JPH03181560A - Aromatic poly(amide/imide) resin composition - Google Patents

Abstract

PURPOSE:To obtain a resin composition having extremely improved melt fluidity without impairing heat resistance and mechanical characteristics by blending a specific aromatic poly(amide/imide) resin with a specific liquid crystalline aromatic polyester. CONSTITUTION:(A) 80-99 pts.wt., preferably 88-97 pts.wt. aromatic poly(amide/ imide) resin capable of melting and flowing, prepared from an aromatic diamine consisting essentially of an aromatic diamine having (thio)ether bond shown by formula I (Ar is bifunctional aromatic group; X is S or O) and an aromatic polycarboxylic acid compound, containing >=50mol% one of repeating units shown by formula II, formula III and formula IV (Ar' is tetrafunctional aromatic residue) is blended with (B) 20-1 pt.wt., preferably 12-3 pts.wt. liquid crystalline aromatic polyester having a transition point from a solid phase to a liquid crystalline phase between 200-350 deg.C to give a resin composition.

Description

DETAILED DESCRIPTION OF THE INVENTION [Background of the Invention] <Industrial Application Field> The present invention relates to an aromatic poly(amide/imide) resin composition having excellent melt moldability.

More specifically, the present invention provides aromatic compounds that have excellent heat resistance and good melt flowability and are useful as super engineering plastics, matrix resins for advanced composite materials, heat-resistant films, heat-resistant fibers, heat-resistant coating materials, etc. Poly (
amide/imide) resin composition.

<Conventional technology> Aromatic polymers with amide viscosity or imide bonds in the polymer main chain have excellent heat resistance and mechanical properties, and are used in practical applications such as heat-resistant films, heat-resistant fibers, and special molding materials. There is. However, most of them do not melt at all, or even if they do melt, their fluidity is extremely poor, making it difficult to apply general molding methods such as injection molding and extrusion molding.

Various studies have been made to improve these drawbacks. For example, efforts are being made to introduce aliphatic units into the main chain of polymers, various linking functional groups, and bulky substituents into side chains. Among these methods, the method of introducing -3- or -O- as a linking functional group into the main chain of the polymer is currently considered to be the most superior method. In particular, poly(amide/imide) resins obtained from aromatic diamines having thioether bonds have an excellent balance of heat resistance, mechanical properties, and moldability (Japanese Patent Application Laid-Open No. 60-226527,
(See 60-226528, 62-15227, 62-15228, etc.). However, although the moldability has been improved, improvement in the negative layer has been desired.

By the way, polyoxybenzylene (
It is well known to add liquid crystalline aromatic polyester resins, such as copolymers);
Aromatic polyimide resins such as EL (Du Pon 1 product) originally have poor melt fluidity, while aromatic polyimide resins with excellent melt fluidity such as ULTIEM (02 Company product) Since these resins have poor heat resistance, it was unknown that adding a liquid crystalline aromatic polyester resin to these resins would provide an aromatic polyimide resin that satisfies both heat resistance and melt fluidity. Such 314 circumstances are similarly recognized for aromatic polyamides and aromatic polyamideimide resins.

[Summary of the invention]

Means for Solving the Problems> The present invention is based on the general formula (IV) (wherein -Ar- is a divalent aromatic residue;
X- is -S-1 or 10-. ), which is obtained from an aromatic diamine whose main component is an aromatic diamine having an ether bond or a thioether bond (hereinafter referred to as a (thio)ether bond), and an aromatic polycarboxylic acid compound. Aromatic poly(amide/
When a specific amount of a commercially available aromatic polyester resin having a phase transition point within a specific temperature range is blended with an aromatic poly(amide/imide) resin in a specific amount, the heat resistance and mechanical properties inherent to the aromatic poly(amide/imide) resin are was completed based on the discovery that a significant improvement in melt fluidity was achieved.

Therefore, the aromatic poly(amide/imide) resin composition according to the present invention is a melt-flowable aromatic poly(amide/imide) resin composition containing 50 mol% or more of any of the repeating units of the following formulas (1), (II), and (III). 80 to 99 parts by weight of poly(amide/imide) resin with a transition point from solid phase to liquid crystal phase of 200 to 350°C
It is characterized in that 20 to 1 part by weight of a liquid crystalline aromatic polyester resin having an H temperature between 1 and 2 (total F weight of both is 100 parts by weight) is blended.

(In the formula, -Ar- is a divalent aromatic residue, and is a tetravalent aromatic residue.) [Detailed description of the invention] Aromatic poly(amide/imide) resin> This invention The aromatic poly(amide/imide) resin to which this is applied is the following (A
), (B), (C) and (D).

(A) 50 mol% of the repeating unit represented by formula (1)
A melt-flowable aromatic polyamide resin containing the above.

