
~50 parts by weight can be used. If it is less than 5 parts by weight, there will be no reinforcing effect, which is a feature of the present invention, and 100 parts by weight or less! If it is used in excess of a certain amount, problems may occur in terms of physical properties or moldability.

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

(1) After pre-mixing polyimide powder and reinforcing fibers using a mortar, Henschel mixer, drum blender, tumbler blender, ball mill, ribbon blender, etc., and then kneading with a commonly known melt mixer, hot roll, etc., Grind into perefut or powder.

(2) Polyimide powder is dissolved or suspended in a battering machine solvent in advance, reinforcing fibers are impregnated with this solution or suspension, and then the solvent is removed in a hot oven, and then it is made into pellets or powder. do. In this case, the solvent may be, for example, N,N-dimethylformamide, N,N-dimethylmethoxyacetamide, N-methyl-2-pyrrolidone, ll
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, tetramethyl urea, hexamethyl phosphoramide, phenol, m
-cresol, p-cresol, 0-cresol, anisole, p-chlorophenol and the like. Further, these organic solvents may be used alone or in combination of two or more.

(3) After impregnating reinforcing fibers in a solution in which polyamic acid, which is a precursor of the polyimide of the present invention, is dissolved in the above-mentioned solvent, heat treatment is performed at 100 to 400°C, or a commonly used imidization process is performed. After chemical imidization using a
Remove the solvent and make 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 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 may 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 and put into practical use by known molding methods such as injection molding, extrusion molding, compression molding, and rotary molding.

C Example] The present invention will be specifically explained with reference to Examples, Synthesis Examples, and Comparative Examples.

Synthesis Example 309 g of 3-nitrophenoxybenzoyl chloride was placed in a 21 flask equipped with a stirrer, reflux condenser, and thermometer.
(1.11 mol), diphenyl ether 85.5 g
(0,502 mol), 1,2-dichloroethane 11 are charged.

While stirring so that the temperature does not exceed 40° C., 198 g (1.49 mol) of anhydrous aluminum chloride is added in portions over 1.5 hours. After stirring for 11 hours at 55-60°C, it is cooled and discharged into water 21.

After washing the separated organic layer with a 5% aqueous NaOH solution, the solvent is distilled off under reduced pressure to obtain a crude dinitro compound of the following formula as a yellowish brown oil. Yield: 312. (Yield 95%) This crude dinitro compound was mixed with 1.5 ml of 2-methoxyethanol.
1 and charged into a flask for catalytic reduction equipped with a reflux condenser, a thermometer, and a stirrer, and 5 g of 5% Pd/C16 was added thereto. When hydrogen is introduced at 30-35° C. with vigorous stirring, hydrogen absorption stops in 7.5 hours. The obtained crystals are hot filtered to remove Pd/C, and upon cooling, pale yellow crystals are precipitated. After filtration, washing, and drying, the desired aromatic diamine was obtained as pale yellow crystals.

Yield: 253 (yield: 85%) The crude crystals thus obtained were further recrystallized from 2-methoxyethanol to obtain a pure product.

Pale yellow crystal m p 169.5-1715°C Elemental analysis CHN Cal lcd (χ”) 77.01 4.76
4.730bsd (χ) 76.86 4.59
4.65IR (KBr cltsk am-')
: 3380 (amino group) 1630 (carbonyl group) 1220 (ether bond) MS CFD method") : 592 (M"), 29
6(M"/2>[Example] The present invention will be further described in detail below with reference to 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 59.2 kg (100 mol) of 4,4'-bis(3-(4-aminophenoxy)benzoyl)diphenyl ether and N,N-dimethylacetamide were placed in a container equipped with a stirrer, a reflux condenser, and a nitrogen inlet tube. Charge 186.9 g of pyromellitic dianhydride 2 in a nitrogen atmosphere at room temperature.
0.9 was added to the solution, taking care not to increase the temperature of the solution, and the mixture was stirred at room temperature for about 24 hours to obtain a polyamic acid solution. The logarithmic viscosity of this polyamic acid is 0.69 dl/
It was g. (Measurement temperature: 35°C, N,N-dimethylacetamide solvent, concentration: 0.5g/dl, all values shown below were carried out under the same conditions.)Additionally, 535kg of N,N-dimethylacetamide was added to this ton volume. , 40.8 Kg (40
0 mol) of triethylamine and 60.3 Kg (6
00 mol) of acetic anhydride was added dropwise. Approximately 24 more at room temperature
After stirring for an hour, the solution was discharged into 2,500 p of water with strong stirring, the precipitate was filtered off, washed with methanol, and dried under reduced pressure at 150°C for 24 hours to give 72.5 kg (yield: approx. 97 kg). .0%) of pale yellow polyimide powder was obtained. The glass transition temperature of this polyimide powder is 227°C (measured by DSC method), and the 5% weight loss air temperature is 540°C (DTA
-Measured by TG method).

The measurement results of elemental analysis were as follows.

Calculated value (χ) 74.42 3.38 3.62 (χ
) 74.35 3.30 3.58 Production Examples 2 to 5 The same procedure as Production Example 1 was carried out using various acid dianhydrides shown in Table 1 instead of the pyromellitic dianhydride used in Production Example 1. Table 1 shows the polyimide resin synthesis conditions and the logarithmic viscosity and glass transition temperature of the produced polyimide powder. Physical properties are also described.

