JPH02308856A - Aromatic polyimide resin composition - Google Patents

Abstract

PURPOSE:To obtain a composition having excellent molding properties and improved fluidity under high shear rate without damaging heat resistance and mechanical characteristics by blending a polyimide resin capable of melting and flowing with a fluororesin. CONSTITUTION:70-99.9 pts.wt. aromatic polyimide resin containing >=50mol% repeating unit shown by the formula (Ar is bifunctional aromatic residue; Ar' is tetrafunctional aromatic residue), capable of melting and flowing is blended with 30-0.1 pt.wt. fluororesin. The polyimide resin is obtained by reacting an aromatic tetracarboxylic acid (dianhydride) with 1,4-bis(4-aminophenylthio) benzene, etc.

Description

DETAILED DESCRIPTION OF THE INVENTION [Background of the Invention] <Industrial Application Field> The present invention relates to a novel aromatic polyimide resin composition.

The aromatic polyimide resin produced by the present invention has excellent heat resistance and excellent melt moldability.
It is useful as super engineering plastics, heat-resistant fibers, heat-resistant films, heat-resistant coating materials, etc.

<Prior Art> It is known that an aromatic polyimide with extremely excellent heat resistance can be obtained by reacting an aromatic tetracarboxylic dianhydride with an aromatic cyamine (C.

E, 5ROOG, “Journal of Polymer Science, Macromolecule φ Review”, Volume 11,
p. 161, 1976). However, the aromatic polyimides that have been generally proposed so far are difficult to melt and mold, and their uses have been limited.

Aromatic polyimides using aryloxy dianhydrides as acid anhydrides have been studied to improve these drawbacks (Japanese Patent Publication Nos. 57-20966 and 57-20).
967, etc.), polyetherimide “Ultem”
(General Electric Company's product name). This type of aromatic polyimide is melt-molded (injection,
It has excellent extrusion moldability, but on the other hand, its heat resistance and solvent resistance are lower than conventional aromatic polyimides.

On the other hand, aromatic polyimides obtained by the reaction of aromatic diamines having (thio)ether bonds with pyromellitic dianhydride (JP-A-59-170122, JP-A-61
-250031, etc.) and polyimide sulfone resin (U.S. Pat. No. 4,398,021, etc.), which have been reported to be able to be melt-molded without significantly reducing heat resistance; Its fluidity is low (it is not practical in the engineering and electronics fields, which require a balance between heat resistance, mechanical properties, and formability).

Compared to these aromatic polyimides, novel aromatic polyimides obtained by the reaction of aromatic diamines having thioether bonds with specific aromatic tetracarboxylic dianhydrides (JP-A No. 62-15228, JP-A No. 62-15228, 1986-
309524, etc.) has an excellent balance of heat resistance, mechanical properties, and moldability, but further improvement in moldability has been desired. In particular, there were problems with the flow characteristics under high shear rates, and urgent improvements were needed.

By the way, it is well known that fluororesin, typified by poly(tetrafluoroethylene), is added to aromatic polyimide resin for the purpose of improving sliding properties and mold release properties. Conventional aromatic polyimide resins have inherently poor melt flowability, while aromatic polyimide resins with excellent melt flowability, such as Ultem, have poor heat resistance. / It has been difficult to provide an aromatic polyimide resin that satisfies both melt fluidity.

[Summary of the invention]

Means for Solving the Problems> The present inventors have developed a method using a thioether bond-containing aromatic diamine represented by the general formula (TI) (in the formula, 8 is a divalent aromatic residue) as a main component. and an aromatic tetracarboxylic dianhydride represented by the general formula (m)O ]111 O (wherein Ar' is a tetravalent aromatic residue). By blending a specific amount of fluororesin with flowable aromatic polyimide resin, improved moldability and improved flow characteristics under high shear speeds are achieved without impairing the original heat resistance and mechanical properties. The present invention was completed by confirming that the present invention is possible.

That is, the aromatic polyimide resin composition excellent in melt flowability according to the present invention is a melt flowable aromatic polyimide resin containing 50 mol % or more of the repeating unit represented by the following formula (I) with a weight of 70 to 99.9%. Part of fluororesin 30-0,
1 part by weight (the total amount of both is 100 parts by weight).