U 　　　　0 (B) formula () 50 moles of the repeating unit represented by Containing % or more, Melt-flowable aromatic polyamide Doimi De resin.

○ (C) formula () 50 moles of the repeating ili position shown in Containing % or more, Melt-flowable aromatic polyimide De resin.

(D) Formula (1) () repeating unit indicated by A solution containing 50 mol% or more of at least two of the following. Melt-flowable aromatic poly(amide/imide) resin.

In the above formulas (1) to (III), -Ar- is a divalent aromatic residue, -X- is -S- or 10-, and these aromatic poly(amide/imide) resins are It is obtained by reacting an aromatic diamine, including an aromatic diamine having (thio)ether viscosity, with an aromatic polycarboxylic acid compound.

(1) Aromatic diamine The aromatic (thio)ether diamine thus reacted with the aromatic polycarboxylic acid compound has the general formula (IV
) [In the formula, -Ar- is a divalent aromatic residue.

-X- is -S- or 10-. ]. Here, the divalent aromatic residue is [wherein A is 0SCOSOSSO2 and 2n in Co]
Either. However, n represents an integer of 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, or a nitro group.

as bSCSds e-, fs g are each 0 to 4
indicates an integer. m represents a number from 0 to 20. ] is preferred. Specific examples of such aromatic (thio)ether diamines include the following.

Specific examples of aromatic thioether diamine include 14-
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)biphenyl, 4,4'-bis(4-aminophenylthio)diphenyl ether, 44'-bis (4-aminophenylthio)diphenyl sulfide, 1,4bis(4-
(4-aminophenylthio)phenylthio)benzene,
α,ω-diaminopoly(14-thiophenylene) oligomer, 4,4'-bis(4-aminophenylthio)
Benzophenone, 4.4'-bis(4-aminophenylthio)diphenyl sulfoxide, 44'-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. can be mentioned. Among these, preferred are 4.4'-bis(4-aminophenylthio)biphenyl, 4.4'
-bis(4-aminophenylthio)diphenyl sulfide, 4.4'-bis(4-aminophenylthio)benzophenone, 4.4'-bis(4-aminophenylthio)diphenylsulfone.

Specific examples of aromatic ether diamines include 14-bis(4-aminophenoxy)benzene, 1°3-bis(4
-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)
Examples include benzophenone, 4°4'-bis(4-aminophenoxy)diphenylsulfone, 2,2-bis(4-(4-aminophenoquine)phenyl)propane, etc. Among these, preferred are 4 ,4′ bis(
4-aminophenoxy)biphenyl, 4゜4'-bis(4-aminophenoxy)diphenylsulfone, 2,2
-BisC4-<4-aminophenoxy)phenyl]propane.

Two or more kinds of the above aromatic (thio)ether diamines can be used in combination within each group and/or between each group.

The amount of these aromatic (thio)ether diamines used is
The amount is 50 mol% or more, preferably 70 mol% or more, based on the total amount of aromatic diamine to be reacted with the aromatic polycarboxylic acid compound. If the amount used is less than 50 mol%, the balance between heat resistance, mechanical properties, and moldability of the resulting resin will be poor, which is not preferable. Up to 50 mol% may be replaced with other aromatic diamines to further improve heat resistance.

Specific examples of such other aromatic diamines include p-
Phenylene diamine, m-phenylene diamine, tolylene diamine, 2-chloro-1,4 phenylene diamine,
4-chloro-1,3-7 22-diamine, 4-4'
-diaminobiphenyl, 3,3'-dimethyl-4,4
'-diaminobiphenyl, 33'-dichloro-4,4
'-diaminobiphenyl, 4.4'-diaminodiphenyl ether, 3.4'-diaminodiphenyl ether, 4.4'-diaminodiphenyl sulfate,
f-do, 4.4'-diaminodiphenylsulfone, 3°4'-diaminodiphenylsulfone, 3.3'diaminodiphenylsulfone, 4.4'-diaminobenzophenone, 3.3'-diaminobenzophenone, 3.4
'-Diaminobenzophenone, 4゜4'-diaminodiphenylmethane, 3,3'-diaminodiphenylmethane, 1,3-bis(3-aminophenoxy)benzene, 2,2-bis[4-(3-aminophenoxy)phenyl] Propane, etc. can be mentioned.

(2) Aromatic polycarboxylic acid compound The aromatic polycarboxylic acid compound used in the present invention is an aromatic dicarboxylic acid compound, an aromatic tricarboxylic acid compound, or an aromatic tetracarboxylic acid compound. Here, the term "carboxylic acid compound" refers to the carboxylic acid itself and -C
It means a functional derivative with respect to OOH.

Here, the "functional derivatives of r-COOH" are typically acid anhydrides, acid halides, and esters. An amide bond or the like is formed by dehydrohalogenation or dealcoholization reaction.

