JPH0364356A - Aromatic polyimide resin composition - Google Patents

Abstract

PURPOSE:To obtain an aromatic polyimide resin composition having very excellent heat resistance and very good melt moldability by mixing a melt-flowable aromatic polyimide resin with an aromatic polyphenylene thioether resin. CONSTITUTION:The title composition is obtained by mixing 50-99.9 pts.wt. melt-flowable aromatic polyimide resin (A) having at least 50mol% repeating units of formula I (wherein Ar is a bivalent aromatic residue; and Ar' is a tetravalent aromatic residue) with 50-0.1 pt.wt. aromatic polyphenylene thioether (B) having at least 90mol% repeating units of formula II. By mixing resin A with resin B in this way, a resin composition improved in moldability and compatibility without detriment to the heat resistance and mechanical properties inherent in resin A can be obtained. The resin having repeating units of formula I can be obtained from an aromatic diamine based on a thioether bond- containing aromatic diamine of formula III (wherein Ar is as defined above) and an aromatic tetracarboxylic acid dianhydride of formula IV.

Description

DETAILED DESCRIPTION OF THE INVENTION [Background of the Invention] <Industrial Application Field> The present invention relates to a novel aromatic polyimide tree WB 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 octa-aromatic diamine (C1E, 5ROOG, "
Journal of Polymer Science, Macromolecule Review, Volume 11, Page 161, 1976
Year). 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 (JP-A-6215228, JP-A-63 -3
No. 09524, etc.) have 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, polyphenylene thioether resins represented by "Rydon" and "Tovren" have good fluidity and excellent heat resistance, so they have been actively investigated as fluidity improvers for heat-resistant resins. However, these polyphenylene thioethers have poor compatibility with many heat-resistant resins, and their blending causes a decline in the physical properties of heat-resistant resins, making it difficult to use them for the purpose of improving fluidity.

Although the use of various epoxy resins such as bisphenol-based and Talesol novolac-based resins has been proposed for the purpose of improving compatibility, the necessity to use such components is itself already unsatisfactory.

[Summary of the invention]

<Means for Solving the Problems> The present inventors have developed an aromatic diamine having a thioether bond as a main component represented by the general formula (m) (wherein A is a divalent aromatic residue). When blending the aromatic diamine with the general formula (IV), not only the moldability is improved but also the compatibility is good, so that the aromatic polyimide resin can be mixed without using a compatibilizer. It was confirmed that the original heat resistance and mechanical properties were not significantly impaired, and the present invention was completed.

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 to 99.9% by weight of repeating units represented by the following formula (I). The aromatic polyphenylene thioether resin containing 90 mol % or more of the repeating unit represented by the following formula (II) in 50 to 0.0 parts. 1 part by weight (the total amount of both is 100 parts by weight).

(In the formula, Ar' is a tetravalent aromatic residue.) A specific amount of aromatic polyphenylenethioether is added to a melt-flowable aromatic polyimide resin obtained from Resin 111 0 0 (wherein, Ar is a divalent aromatic residue. Also, Ar'
is the aromatic residue of 4gE. ) [Detailed Description of the Invention] The aromatic polyimide resin composition of the present invention having excellent melt fluidity is a composition in which an aromatic polyphenylene thioether resin is blended with an aromatic polyimide resin.

[I) 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:

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

(In the formula, Ar is a divalent aromatic residue) (In the formula, Ar
' is a tetravalent aromatic residue) A specific example of Ar is, for example, υ υ (A is any one of 0, C01SO1SO2, 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. alb-C5ds es f is 0 to 4, respectively.
indicates an integer. m represents a number from 0 to 20. ).

Specific examples of Ar' are, for example, (-B- is -o-1-s--co-1-8O2 and F3 Further, g is 0 or 1. ).

Specific examples of aromatic thioether diamines represented by general formula (III) 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, aω-diaminopoly( I,4-thiophenylene) oligomer, 4.4'
-bis(4-aminophenylthio)benzophenone,
4.4'-bis(4-aminophenylthio)diphenylsulfoxide, 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, and the like. At least one of these is used. The amount of diamine of formula (m) 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 mol % of this formula (m) aromatic thioether diamine. That is, up to 50 mol% of this diamine component may be replaced with another aromatic diamine.

