JPH0364357A - Aromatic polyimide resin composition - Google Patents

Abstract

PURPOSE:To obtain an aromatic polyimide resin composition improved in moldability and melt flow without detriment to its heat resistance and mechanical properties by mixing a specified aromatic polyimide resin with an aromatic poly(ether)sulfone resin. CONSTITUTION:50-99.9 pts.wt. melt-flowable aromatic polyimide resin having at least 50mol% repeating units of formula I (wherein Ar is a bivalent aromatic residue, and Ar' is a tetravalent aromatic residue) is mixed with 50-0.1 pt.wt. aromatic poly(ether)sulfone resin having at least 50mol% repeating units of formula II (wherein x is 0-1) and having a glass transition temperature of 100-350 deg.C, an intrinsic viscosity of 0.4-1.0dl/g (as measured in a 0.5% N- methylpyrrolidone solution of the corresponding polyamic acid at 30 deg.C) and a mol.wt. (in terms of the mol.wt. of PS, gel permeation chromatography) of 1X10<4> to 1X10<5> to obtain 100 pts.wt. title composition.

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 diamine (C).

"Journal of Polymer Science, Macromolecule Review" by E. 5ROOG, Volume 11,
p. 161, 1976). However, the aromatic polyimides that have been proposed for use in shells have been difficult to melt and mold, and their applications 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; It has low fluidity and is not practical in the engineering and electronics fields, which require a balance between heat resistance, mechanical properties, and moldability.

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, υdel, Radel
(Raydel) (Amoco Performance Products, Inc., USA), Vlctorex (Pictrex) PI
Aromatic poly(ether) sulfone resins represented by ES (IC1, UK) are widely used as super engineering plastics with good melt flowability. When added to aromatic polyimide resins that have excellent melt flowability, no significant improvement effect was observed, and in some cases, a decrease in heat resistance/mechanical properties was observed, resulting in both heat resistance and melt flowability being reduced. It has been difficult to provide an aromatic polyimide resin that satisfies the requirements.

[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 (II) (wherein Ar is a divalent aromatic residue) as a main component. A melt-flowable aromatic diamine obtained from an aromatic diamine and an aromatic tetracarboxylic dianhydride represented by the general formula (III) (wherein Ar' is a tetravalent aromatic residue) It was confirmed that by blending a specific amount of aromatic poly(ether) sulfone resin with polyimide resin, improvement in moldability was achieved without substantially impairing the original heat resistance and mechanical properties, and the present invention was developed. I was able to complete it.

That is, the aromatic polyimide resin composition excellent in melt flowability according to the present invention comprises 50 to 99.91 W parts of a melt flowable aromatic polyimide resin containing 50 mol% or more of repeating units represented by the following formula (1). 50 to 0.1 parts by weight of an aromatic poly(ether) sulfone resin containing 50 mol% or more of the repeating center represented by the following formula (n) (the total amount of both is 100 parts by weight) is blended into the resin. It is characterized by the following.

υ (where Ar is a divalent aromatic residue. Also, Ar'
is a tetravalent aromatic residue. ) (In the formula, Ar' is a divalent aromatic residue. Also, X is 0 or 1.) [Detailed Description of the Invention] Aromatic polyimide resin composition with excellent melt fluidity according to the present invention The product is a mixture of aromatic polyimide resin and aromatic poly(ether) sulfone resin.

(1) Aromatic polyimide resin The aromatic polyimide resin to which the present invention is applied has the formula (I)
It has 50 to 100 mol% of repeating units represented by
It is an aromatic polyimide resin that can be melted and flowed.

Raw Materials> Such aromatic polyimide resins have, for example, the following formula (I
It is obtained by reacting an aromatic diamine containing at least 50 mol % of an aromatic diamine having a 6-thioether bond represented by II) with an aromatic tetracarboxylic acid (dianhydride) represented by the following formula (rV).

(wherein Ar is a divalent aromatic residue) U
Specific examples of Ar (wherein Ar' is a tetravalent aromatic residue) include (-B- is -〇-5-s--co-1-S O2f (A is o , coSso, so2, and CnH2□.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. albSc, dSe, and f each represent an integer of O to 4. m represents a number from 0 to 20. ).

Specific examples of Ar' are, for example, Further, g is 0 or 1. ).

Specific examples of aromatic thioether diamines represented by the general formula (DI) that are reacted with aromatic tetracarboxylic acids (dianhydrides) include 1,4-bis(4-aminophenylthio)benzene, 13-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.

