JPH04220419A - Heat-resistant resin composition - Google Patents

Abstract

PURPOSE:To obtain a resin compsn. excellent in heat resistance, melt flowability, and mechanical strengths by melt mixing a specific polyamideimide resin precursor, a specific org. compd., and a polyphenylene sulfide resin. CONSTITUTION:A polyamideimide resin precursor mainly comprising structural units shown by the formula (wherein Ar is a trivalent arom. group contg. at lest one 6C ring; R is a divalent arom and/or aliph. group; and R1 is H, alkyl, or phenyl), a polyphenylene sulfide resin (e.g. T-4, a product of Tohprene Co., Ltd.), and an org. compd. having at least two NCO groups in the molecule (e.g. 4,4'-diphenylmethane diisocyanate) are melt mixed.

Description

[Detailed description of the invention]

0001

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention particularly relates to a resin composition having excellent heat resistance, melt flowability, and mechanical strength.

0002

[Prior Art] Polyamide-imide resin is a plastic material with excellent heat resistance, mechanical strength, electrical properties, and chemical resistance, but it has poor melt flowability and is difficult to injection mold, making it difficult to injection mold. Currently, molding is carried out using the method.

On the other hand, polyphenylene sulfide resins are characterized by excellent heat resistance, electrical properties, solvent resistance, and particularly excellent melt flowability, but they also have the drawback of being brittle. As a technique for improving the melt fluidity of polyamide-imide resin, a technique of blending polyphenylene sulfide resin has already been proposed (Japanese Patent Publication No. 57-9754). However, although this technique maintains the high heat resistance of the polyamide-imide resin, the mechanical strength is lost due to the brittleness of the polyphenylene sulfide resin. This tendency is observed regardless of the amount of polyphenylene sulfide resin used, but it becomes particularly noticeable when the amount exceeds 30% by weight, and the mechanical strength as a plastic material cannot be maintained. The above is the conventional technology, and for this reason, the current situation is that a material with well-balanced heat resistance, mechanical properties, and fluidity has not yet been obtained.

0004

Problems to be Solved by the Invention The problems to be solved by the present invention are to improve the decrease in mechanical strength that occurs when polyphenylene sulfide resin is blended for the purpose of improving the melt flowability of polyamideimide resin. It is. This is particularly an improvement in mechanical strength when 30% by weight or more of polyphenylene sulfide resin is mixed, which was not possible with conventional techniques. The present invention has made it possible to create a new material with a composition containing a large amount of polyphenylene sulfide resin, that is, a composition with excellent fluidity.

[0005]

[Means for Solving the Problems] That is, the object of the present invention is to (A) general formula (1)

[0006]

[Case 2]

(In the formula, Ar is a trivalent aromatic group containing at least one 6-membered carbon ring, R is a divalent aromatic and/or aliphatic group, and R1 is hydrogen, an alkyl group, or a phenyl group. ) A resin composition obtained by melt-kneading a polyamideimide resin precursor having a unit represented by (B) a polyphenylene sulfide resin (C) an organic compound having two or more isocyanate groups in the molecule as a main structural unit. achieved by. The polyamideimide resin precursor which is the component (A) used in the resin composition of the present invention has the general formula (1
) with the repeating unit represented as the main structural unit 50~
It has 100 mol%, preferably 70 to 100 mol%, most preferably 100 mol%, and has 5 as other structural units.
An amount of less than 0 mol %, preferably less than 30 mol %, most preferably 0 mol % of a polyamide having the following general formula (2) and/or a polyimide precursor having the general formula (3) and/or ( It is a polymer that may have polyimide units having the general formula 4). [In formula Ar
1 is a divalent aromatic group or aliphatic group containing at least one carbon 6-membered ring, Ar2 is a tetravalent aromatic group containing at least one carbon 6-membered ring, and R is represented by the general formula (1 )
has the same meaning as ]

[0008]

[Chemical 3]

[0009] Also included are structures in which the amic acid bond in the structure of general formula (1) is dehydrated and ring-closed, so that a portion thereof, preferably less than 50 mol%, more preferably less than 30 mol%, has become an imide bond. It will be done. Specific examples of Ar in general formula (1) include the following.

0010

[C4]

Among these, the following are preferred.

0012

[C5]

Further, R is a divalent aromatic and/or aliphatic group, and specific examples thereof include the following.

[0014]

[C6]

[0015] Among these, the following are preferable:

[0016]

[C7]

[0017] Particularly preferred are the following.

[0018]

[Chemical formula 8]

The most preferred are the following.

[0020]

[Chemical formula 9]

Next, specific examples of Ar1 in general formula (2) are as follows.