Examples of other aromatic diamines include p-
Phenyl diamine, m-Phenyl 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, 4.41-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(4aminophenoxy)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
-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), diphenylsulfonetetracarboxylic acid (dianhydride)
, diphenyl ether tetracarboxylic acid (dianhydride),
Examples include diphenylsulfide 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 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 about 100-350°C, preferably 220-300°C. In addition, considering mechanical properties and moldability, the intrinsic viscosity is 0.4 dl/g (0.5% N-methylpyrrolidone (NMP) of the corresponding polyamic acid
) solution, measured at 30°C) or more, 1.0 dl/g
The following is desirable.

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 (T). It is clear from the above that this aromatic polyimide may contain a plurality of types of repeating units of formula (I) regarding A' and Ar'. 5
Repetitions other than formula (I) occupying up to 0 mol% 111
An example of the first position is an aromatic tetracarboxylic acid of formula (IV) (
It is also clear from the foregoing that it is the 111-position of an aromatic imide consisting of anhydride) and an aromatic diamine other than the formula (III) described above. 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 (mV). (anhydride)
and/or may be formed from diamines other than aromatic diamines.

[■] Aromatic polyphenylene thioether resin The resin to be blended with the above aromatic polyimide resin is an aromatic polyphenylene thioether resin.

The aromatic polyphenylene thioether resin (hereinafter sometimes referred to as PPS) to which the present invention is applied is expressed by the following formula (II
) is a polymer having 90 mol% or more of repeating units represented by the formula.

Examples of repeating units that may be contained in an amount up to 10 mol% include +Ar-8+ groups containing the Ar group exemplified with respect to formula (I), but more specifically, the following units: (Formula (II')).

(R: hydrocarbon residue having about 1 to 10 carbon atoms, or halogen atom m: 1 to 4) The aromatic polyphenylene thioether resin targeted by the present invention may be an oligomer with a molecular weight of about 1000 to 5000, or Although a polymer having a molecular weight of 10,000 or more may be used, the latter polymer is generally preferred. In addition, the molecular weight here is a weight average molecular weight, and is measured by a light scattering method. Among them, the viscosity is 300℃, shear rate 7 = 102 (s, ec-'
) with I x 102 ~ I x 10' Boise (L/D-30
) is particularly preferred.

PPS may have a crosslinked structure if the units contained up to 10 mol% are trifunctional (or more) as described above, but if it consists only of formula (II) Alternatively, even if the monomers of formula (■') are difunctional, they are originally linear structures, but can be given a crosslinked structure by mild oxidation. In the invention, aromatic polyimide resin (I
) The aromatic polyphenylene thioether resin may have a crosslinked structure such as these, as long as the intended fluidity improvement effect can be achieved while maintaining the solubility of the aromatic polyphenylene thioether resin.

Such PPS is prepared by mixing p-dichlorobenzene (preferably p-dichlorobenzene) and, if necessary, its dihalogen which provides the group of formula (■') in a suitable solvent or dispersion medium (
It can be produced by subjecting it to a dehalogenation/sulfurization reaction with an alkali sulfide (preferably Na 2 S) in the presence of N-methylpyrrolidone (preferably N-methylpyrrolidone).

Such PPS can be manufactured manually in the market, for example, the "Rydon PPS" manufactured by Philibus Petroleum Corporation in the United States
-4'', ``Rydon P-6'', and Nippon Topren's ``
Toblen T-1'' can be exemplified.

(II[) Blend/Production of Composition The composition of the present invention, which is a mixture of an aromatic polyimide resin and an aromatic polyphenylene thioether 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 polyphenylene thioether resin added, if it is too small, the effect will not be recognized, and if it is too large, the performance of the molded product will deteriorate. Therefore, based on the total ff1 (I00 parts by weight) of aromatic polyimide resin and aromatic polyphenylene thioether resin, the amount of aromatic polyphenylene thioether resin should be 50 to 0.1 parts by weight, preferably 15 to 3 parts by weight. Blend.