Examples 1 to 5, Comparative Examples 1 to 2 Carbon fibers having an average diameter of 12 μm, a length of 311 Il, and an aspect ratio of 250 (manufactured by Toshi Co., Ltd., Add the amount shown in Table 2 (trade name Trading Card) and mix with a drum blender.
<Manufactured by Kakuda Manufacturing Co., Ltd.) after mixing, caliber 30ffllll+
After melt-kneading at a temperature of 400°C using a single-screw extruder,
The strands were air cooled and cut to obtain pellets.

The obtained pellets were injection molded using an injection molding machine (Aburg Allround A-220, manufactured by Aburg AG, West Germany) at an injection pressure of 500 kg/cd and a cylinder temperature of 400°C.
, mold temperature: 180° C.) Tensile test pieces, bending test pieces, Izont impact strength test pieces, and mold shrinkage rate measurement test pieces were obtained.

Tensile test follows ASTM D-638, bending test follows AST
Mo-790, Izotsu impact strength test is ASTM
The heat distortion temperature was determined according to ASTM D-684, and the molding shrinkage rate was determined according to STM D-955. Table 2 shows the results.

Examples 6 to 10, Comparative Examples 3 to 4 Silane-treated glass fibers with a fiber length of 3 mm and a fiber diameter of 13 μm (Nitto Boseki Co., Ltd. Manufactured by C5-3PE-
476S) in the amount shown in Table 3 and mixed with a drum blender mixer (manufactured by Shuen Seisakusho).
After melt-kneading at a temperature of 310 to 350° C. using a single-screw extruder, the strands were air-cooled and cut to obtain pellets.

Various test pieces were prepared from the obtained pellets in the same manner as in Example 1, and various physical properties were measured. Table 3 shows the results.

Examples 11 to 15, Comparative Examples 5 to 6 For each 100 parts by weight of the polyimide powder obtained in Production Examples 1 to 5, the cross-sectional diameter was 0.2 μm, and the average fiber length was 20 μm.
Potassium titanate fiber (Tismo D manufactured by Otsuka Chemical Co., Ltd.)
) in the amount shown in Table 4, and added it to a drum blender mixer (
After mixing with a 301-diameter single-screw extruder at a temperature of 310 to 350°C, the strands were air-cooled and cut to obtain pellets.

Various test pieces were prepared from the obtained pellets in the same manner as in Example 1, and various physical properties were measured.The results are shown in Table 4.

Examples 16 to 20, Comparative Examples 7 to 8 Aromatic polyamide fibers with an average fiber length of 31 (manufactured by DuPont, trade name Kevlar) were added to 1041 parts of each of the polyimide powders obtained in Production Examples 1 to 5. After adding the amount shown in 5 and mixing with a drum blender (manufactured by Shuen Seisakusho), 310 to 3
After melt-kneading at a temperature of 50° C., the strands were air-cooled and cut to obtain pellets.

Various test pieces were prepared from the obtained pellets in the same manner as in Example 1, and various physical properties were measured. In addition, the fluidity test during the molding process was conducted under injection molding conditions (injection pressure 500Kg7cII, cylinder temperature 400℃, mold temperature 180℃).
The flow length was determined by measuring the spiral flow with a thickness of 0 mm and a wall thickness of 2.0 mm. Table 4 shows the results.

〔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.

Patent Applicant Mitsui Toatsu Chemical Co., Ltd. Procedural Amendment (Issued by 岨) July 6, 1988 Director General of the Patent Office Yoshi 1) Mr. Moon Tsuyoshi■, Indication of the case Relationship with Patent Application No. 134826 of 1985 Patent application Address: 3-2-5-4 Kasumigaseki, Chiyoda-ku, Tokyo Number of inventions to be increased by the amendment: 0 5: Detailed explanation of the invention in the specification to be amended: 6: Contents of the amendment: (1) Details 3rd line from the bottom of calligraphy 3: ``(Special application 1986-29
'7641)
5) Correct it as J.

(2) Page 21, lines 2 to 5 of the specification tube ``Table 1 shows the polyimide resin synthesis conditions and the logarithmic viscosity and glass transition temperature of the produced polyimide powder.Table 1 shows the production conditions of Production Example 1, the produced polyimide Table 1 shows the polyimide resin synthesis conditions, logarithmic viscosity of polyamic acid, glass transition temperature, elemental analysis value, and 5% thermal decomposition temperature of the obtained polyimide powder. Ta. Correct it as j.

Claims (5)

[Claims] (1) Formula (I) ▲Mathematical formulas, chemical formulas, tables, etc.▼(I) (In the formula, R is an aliphatic group with 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 to 100 parts by weight of reinforcing fibers. (2) The polyimide resin composition according to claim 1, wherein the reinforcing fibers are carbon fibers. (3) The polyimide resin composition according to claim 1, wherein the reinforcing fibers are glass fibers. (4) The polyimide resin composition according to claim 1, wherein the reinforcing fibers are potassium titanate fibers. (5) The polyimide resin composition according to claim 1, wherein the reinforcing fibers are aromatic polyamide fibers.