Specific examples of these aromatic polycarboxylic acid compounds include the following.

(a) Aromatic dicarboxylic acid compounds such as isophthalic acid (dichloride) and terephthalic acid (dichloride).

(b) Aromatic tricarboxylic acid compounds trimellitic acid, trimellitic anhydride (chloride), etc.

(c) Aromatic tetracarboxylic acid compound general formula [wherein B is O,,51CO1SO1SO2, NHCO
and C, Z2. Either. However, 2 is a hydrogen atom or a halogen atom, and p represents an integer of 1 to 10. Y is an alkyl group having 1 to 20 carbon atoms, 7 to 2 carbon atoms
0 aralkyl group, a cycloalkyl group having 3 to 20 carbon atoms, an aryl group having 6 to 20 carbon atoms, a halogen group, or a nitro group. h represents an integer of O~2, and iS j is an integer of O~3, respectively. k is O or 1. ]
Aromatic tetracarboxylic acids or functional derivatives thereof, particularly dianhydrides, are representative.

Specific examples of such aromatic tetracarboxylic acid compounds include pyromellitic acid (dianhydride), benzophenonetetracarboxylic acid (dianhydride), biphenyltetracarboxylic acid (dianhydride), and diphenylsulfonetetracarboxylic acid (dianhydride). dianhydride), diphenyl ether tetracarboxylic acid (dianhydride), diphenyl sulfide tetracarboxylic acid (dianhydride), benzanilide tetracarboxylic acid (dianhydride), hexafluoropropane-2,2-bis(anhydride) phthal One example is acid. Among these, preferred are pyromellitic acid (dianhydride), biphenyltetracarboxylic acid (dianhydride), diphenylsulfonetetracarboxylic acid (dianhydride), diphenyl ethertetracarboxylic acid (dianhydride), and the like.

(3) Polymer The glass transition temperature (Tg) of the aromatic poly(amide/imide) resin obtained by the reaction of the above aromatic polycarboxylic acid compound and aromatic diamine is preferably 200.
~300°C. In addition, from the balance of mechanical properties and moldability of the resin, it is desirable that the intrinsic viscosity of the aromatic poly(amide/imide) resin be in the range shown below (0, 2
%N-methylpyrrolidone solution (hereinafter referred to as NMP solution), measured at 30°C).

Aromatic polyamide: 0.6-1.5 dl/g Aromatic polyamide-imide: 0.5-1. 0 dl/g of aromatic polyimide 0.4-1.0 dl/g* (*0 of polyamic acid
．． 5% NMP solution, measured at 30°C) Liquid crystalline aromatic polyester resin> The liquid crystalline aromatic polyester resin to which the present invention is applied is as follows:
It is an aromatic polyester resin having a transition point from a solid phase to a liquid crystal phase between 200 and 350°C.

Here, "liquid crystallinity" means exhibiting an intermediate phase (mesophase) located between a crystal and a liquid, which has both the molecular regularity of a crystal and the fluidity of a liquid in a certain temperature range.

In general, in liquid crystalline polyesters, when the transition point is exceeded and the liquid crystal temperature region is reached, the melt viscosity decreases and molding becomes easier, but when the transition point is low (less than 200°C)
This is not preferred because it lowers the heat resistance of the poly(amide/imide) resin.

On the other hand, if the transition point is high (over 350° C.), the effect of improving melt moldability is small and undesirable.

Therefore, as a resin that satisfies both heat resistance and melt moldability, it is important to use a liquid crystalline aromatic polyester resin whose transition point is between 200 and 350°C.

Specific examples of preferred aromatic polyester resins include Vectra A950 (transition point: 280°C) (manufactured by Hoechst Celanese) and Econol E6000 (transition point: 321°C) (manufactured by Sumira Chemical Co., Ltd.). I can do it.

Blending> The composition of the present invention in which a liquid crystalline aromatic polyester resin is blended with an aromatic poly(amide/imide) resin can be obtained by various known methods. for example,
Aromatic poly(amide/imide) resin and liquid crystalline aromatic polyester resin are pre-prepared (iii) using a Henschel mixer or the like.
Examples include a method of mixing, melt extruding, and then forming pellets.

The amount of liquid crystalline aromatic polyester resin added is 20 to 1 part by weight of liquid crystalline aromatic polyester resin to 80 to 99 parts by weight of aromatic poly(amide/imide) resin, preferably aromatic poly(amide/imide) resin. 88 to 97 parts by weight and 12 to 3 parts by weight of the liquid crystalline aromatic polyester resin (the total weight of both is 100 parts by weight). If the amount of liquid crystalline aromatic polyester resin added is less than 1 part by weight, no effect will be observed due to its addition; on the other hand, if the amount added exceeds 20 parts by weight, the anisotropy of the molded product will increase and the surface condition will deteriorate. or
performance may deteriorate.