Katana-diaminopoly(1,4-thiophenylene) onogomer, 4.4'-bis(4-aminophenylthio)benzophenone, 4.4'-bis(4-aminophenylthio)diphenyl sulfoxide, 4゜4'-bis (
4-aminophenylthio)diphenylsulfone, 3.3
' -bis(4-aminophenylthio)diphenylsulfone, 2.2-bis(4(4-aminophenylthio)
phenyl)pronokun, 4,4'-bis(4-aminophenylthio)diphenylmethane, and the like. At least one of these is used. Formula (I
The amount of diamine used in II) is 50 mol% or more.

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

Specific examples of such other aromatic diamines include p-
Phenylene diamine, m-phenylene diamine, tolylene diamine, 2-chloro-1,4-phenylene diamine, 4-chloro-1,3-phenylene diamine, 4.4'
-diaminobiphenyl, 3,3'-dimethyl-4,
4'-diaminobiphenyl, 3,3'-dichloro-4
, 4'-diaminodiphenyl, 4.4'-diaminodiphenyl ether, 3.4'-diaminodiphenyl ether, 4.4'-diaminodiphenyl sulfide, 4゜4'-diaminodiphenyl sulfone, 3.4
'Diaminodiphenylsulfone, 3. 3'-diaminodiphenylsulfone, 4.4'-diaminobenzophenone, 3.3'-diaminobenzophenone,
3.4'-diaminobenzophenone, 4.4'-diaminodiphenylmethane, 3.3'-diaminodiphenylmethane, 1,4-bis(4-aminophenoxy)benzene, 1,3-bis(4-aminophenoxy)benzene ,
1.3-bis(3-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) diphenyl sulfone, 4゜4' -
Bis(3-aminophenoxy)diphenylsulfone, 2
,2-bis(4-(4-aminophenoxy)phenyl)
Propane, 2,2-bis[4(3-aminophenoxy)
phenyl]propane, and the like. At least one of these is used.

On the other hand, the aromatic tetracarboxylic acid (dianhydride) of the general formula (IV) 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), diphenylsulfoshitetracarboxylic acid (dianhydride)
, diphenyl ether tetracarboxylic dianhydride),
Examples include diphenyl sulfide tetracarboxylic acid (dianhydride), benzanilide tetracarboxylic acid (dianhydride), hexafluoropropane-2,2-bis(anhydride) phthalic acid, and the like. At least one of these is used.

Aromatic polyimide resin> By reacting the above aromatic diamine with aromatic tetracarboxylic acid (dianhydride), 50 repeating units of formula (1)
An aromatic polyimide resin containing at least mol % is obtained. The glass transition temperature of this resin is about 100-350°C, preferably 220-300°C. Furthermore, when considering mechanical properties and moldability, the intrinsic viscosity is 0.4 dl/r (0.5% N-methylpyrrolidone (NM) of the corresponding polyamic acid).
P) Solution measured at 30°C) or more, 1.0 dl/
It is desirable that it is less than g.

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 (1). It is clear from the foregoing that this aromatic polyimide may contain a plurality of types of repeating units of formula (1) in terms of Ar and Ar'. By repeating this aromatic polyimide,
An example of a repeating medium other than formula (I) that occupies up to 50 mol% of the position is an aromatic tetracarboxylic acid (anhydride) of formula (IV>) and an aromatic diamine other than formula (m) described above. It is also clear from the above that it is an aromatic imide unit with
) is an aromatic tetracarboxylic acid of formula (IV) (
It may be formed from a tetracarboxylic acid (anhydride) other than anhydride) and/or a diamine other than aromatic diamine.

[■] Aromatic poly(ether) sulfone resin The resin to be blended with the above aromatic polyimide resin is an aromatic poly(ether) sulfone resin.

The aromatic poly(ether) sulfone resin to which the present invention is applied is a polymer containing 50 mol% or more of repeating units represented by the following formula (n).

Specific examples of Ar' include, for example, Ar as exemplified with respect to formula (1) above, and the same or different one selected for formula (1) can be used in formula (II), but more specific Specifically, there are the following.

Here, Ar' is a divalent aromatic residue.

In the present invention, the target aromatic poly(ether) sulfone resin preferably has a molecular weight of about 1×10 4 to 1×10 5 . In addition, the molecular weight here is a number average molecular weight in terms of polystyrene, and is measured by GPC (gel filtration chromatography).

Such aromatic poly(ether) sulfone resins can be produced by any convenient method. Suitable production methods include, for example, desalination (alkali metal halogenide) and etherification reaction of an aromatic dil\rogen compound containing 4,4-dichlorodiphenylsulfone and an alkali metal salt of bisphenols. There is.

Such aromatic poly(ether) sulfone resins are available on the market, such as ``Needel'' and ``Raydel'' from Amoco Barf Oman Products in the United States, and ``Pictrex PE5j'' from tC1 in the UK. I can give an example.

