JPS63305166A - Polyimide resin composition - Google Patents

Abstract

PURPOSE:To obtain the title composition improved in heat resistance and mechanical strengths without detriment to the excellent properties inherent in a polyimide, by adding an aromatic polyamide-imide to a polyimide having repeating units of a specified formula. CONSTITUTION:The title composition comprising 99.9-50wt.% polyimide having repeating units each represented by formula I (wherein X is a direct bond, a 1-10C bivalent hydrocarbon group, a hexafluorinated isopropyledene, carbonyl, thio or sulfonyl, Y1-Y4 are each H, a lower alkyl, a lower alkoxyl, Cl or Br 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 composed of aromatic groups bonded to each other directly or through bridging members) and 0.1-50wt.% aromatic polyamide-imide (e.g., an aromatic polyamide-imide having repeating units of formulas II and III). This composition is improved in heat resistance and mechanical strengths without detriment to the mechanical, thermal and electrical properties and solvent resistance inherent in a polyimide.

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 showing excellent properties have been developed.

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 improved heat resistance and/or mechanical strength in addition to the excellent properties inherently possessed by polyimide.

[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 polyamide-imide is a resin composition that is particularly effective for the above-mentioned purpose. They discovered this and completed the present invention.

The inventor first described mechanical properties, thermal properties, electrical properties,
As a polyimide having excellent solvent resistance and heat resistance, the formula (where X is a direct bond, a divalent hydrocarbon group having 1 to 10 carbon atoms, a hexafluorinated isopropylidene group, a carbonyl group, a thio group, or a group selected from the group consisting of sulfonyl groups, Y, , Y2, y3 and Y4 are hydrogen,
Represents a group selected from the group consisting of a lower alkyl group, a lower alkoxy group, chlorine or bromine, and R is an aliphatic group having 2 or more carbon atoms, a cycloaliphatic group, a monocyclic aromatic group, or a fused polycyclic group. The formula aromatic group represents a tetravalent group selected from the group consisting of non-fused polycyclic aromatic groups in which aromatic groups are interconnected directly or through a bridge member. ) We have discovered a polyimide having a repeating unit represented by: (Patent application No. 59-265220.60-205283
．． 6゜-224812, 61-076475, 61-2
74206 etc.). The above polyimide is a new heat-resistant resin that has many good physical properties.

The purpose of the present invention is to develop polyimides without impairing their inherent mechanical, thermal and electrical properties and solvent resistance.
Furthermore, it is an object of the present invention to provide a polyimide resin composition with improved heat resistance and mechanical strength.

That is, the present invention provides a polyimide 99.9 having a repeating unit represented by the formula (wherein X, Y1, Y2+ Y3, Y4 and R are the same as before)
50% by weight and 0.1 to 50% by weight of aromatic polyamideimide.

The production of the polyimide used in the present invention is based on the above-mentioned patent application filed in 1973.
9-265220 and the like.

That is, a polyamide acid obtained by reacting an ether diamine represented by the formula (wherein X, y, , y2, Y3 and Y4 are the same as before) and one or more tetracarboxylic dianhydrides in an organic solvent. is obtained by imidizing.

Diamines used in this method include bis(4-(
3-aminophenoxy)phenylcomethane, 1.1-bis(4-<3-aminophenoxy)phenyl]ethane,
1.2-bis[4-(3-aminophenoxy)phenyl]ethane, 2.2-bis[4-(3-aminophenoxy)phenyl]propane, 2-(4-(3-aminophenoxy)phenyl) - 2-(4-(3-aminophenoxy)-3-methylphenyl]propane, 2.2-bis(4-(3-aminophenoxy)-3-methylphenyl)propane, 2-(4-(3-amino phenoxy)phenyl) -2-(4-(3-aminophenoxy)-3
,5-dimethylphenyl]propane, 2,2-bis[4
-(3-aminophenoxy)-3,5-dimethylphenyl]propane, 2,2-bis(4-(3-aminophenoxy)phenylcobutane, 2,2-bis(4-<3-aminophenoxy)phenyl ) −1,1,1,3,3,
3-hexafluoropropane, 4,4'-bis(3-aminophenoxy)biphenyl, 4,4'-bis(3-aminophenoxy)-3-methylbiphenyl, 4,4'-
Bis(3-aminophenoxy)-3,3'-dimethylbiphenyl, 4,4'-bis(3-aminophenoxy)-
3,5-dimethylbiphenyl, 4,4'-bis(3-aminophenoxy)-3,3', 5゜5'-tetramethylbiphenyl, 4,4'-bis(3-aminophenoxy)-3,3 '-dichlorobiphenyl, 4,4'-bis(
3-aminophenoxy)-3,5-dichlorobiphenyl, 4,4'-bis(3-aminophenoxy') -3,
3(5,5'-tetrachlorobiphenyl, 4,4'-bis(3-aminophenoxy)-3,3'-dibromobiphenyl, 4,4'-bis(3-aminophenoxy)-3
,5-dibromobiphenyl, 4,4'-bis(3-aminophenoxy)-3,3) 5,5'-tetrabromobiphenyl, bis(4-(3-aminophenoxy)phenyl)ketone, bis(4 -(3-aminophenoxy) phenyl fusulfide, bis(4-(3-aminophenoxy)-3-methoxyphenyl fusulfide, (4-(3
-aminophenoxy)phenyl)(4-(3-aminophenoxy)-3,5-dimethoxyphenyl)sulfide, bis(4-(3-7minophenoxy)-3,5-dimethoxyphenyl)sulfide, bis(4-( Examples include 3-aminophenoxy)phenyl]sulfone, which may be used alone or in combination of two or more.