(In the formula, Ar is a divalent aromatic residue. Also, Ar'
is a tetravalent aromatic residue. ) [Detailed Description of the Invention] The aromatic polyimide resin composition of the present invention having excellent melt fluidity is a composition in which a fluororesin is blended with an aromatic polyimide resin.

[■] Aromatic polyimide resin The aromatic polyimide resin to which the present invention is applied has the formula (I)
It is a melt-flowable aromatic polyimide resin having 50 to 100 mol% of repeating units represented by:

1]11 Such an aromatic polyimide resin has, for example, the following formula (n
) and an aromatic diamine containing at least 50 mol% of an aromatic diamine having a thioether bond represented by the formula (I
Aromatic tetracarboxylic acid (dianhydride) represented by I[)
Obtained by reaction with

(In the formula, Ar is a divalent aromatic residue)1]l] (In the formula, Ar' is a tetravalent aromatic residue) Specific examples of Ar include f (A is o , co, s○, SO2, and CnH2n.However, n is an integer from 1 to 10.Y
represents an alkyl group having 1 to 20 carbon atoms, an aralkyl group having 7 to 20 carbon atoms, a cycloalkyl group having 3 to 20 carbon atoms, an aryl group having 6 to 20 carbon atoms, a halogen group, and a nitro group. a, b, cSd, e, and f each represent an integer of 0 to 4. m represents a number from 0 to 20. ).

Specific examples of Ar' include (-B- is -o-1-s-1-co-1-SO2-2
It is also gSO or 1. ).

Specific examples of aromatic thioether diamines represented by general formula (II) that are reacted with aromatic tetracarboxylic acids (dianhydrides) include 1,4-bis(4-aminophenylthio)benzene, 1.3- Bis(4-aminophenylthio)
Benzene, 2,4-bis(4-aminophenylthio)nitrobenzene, 2,5-dimethyl-1,4-bis(4-
aminophenylthio)benzene, 4,4'-bis(
4-aminophenylthio)diphenyl, 4.4'-
bis(4-aminophenylthio)diphenyl ether,
4.4' ~bis(4-aminophenylthio)diphenyl sulfide, 1.4-bis(4-(4-aminophenylthio)phenylthio)benzene, α.

ω-diaminopoly (I,4-thiophenylene) oligomer, 4,4'-bis(4-aminophenylthio)
Benzophenone, 4.4'-bis(4-aminophenylthio)diphenyl sulfide, 4゜4'-bis(
4-aminophenylthio)diphenylsulfone, 3.3
'-bis(4-aminophenylthio)diphenylsulfone, 2,2-bis(4-(4-aminophenylthio)phenyl)propane, 4,4'-bis(4-aminophenylthio)diphenylmethane, etc. be able to. At least one of these is used. Formula (It
) The amount of diamine used is 50 mol% or more.

The aromatic diamine component to form the aromatic polyimide resin according to the invention consists of at least 50 mole % of this formula (II) aromatic thioether diamine. That is, up to 50 mol% of this diamine component may be replaced with another aromatic diamine.

Specific examples of such other aromatic diamines include p-
Phenylenediamine, m-phenylenediamine, tolylenediamine, 2-chloro-1,4-phenylenediamine, 4-chloro-1,3-phenylenediamine, 4.4'
-diaminobiphenyl, I
3,3'-dimethyl-4□4'-diaminobiphenyl, 3,3'-dichloro-4,4'-diaminobiphenyl, 4,4'-diaminodiphenyl ether,
3.4'-diaminodiphenyl ether, 4.4'
-Diamino diphenyl sulfide, 4゜4'-diaminodiphenylsulfone, 3.4'-diaminodiphenylsulfone, 3.3'-diaminodiphenylsulfone, 4.4'-diaminobenzophenone, 3.3
'-diaminobenzophenone, 3.4'-diaminobenzophenone, 4.4'-diaminodiphenylmethane, 3.3' ~diaminodiphenylmethane, ],
]4-bis4-aminophenoxy)benzene, 1,3-
Bis(4-aminophenoxy)benzene, ], ]3-bis3-aminophenoxy)benzene, 4.4'-bis(4-aminophenoxy)diphenyl ether, 4゜4'-bis(4-aminophenoxy)biphenyl, 4.
4'-bis(4-aminophenoxy)diphenyl sulfide, 4.4'-bis(4-aminophenoxy)
Benzophenone, 4.4'-bis(4-aminophenoxy)diphenylsulfone, 4°4'-bis(3-
aminophenoquine) diphenylsulfone, 2,2-bis(4-(4-aminophenoxy)phenyl)propane,
Examples include 2,2-bis[4-(3-aminophenoxy)phenyl]propane. At least one of these is used.