(III) Blend/Production of Composition The composition of the present invention, which is a mixture of an aromatic polyimide resin and an aromatic poly(ether) sulfone resin, 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 aromatic poly(ether) sulfone resin added, if it is too small, no effect will be observed, and if it is too large, moldability or performance of the molded product will deteriorate. Therefore, aromatic polyimide resin and aromatic poly(
Based on the total amount (100 parts by weight) of aromatic poly(ether) sulfone resin, the content of aromatic poly(ether) sulfone resin is 50 to 0.
．． It is blended in an amount of 1 part by weight, preferably 40 to 3 parts by weight.

The composition according to the invention falls within the category of thermoplastic resin compositions. Accordingly, various auxiliary materials can be incorporated in accordance with the practice for such resin compositions. An example of such an auxiliary material is a bulking agent. Typical examples of fillers include (aBn fibrous filler; glass fiber, carbon fiber, boron fiber, aramid fiber, alumina fiber, silicon carbide fiber, etc.; (b) inorganic filler: Myriki;
Examples include talc, clay, graphite, carbon black, silica, asbestos, molybdenum sulfide, magnesium oxide, calcium oxide, etc. (c) Compatible thermoplastic resin: polyamide, polyimide, etc.

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

(IVI Experimental Examples The following Examples and Comparative Examples are for explaining the present invention more specifically. The scope is not limited by these Examples.

Examples 1 to 5 and Comparative Examples 1 to 5 Aromatic polyimide resins (in pellet form or fine powder form) represented by structures (A) to (C) of the following formulas were heated at 330 to 350°C.
Using a plastic bender, an aromatic poly(ether) sulfone resin was mixed and kneaded, and this was compression molded at 300 to 350°C to create a test island, and the maple characteristics etc. were measured. In addition, L/D-
The melt viscosity and flow state were measured under the following conditions: 10 (L: 10 mm x D: 1 die). In addition, differential thermal analysis (DuPon
t 910 Dlf'rerent1al Scann
lng Ca1orIn+eter), 3
Once heated to 50℃, cooled to room temperature, then heated to 10℃
The glass transition temperature was measured by increasing the temperature at a rate of 1/min.

As a result, the systems containing aromatic poly(ether) sulfone resin (Examples 1 to 5) were different from the systems containing no aromatic poly(ether) sulfone resin (Comparative Examples 1 to 5).
3> and a known melt-molded polyimide (Comparative Example 4.5), it was clear that improved formability was achieved without almost impairing the original heat resistance and mechanical properties ([ (See Table 1).

[1nh of polyamic acid - 0,54 dl/g (0,5
%NMP solution, measured at 30°C). Glass transition temperature 241
℃. ] [ηlnh of polyamic acid -0,52 dl/g (0,
5% NMP solution, 30°C). Glass transition temperature 244℃
. ] [Polyamic acid y71nh-0°54dl/g (0,
5% NMP solution, 30°C). Glass transition temperature 254℃
. ] Comparison f16 Aromatic polyimide resin 90 shown by the structure (D) of the following formula
The weight part was mixed with "Pictrex P" using a high-speed mixer.
I mixed ES 4100GJ 10 weight QN5, but 4
There was no melting or flow at temperatures below 50°C.

[Y7inh of polyamic acid -0,62 dl/g (0
, 5% NMP solution, measured at 30°C). Glass transition temperature 400°C or higher (unclear). [Comparative Example 7] 20 parts by weight (fine powder) of the aromatic polyimide resin represented by the structure (A) was added to the aromatic polysulfone resin (needle) at 330° C. using a Brabender blastograph at 30 rpm for 10 minutes. 80 parts by weight of P-1700) were mixed and kneaded. Regarding this, using a 40 ton press,
A test piece for a tensile test was prepared at 320°C, and the tensile strength was measured.

In addition, the melt viscosity, compatibility state, flow state, and glass transition temperature were measured/observed (the AI11 standard method is the same as in Example 1). The results are shown in Table 3, and both heat resistance and mechanical strength were insufficient.

Table 3

[Brief explanation of drawings]

FIG. 1 is a graph showing the melt viscosity of Example 5 and Comparative Example 3.

Claims (1)

[Scope of Claims] A melt-flowable aromatic polyimide resin containing 50 mol% or more of repeating units represented by the following formula (I) 50-99.
Aromatic polyether) sulfone resin containing 50 mol% or more of the repeating unit represented by the following formula (II) in 9 parts by weight
An aromatic polyimide resin composition having excellent melt fluidity, characterized in that it contains 0.1 part by weight (the total amount of both is 100 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. ) ▲There are mathematical formulas, chemical formulas, tables, etc.▼(II) (In the formula, Ar'' is a divalent aromatic residue. Also, x is 0 or 1.)