[0022]

[Chemical formula 10]

Further, specific examples of Ar2 in general formulas (3) and (4) include the following.

[0024]

[Chemical formula 11]

Each of the structural units represented by the general formulas (1), (2), (3), and (4) has one or more types corresponding to different Ar, Ar1, Ar2, and R in the polyamideimide resin precursor. May exist. That is, the polyamide-imide resin precursor of the present invention can take the form of various copolymers. The polyamide-imide resin precursor can be manufactured by various known methods (for example, Japanese Patent Publication No. 42-15637, Japanese Patent Publication No. 46-15513, etc.), and the polyamide-imide resin precursor of the present invention can be manufactured by any of the methods. It's okay. For example, one or more aromatic tricarboxylic anhydride monochlorides

[0026]

[Chemical formula 12]

and one or more diamines

002
8]

[Chemical formula 13]

and optionally dicarboxylic acid dichloride,

[0030]

[Chemical formula 14]

Aromatic tetracarboxylic anhydride

0032
]

[Chemical formula 15]

in the presence of a hydrogen chloride acceptor such as triethylamine, sodium hydroxide, etc., in a non-basic organic solvent partially miscible with water, such as acetone, methyl ethyl ketone,
It can be obtained by reacting tetrahydrofuran, dioxane, etc. with water in a mixed solvent.

Next, (B) used in the resin composition of the present invention
) component polyphenylene sulfide resin (sometimes abbreviated as polyphenylene sulfide) has the general formula

[0035]

[Chemical formula 16]

It is a polymer containing 70 mol % or more, more preferably 90 mol % or more of the repeating unit represented by the formula: If the repeating unit is less than 70 mol %, it is difficult to obtain a composition having specific properties. Various known methods can be used to obtain this polymer, but sodium sulfide and p
A preferred method is to react with -dichlorobenzene in an amide solvent such as N-methylpyrrolidone or dimethylacetamide or a sulfone solvent such as sulfolane. At this time, it is a preferable method to add an alkali metal carboxylate such as sodium acetate or lithium acetate in order to adjust the degree of polymerization. Meta bonds, within the range of less than 30 mol% as a copolymerization component and do not significantly affect the crystallinity of the polymer.

[0037]

[Chemical formula 17]

[0038] Ether bond,

[0039]

[Chemical formula 18]

[0040] Sulfone bond,

[0041]

[Chemical formula 19]

[0042] Biphenyl bond,

[0043]

[C20]

[0044] Amino group-substituted phenyl sulfide bond,

[
0045

[C21]

Carboxyl group-substituted phenyl sulfide bond,

[0047]

[C22]

Although it may contain other alkyl, nitro, phenyl, alkoxy group-substituted phenyl sulfide bonds, trifunctional phenyl sulfide bonds, etc., the copolymerization component is preferably less than 10 mol %. Furthermore, polyphenylene sulfide in which the SH terminal group concentration is adjusted is also included in the present invention. Depending on the composition of the composition, kneading conditions, etc., polyphenylene sulfide having an SH terminal group concentration of 10 mg equivalent or more per 1 kg of resin may give preferable results, and further, 20 mg equivalent or more may give more preferable results. Various methods can be considered for introducing the SH group, but there are no particular limitations, for example, hydrochloric acid,
SH groups can be easily introduced at the terminals by treating with acetic acid or the like, or by treating purified polyphenylene sulfide with a solvent such as hydrochloric acid, acetic acid, or acetone.