The composition according to the invention falls within the category of thermoplastic resin compositions. Accordingly, various auxiliary materials can be included in accordance with the practice for such resin compositions. An example of such an auxiliary material is a filler. Typical examples of fillers include (a) fibrous fillers such as glass fiber, carbon fiber, boron fiber, aramid fiber, alumina fiber, silicon carbide fiber, etc., (b) inorganic filler: Myroku,
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, including various parts in the electrical and electronic fields, housings, automobile parts, aircraft interior materials, TFFL moving parts, gears, insulating materials, heat-resistant films, heat-resistant varnishes, heat-resistant fibers, etc. Is possible.

(mV) 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 (in pellet form or fine powder form) represented by structures (A) to (D) of the following formulas were heated at 330 to 350°C.
Using a Brabender, an aromatic polyphenylene thioether resin was kneaded for 42 hours, and this was compression molded at 300 to 350°C to prepare a test piece, and its mechanical properties etc. were measured.

Also, at 370"C, using a Koka type flow tester, L
The melt viscosity and flow state were measured under the conditions of /D-10 (L10+nXD1 mm die). In addition, the differential heat content Fr
(Du Pont 910 DIf Terental
? c'anning Calorimeter), the temperature was raised to 350°C, and then cooled to room temperature.
Thereafter, the temperature was raised at a rate of 10° C./min, and the glass transition temperature was measured.

As a result, the systems containing aromatic polyphenylene thioether resin (Examples 1 to 3) were different from the systems containing no aromatic polyphenylene thioether resin (Comparative Example 1).
-4) and known melt-flowable polyimide resins (Comparative Examples 5-6), it has improved formability and good compatibility without significantly impairing the original heat resistance and mechanical properties. One thing was clear. ([Table 1] and [Table 2]
Table]) [η1nh of polyamic acid - 0,54 dl/g (0,5
%NMP solution, measured at 30°C). Glass transition temperature 241
°C ] [n Inh of polyamic acid -0.52 dl/g (
0.5% NMP solution, measured at 30°C).

Glass transition temperature 244°C. ] [ηinh of polyamic acid -0,50 dl/g (0
, 5% NMP solution, 30°C). Glass transition temperature 261℃
] [ηinh of polyamic acid -0.54 dl/g (0
, 5% NMP solution, measured at 30°C).

Glass transition temperature 254°C. ] [Table 1] 1) Kneading with a Brabender Plastograph 2) Preheating using a 4Cl hydraulic press for 10 minutes / Holding for 5 minutes after pressurizing to 150 kg/cJ gauge pressure Comparative Example 7 Shown by the structure (E) of the following formula Aromatic polyimide resin 90
Add "Toprene T-4J" to the weight part using a high-speed mixer.
Although 10ffi parts were blended, it did not melt and flow at temperatures below 450°C.

A test piece for a tensile test was prepared at 310°C, and the tensile strength was measured. Furthermore, the melt viscosity, flow state, and glass transition temperature were measured/observed (the measurement method was the same as in Example 1).

The results are shown in Table 3, and both heat resistance and mechanical strength were inadequate.

[Table 3] [η1nh of polyamic acid =0. 62dl/r(0
, 5% NMP solution, 1113 constant at 30°C). Glass transition temperature 400°C or higher (unclear). ] Comparative Example 8 Aromatic polyimide resin shown by the above structure (A) 2O
Aromatic polyphenylene thioether tree IJfI ()-Brene T was added to a portion of ffi (fine powder) at 330°C using a Brabender plastograph at 30 rpm for 10 minutes.
-1) 80 parts by weight were mixed and kneaded. Regarding this, 40
Using a ton press,

[Brief explanation of drawings]

FIG. 1 is a graph showing the melt viscosity of Example 6 and Comparative Example 4.

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 polyphenylene thioether resin 5 containing 90 mol% or more of repeating units 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 to 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. ) ▲ Contains mathematical formulas, chemical formulas, tables, etc. ▼ (II)