On the other hand, the aromatic tetracarboxylic acid (dianhydride) of the general formula (m) to be reacted with such an aromatic diamine component to form an aromatic polyimide resin includes pyromellitic acid (dianhydride), benzophenone, etc. Tetracarboxylic acid (
dianhydride), biphenyltetracarboxylic acid (dianhydride)
, diphenylsulfone tetracarboxylic acid (dianhydride),
Nphenyl ether tetracarboxylic acid (dianhydride), Nphenyl sulfide tetracarboxylic acid (dianhydride), Benzanilide tetracarboxylic acid (dianhydride), Hexafluoropropane-2,2-bis(anhydride) phthalic acid, etc. can be mentioned. At least one of these is used.

Aromatic polyimide resin> By the reaction of the above aromatic diamine and aromatic tetracarboxylic acid (dianhydride), 50 repeating units of formula (I)
An aromatic polyimide resin containing at least mol % is obtained. The glass transition temperature of this resin is approximately 100 to 350° C1, preferably 220 to 3006 C1. Also, considering mechanical properties and moldability, the intrinsic viscosity is 0.4 cll/g.
(0.5% N-methylpyrrolidone of the corresponding polyamic acid (
NMP) solution at 30°C,
1. It is desirable that it is 0 dl/g or less.

The aromatic polyimide which is the main component of the composition of the present invention contains 50 mol% or more of repeating units represented by formula (I). It is clear from the foregoing that this aromatic polyimide +: may contain a plurality of types of repeating units of formula (I) in terms of Ar and Ar'. And the repetition of this aromatic polyimide +1
Repetitions other than formula (I) occupying up to 50 mol% of the 1-position! It f, 17: - Examples of aromatic TeI of formula (m)
- It is also clear from the above that it is an aromatic imide unit consisting of lacarponic acid (anhydride) and an aromatic diamine other than the above-mentioned formula (If). Incidentally, since the concept of copolyimide is already well known, up to 50 mol% of the repeating units (other than those of formula (I)) are tetracarboxylic acids other than the aromatic tetracarboxylic acid (anhydride) of formula (In). (anhydride) and/or diamines other than aromatic diamines.

(n) Fluororesin The fluororesin to which the present invention is applied has a continuous heat resistance temperature of 150
It is desirable that the material be a fluororesin with a temperature of ℃ or higher. Such fluororesins include homopolymers or copolymers of perfluoroolefins, such as tetrafluoroethylene, hexafluoropropylene, etc. (particularly, fluoroolefins such as vinyl fluoride, vinylidene fluoride, perfluoroalkyl vinyl ethers, etc.). (copolymer of). To give a specific example, poly(tetrafluoroethylene (hereinafter referred to as tetrafluoroethylene))
, poly(tetrafluoroethylene/perfluoroalkyl vinyl ether), poly(tetrafluoroethylene/hexafluoropropylene (hereinafter referred to as hexafluoropropylene))
, poly(tetrafluoroethynone/ethylene), etc. These may be normal high molecular weight substances (number average molecular weight 1×10 to 1×10 2 ) or low molecular weight substances having a molecular weight of less than 1×10 6 . Examples of commercially available products include "Fluon" and "Aralon C0PJ" from Asahi Glass Co., Ltd., and "Neoflon PFAJ" and "Neoflon FEPJ" from Daikin Industries, Ltd.

[■] Blend/Production of Composition The composition of the present invention, which is a mixture of an aromatic polyimide resin and a fluororesin, can be produced by various known methods. That is, for example, there is a method in which these are premixed using a Henschel mixer or the like, and then melt-extruded to form pellets.

Regarding the amount of fluororesin added, if it is too small, no effect will be observed, and if it is too large, the moldability or performance of the molded product will deteriorate. Therefore, the total amount of aromatic polyimide resin and fluororesin (I00 parts by weight)
Based on the standard, the fluororesin is blended in an amount of 30 to 0.1 part by weight, preferably 20 to 1 part by weight.