The tetracarboxylic dianhydride used at this time is a tetracarboxylic dianhydride represented by (wherein R is the same as before).

The tetracarboxylic dianhydride used by beating is
Ethylenetetracarboxylic dianhydride, butanetetracarboxylic acid, cyclopentanetetracarboxylic dianhydride, pyromellitic 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)methanihydride, bis(3,4-dicarboxyphenyl)methanihydride, 4
．． 4'-(p-phenylenedioxy)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-benzenetetracarboxylic dianhydride, 3, 4,9.10-perylenetetracarboxylic dianhydride, 2.3.6.7-anthracenetetracarboxylic dianhydride, 1.2.7.8-phenanthrenetetracarboxylic dianhydride, etc. 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. It can be used in the composition of the present invention.

Examples of diamines that can be used in combination include m-phenylenediamine, 0-phenylenediamine, and p-phenylenediamine.
-phenylenediamine, m-aminohensylamine, p
-aminohensylamine, 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-(4-aminophenoxy)phenyl)methane,
1.1-bisC4-(4-aminophenoxy)phenyl]ethane, 1.2-bis[4-(4-aminophenoxy)phenyl]ethane, 2.2-bis(4-(4-aminophenoxy)phenyl) ] Propane, 2.2-bis(4-
(4-aminophenoxy)phenylcobutane, 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(4-aminophenoxy)biphenyl, bis(4-(4-aminophenoxy)phenylkoketone, bis(4-(4-aminophenoxy)phenyl)sulfide, bis[4 -(4
-aminophenoxy)phenyl]sulfoxide, 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 and 1,3-bis[4-(3-aminophenoxy)benzoyl]benzenato.

The aromatic polyamide-imide used in the present invention has imide and amide bonds in the repeating unit of the main chain, and has the following general formula (in the formula, the needle is a trivalent aromatic group containing at least one benzene ring). , Z represents a divalent organic group).

A particularly preferred aromatic polyamide-imide in the present invention is an aromatic polyamide-imide having a repeating unit represented by the formula and the formula.

These aromatic polyamideimides are commercially available, for example, from Amoco, USA, under the trade name of TORLON.

The molding resin composition of the present invention comprises the polyimide 99.9 to 99.9.
50% by weight, aromatic polyamideimide in the range of 0.1 to 50% by weight, and the total amount is adjusted to be 100% by weight.

In the polyimide/aromatic polyamide-imide composite resin system of the present invention, the effect of improving heat resistance and/or mechanical strength by the aromatic polyamide-imide is recognized even in small amounts, and the lower limit of its composition ratio is 0.1% by weight. Preferably, it is 0.5% by weight or more.

Furthermore, since aromatic polyamide-imide has a much higher melt viscosity than ordinary thermoplastic sealants, if the amount of aromatic polyamide-imide in the composition is too large, the excellent molding processability of polyimide will be impaired. It becomes impossible to maintain the strength, and the elongation at break also decreases, which is not preferable. Therefore, there is an upper limit to the composition ratio of the aromatic polyamide-imide, 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.

+l) Polyimide powder and aromatic polyamide-imide powder are pre-kneaded into powder using a mortar, Henschel mixer, drum blender, tumbler blender, ball mill ribbon blender, etc.

(2) Polyimide powder is preliminarily dissolved or dissolved in an organic solvent, and aromatic polyamide-imide is added to this solution or suspension, and after uniformly dispersing or melting, the solvent is removed and powdered shall be.

(3) After dissolving or suspending the aromatic polyamide-imide in an organic solvent solution of polyamic acid, which is a precursor of the polyimide of the present invention, the aromatic polyamide-imide is heat-treated at 100 to 400"C, or a commonly used imide is dissolved or suspended. After chemical imidization using a curing agent, 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.