Processing and Applications> When molding the composition of the present invention, various known filler components can be included. Typical examples of filler components include (a) fibrous fillers such as glass fiber, carbon fiber, boron fiber, aramid fiber, alumina fiber,
Silicon-carbide fibers, etc. (b) Inorganic fillers such as mica, talc, clay, graphite, carbon black, silica, asbestos, MgOlCaO%MO82
, potassium titanate, and the like.

In addition, poly(tetrafluoroethylene), polyphenylene sulfide, polysulfone, polyether sulfone,
It is also possible to add polymers such as polyarylsulfone.

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, aircraft structural materials, sliding parts, gears, insulating materials, heat-resistant films, heat-resistant varnishes, heat-resistant fibers, etc. It can be used for various purposes.

[Example of practical experience]

The following Examples and Comparative Examples are provided to further specifically explain the present invention. The scope of the present invention is not limited by these examples.

Examples 1 to 6 and Comparative Examples 1 to 9 Aromatic poly(amide/imide) resins (pellets or fine powder) represented by structures (A) to (F) of the following formulas were
A liquid crystalline aromatic polyester resin is blended and kneaded using a Brabender at 0 to 350°C, and this is mixed and kneaded at 300 to 350°C.
A test piece was made by compression molding, and its mechanical properties were measured.
(as listed in the table). In addition, L/D -10 (L 10mo + XD
The melt viscosity and flow state were measured under the conditions of a 1 mm die). In addition, differential thermal analysis (Du Pont 910Di
frcrncntial Seannlng Color
Use imeter.

The temperature was raised to 350℃, cooled to room temperature, and then heated for 10 minutes.
The glass transition temperature was measured by increasing the temperature at 11 in.

The results are shown in Table 2. From this result, the transition point of aromatic poly(amide/imide) resin is 280℃.
The systems containing liquid crystalline aromatic polyester resin (Examples 1 to 6) are different from the systems containing no liquid crystalline aromatic polyester resin (Comparative Examples 1 to 6) and the systems containing liquid crystalline aromatic polyester resin having a transition point of 200 to 3.
The aromatic It was clear that the moldability was improved without substantially impairing the heat resistance and core properties inherent to the group poly(amide/imide) resin.

(A) [y+inh of polyamic acid -0.54 dl/g (0
, 5% NMP solution, measured at 30°C). Glass transition temperature -
241℃. ] (B) [r of polyamic acid] tnh -0,62dl/z
(0.5% NMP solution, measured at 30'C). Glass transition temperature -232°C. ] (C) [ηInh of polyamic acid -0,59 dl/FC(0
, 5% NMP solution, measured at 30°C). Glass transition temperature -
247℃. ] (D) 0 [ηfnh of polyamic acid -0,52 dl/g (0,
5% NMP melting, 1 constant at 30°C). Glass transition temperature -
234℃. ] (E) [η1nh −〇.

59dl/g (0° 29.6 N M P solution, (measured at 30℃) Glass transition temperature -236°C.

] (F) [η]nh −〇.

79dl/g (○.

2% NMP solution, At 30℃/Igj constant) Glass transition temperature = 224°C.

] <Table> l) Kneading with a Brabender Plastograph 2) 40) Hydraulic press, preheated for 10 minutes/pressurized to 150 kg/cj gauge pressure and held for 5 minutes. Figure 1 shows Example 3 and Comparative Example 3. The g-melt viscosity (measured with a Koka type flow tester at 370°C, L10 open/D1m+* die) is shown. In FIG. 1, (a) is of Example 3,
(b) is the melt viscosity of Comparative Example 3.

[Brief explanation of drawings]

FIG. 1 is a graph showing the melt viscosity of Example 3 and Comparative Example 3. (a)... Melt viscosity of Example 3, (b)... Melt viscosity of Comparative Example 3.

Claims (1)

[Claims] 1. A melt-flowable aromatic poly(amide/imide) resin 80 to 99 containing 50 mol% or more of repeating units of any of the following formulas (I), (II), and (III) 20 to 1 part by weight of a liquid crystalline aromatic polyester having a transition point from a solid phase to a liquid crystal phase between 200 and 350°C (total weight of both is 100 parts by weight) is added to the part by weight. An aromatic poly(amide/imide) resin composition. ▲There are mathematical formulas, chemical formulas, tables, etc.▼(I) ▲There are mathematical formulas, chemical formulas, tables, etc.▼(II) ▲There are mathematical formulas, chemical formulas, tables, etc.▼(III) (In the formula, -Ar- is a divalent It is an aromatic residue, -X- is -S- or -O-, and ▲ has mathematical formulas, chemical formulas, tables, etc. ▼ is a tetravalent aromatic residue.)