The composition according to the invention falls within the category of thermoplastic resin compositions. Accordingly, various auxiliary materials can be formulated according to practice for such resin compositions. An example of such an auxiliary material is a filler. Typical examples of fillers include (a) fibrous fillers: glass fiber, carbon fiber, poron fiber, aramid fiber, alumina InltI;
(b) Inorganic fillers, mica, talc, resin die, graphite, carbon black, silica, asbestos, molybdenum sulfide, magnesium oxide, calcium oxide, etc. (C) Compatible thermoplastics Resin Polyamide, polyimide, etc. can be mentioned.

The composition of the present invention can be used in a wide variety of applications, including various parts in the electrical and electronic fields, housings, automobile parts, aircraft interior applications, sliding parts, gears, insulation materials, heat-resistant films, heat-resistant panels, heat-resistant fibers, etc. It is possible to use it within a range.

(IV) Experimental Examples The following Examples and Comparative Examples are intended to further specifically explain the present invention. The scope is not limited by these examples.

Examples 1 to 5 and Comparative Examples 1 to 6 Aromatic polyimide resins (pellet or fine powder) represented by structures (A) to (D) of the following formulas were heated at 330 to 350°.
In step C, mix and knead the fluororesin using a Brabender,
This was compression molded at 300-350°C to prepare a test piece, and the mechanical properties etc. were determined. In addition, L/D = 10 (L 1
The melt viscosity and flow state were determined under the conditions of 4111 (0 mm x D 1 mm die). In addition, differential thermal analysis (DuPo
nL910 DifTcrential Sc-ann
The glass transition temperature was measured using ing Calorimeter).

As a result, the systems in which fluororesin was blended (Examples 1 to 5) were found to be inherently superior to systems in which fluororesin was not blended (Comparative Examples 1 to 4) and known melt-flowable polyimide resins (Comparative Examples 5 to 6). It was clear that improved formability and improved flow properties under high shear rates were achieved without compromising heat resistance or mechanical properties. (See [Table 1]) [ηinh of polyamic acid = 0. 54dl/g (
0.5% NMP solution, Apl constant at 30°C). Glass transition temperature 241°C. ] [ηinh of polyamic acid -0,61 dl/g (0
, 5% NMP solution, 30°C). Glass transition temperature 235
°C] 1q - [η1nh of polyamic acid - 0,50 dl/g (0,
5% NMP solution, 30°C). Glass transition temperature 261°C
] - mouth - [y+inh of polyamic acid -0.63 dl/g (
0.5% NMPi solution, 1 flll constant at 30°C). Transition temperature in glass 244°C,) ZU- Examples 6 to 8 and Comparative Examples 7 to 8 Using a high-speed mixer, an aromatic polyimide resin represented by the structure (E) of the following formula or the structure (A) above A fluororesin was blended using a fluororesin, and these were tested at 370°C using a Koka type flow tester to measure L/D=10 (L10mm x D1m).
The melt viscosity and flow state were determined under the conditions of (dll).

As a result, it was clear that the system of the comparative example had inferior flow characteristics compared to the system of the example (see [Table 2]).

[ηinh of polyamic acid -0,62 dl/g (0
5% NMP solution, measured at 30°C). Glass transition temperature 400℃
That's all (unintelligible). ] Figure 1 shows the melt viscosity of Example 1 and Comparative Example 1, which were measured at 370°C and L using a Koka type flow tester.
], These are the results measured using an Omm/D 1 mm die.

[Table 2] 1) Measured at 370°C, L/D-10 (mu/mm), shear rate 10'' (see-1) (Koka flow tester).

3) Wako Pure Chemical Industries product 4) Fluon L-150, Asahi Glass product 5) Fluon L
-169, Asahi Glass product

[Brief explanation of drawings]

FIG. 1 is a graph showing the melt viscosity of Example 1 and Comparative Example 1. Taganto's agent Sato -25=

Claims (1)

[Scope of Claims] Melt-flowable aromatic polyimide resins 70 to 99. containing 50 mol% or more of repeating units represented by the following formula (I).
An aromatic polyimide resin composition having excellent melt fluidity, characterized in that 30 to 0.1 parts by weight of a fluororesin (the total amount of both is 100 parts by weight) is blended with 9 parts by weight. ▲There are mathematical formulas, chemical formulas, tables, etc.▼(I) (In the formula, Ar is a divalent aromatic residue. Also, Ar'
is a tetravalent aromatic residue. )