For the melt blending, equipment commonly used for melt blending rubbers, plastics, and materials, such as hot rolls, Banbury mixers, Brabenders, extruders, 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 molding method for the resin composition of the present invention, injection molding or extrusion molding, which forms a uniform melt 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 even if the shape, extrusion film molding, etc. are used.

Furthermore, is the resin composition of the present invention solid? One or more lubricants such as molybdenum disulfide, graphite, boron nitride, -lead oxide, and lead powder can be added. 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 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 3.68 kg (10 moles) of 4,4'-bis(3-aminophenoxy)biphenyl and 52.5 kg of N,N-dimethylacetamide were placed in a reaction vessel equipped with a stirrer, a reflux condenser, and a nitrogen inlet tube. 15 kg, and 2.11 kg of pyromellitic dianhydride (9,
7 mol) was added while being careful not to increase the solution temperature, and the mixture was stirred at room temperature for about 20 hours.

Add 2.0% to this polyamic acid solution at room temperature under a nitrogen atmosphere.
2 kg (20 mol) of triethylamine and 3.0
6 kg (30 mol) of acetic anhydride was added dropwise. 20 at room temperature
After stirring for some time, a yellow slurry was obtained. This slurry was filtered to obtain pale yellow polyimide powder. This polyimide powder was sludged with methanol, separated, and dried under reduced pressure at 180° C. for 8 hours to obtain 5.36 kg of polyimide powder.

The logarithmic viscosity of this polyimide powder was 0.50 dl/g. Here, the logarithmic viscosity is the value measured by using a mixture of p-chlorophenol and phenol (90: 1 (lTfi ratio)) as the solvent, heating and dissolving 0.5 g of polyimide powder in 100 ml of solvent, and then cooling it to 35 ° C. .

Further, the glass transition temperature of this polyimide powder was 256°C as determined by DSC measurement, and the 5% thermal decomposition temperature as determined by DTA-TG measurement was 560°C.

FIG. 1 shows an infrared absorption spectrum of the polyimide powder obtained here.

In this spectrum diagram, 17 is the characteristic absorption band of imide.
Significant absorption was observed around 80 aa-', around 1720 cm-1, and around 1240 cm-', which is the characteristic absorption band of ether bonds.

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 resin synthesis conditions and the logarithmic viscosity and glass transition temperature of the polyimide powder produced. The table also shows the manufacturing conditions of Synthesis Example 1 and the physical properties of the polyimide powder produced.

Examples 1 to 15 The polyimide powders obtained in Synthesis Examples 1 to 6 and the aromatic polyamideimide powder, TORLON 4203L (trademark of Amoco, USA), which is commercially available, are shown in Tables 2 to 4. After tri-blending various compositions as shown above, extrusion was performed while melt-kneading to obtain uniformly blended pellets.

Next, the uniformly mixed pellets obtained above were injection molded using an injection molding machine (Arburg All Round A-220 manufactured by Arburg) at a barrel temperature of 380 to 400°C and a mold temperature of 220°C to create a test piece. The physical and thermal properties of the specimens were measured.

The results are shown in Tables 2-4.

The minimum injection molding pressure is also listed in each table.

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

Comparative Examples 1 to 6 Tables 2 to 4 show the results of measuring the physical and thermal properties of molded products obtained by the same operations as Examples 1 to 15 using compositions outside the scope of the present invention. [Effects of the Invention] According to the method of the present invention, a polyimide resin composition is provided which has significantly improved heat resistance and/or mechanical strength in addition to the excellent properties inherent to polyimide. .

[Brief explanation of the drawing]

FIG. 1 is an infrared absorption spectrum diagram of an example of polyimide used in the polyimide resin composition of the present invention.

Claims (1)

[Claims] 1) Formula ▲ Numerical formula, chemical formula, table, etc. ▼ (In the formula, X is a direct bond, a divalent hydrocarbon group having 1 to 10 carbon atoms, a hexafluorinated isopropylidene group, a carbonyl group , thio group, or sulfonyl group, and Y_1, Y_2, Y_3 and Y_4 each represent a group selected from the group consisting of hydrogen, lower alkyl group, lower alkoxy group, chlorine or bromine. , 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 group in which aromatic groups are interconnected directly or through a bridge member. Represents a tetravalent group selected from the group consisting of polycyclic aromatic groups.) Polyimide having a repeating unit represented by 99.9~
A resin composition comprising 50% by weight of aromatic polyamideimide and 0.1 to 50% by weight of aromatic polyamideimide.