Furthermore, the organic compound having at least two or more isocyanate groups in the molecule, which is component (C) used in the resin composition of the present invention, refers to a compound in which two or more isocyanate groups are bonded to an aromatic or aliphatic group. A general term for compounds that Specific examples of these compounds include:
2,4-tolylene diisocyanate, 2,6-tolylene diisocyanate, 1,4-naphthalene diisocyanate, 1,5-naphthalene diisocyanate, 2,6-naphthalene diisocyanate, 1,3-phenylene diisocyanate, 1,4-phenylene diisocyanate , 4
, 4'-diphenylmethane diisocyanate, 2,2'
-dimethyldiphenylmethane-4,4'-diisocyanate, 3,3'-dimethyldiphenylmethane-4,4'
-diisocyanate, 4,4'-biphenyl diisocyanate, 2,4'-biphenyl diisocyanate, 3,
3'-dimethylbiphenyl-4,4'-diisocyanate, 4,4'-diphenyl ether diisocyanate,
Aromatic polyisocyanates such as 4,4'-diphenylsulfone diisocyanate and triphenylmethane triisocyanate; hexamethylene diisocyanate, 2,
4,4-trimethylhexamethylene diisocyanate,
Aliphatic compounds such as 2,2,4-trimethylhexamethylene diisocyanate, dicyclohexylmethane-4,4'-diisocyanate, xylylene diisocyanate, bis(isocyanatemethyl)cyclohexane, 3-isocyanatemethyl-3,5,5-trimethylcyclohexylisocyanate Polyisocyanates and isothiocyanates corresponding thereto; examples include polyhydric alcohol adducts, water adducts, amine adducts, and isocyanurate modified products of the above-mentioned aromatic or aliphatic polyisocyanates. Among these, preferred are aromatic diisocyanates, such as 2,4-tolylene diisocyanate and 2,4-tolylene diisocyanate.
, 6-tolylene diisocyanate, 1,3-phenylene diisocyanate, 1,4-phenylene diisocyanate, 4,4'-diphenylmethane diisocyanate, 4
, 4'-biphenyl diisocyanate, and 4,4'-diphenyl ether diisocyanate, and more preferred are 2,4-tolylene diisocyanate, 2,6-tolylene diisocyanate, and 4,4'-diphenylmethane diisocyanate. Furthermore, in the present invention, component (C)
You may use a mixture of one or more of these organic compounds.

Next, components (A), (
The blending amounts of B) and (C) are 5 to 95% by weight of the polyamide-imide resin precursor of component (A), preferably 20 to 70% by weight, more preferably 20 to 65% by weight, and component (B). Polyphenylene sulfide resin 5-95% by weight
, preferably 30 to 80% by weight, more preferably 35 to 80% by weight
0.01 to 20 parts by weight, preferably 0.01 to 20 parts by weight of an organic compound having at least two or more isocyanate groups in the molecule, which is component (C), per 100 parts by weight of the 80% by weight composition.
．． 0.01 to 10 parts by weight, more preferably 0.01 to 5 parts by weight. If the amount of polyphenylene sulfide resin is more than this, heat resistance and mechanical properties will be insufficient, and if it is less than this, fluidity will be insufficient. If the amount of the polyamide-imide resin precursor is larger than the amount shown here, the fluidity will be insufficient, and if it is smaller than the amount shown here, the heat resistance and mechanical properties will deteriorate. On the other hand, if the amount of the organic compound as component (C) is less than the amount shown here, the effect of improving mechanical properties will be small, and if it is too large, the fluidity will be insufficient.

[0051] The method of blending each component constituting the resin composition of the present invention is not particularly limited, but for example, a method of blending each component all at once and melt-kneading. A method in which a polyamide-imide resin precursor and a polyphenylene sulfide resin are melt-kneaded in advance, and then component (C) is added and kneaded again. A method in which polyphenylene sulfide resin and component (C) are melt-kneaded, then a polyamide-imide resin precursor is blended and kneaded again. etc. can be mentioned. A preferred method is to melt-knead the polyamide-imide resin precursor with the polyphenylene sulfide resin, then add component (C) and knead again. When kneading with an extruder, a polyamide-imide resin precursor and a polyphenylene sulfide resin are supplied from a first feed port, and a second feed port is provided in a zone where both are sufficiently kneaded, and component (C) is supplied from here. This method is a convenient method. The resin composition of the present invention is produced by melt-kneading each component. At this time, most of the amic acid bonds in the polyamide-imide resin precursor, which is the component (A) of the present invention, are ring-closed to form imide rings and form a polyamide. Although it is considered that the water is converted into imide resin, it is preferable to use a method such as removing the water generated at this time by reducing pressure from the vent port. The melt-kneading temperature is 250 to 400°C, preferably 300 to 380°C, and the kneading method can be carried out using an extruder, kneader, Banbury mixer, roll, or the like.

The resin composition of the present invention may optionally contain other resins; elastomers; various additives such as flame retardants, flame retardant aids, stabilizers, ultraviolet absorbers, and plasticizers; pigments, and fillers. Other ingredients may be added as appropriate. Examples of other resins mentioned include aliphatic, aromatic polyamides, aliphatic, aromatic polyesters, polycarbonates, polysulfones, polyethersulfones, polyetherimides, polyetherketones, polyetheretherketones, polyimides, etc. is given as an example.

Examples of the elastomer include polysulfide rubber, polyester elastomer, polyamide elastomer, polyesteramide elastomer, and silicone rubber.

Examples of various additives include flame retardants such as phosphoric acid esters such as triphenyl phosphate and tricresyl phosphate; decabromo biphenyl, pentabromotoluene, decabromo biphenyl ether, Examples include brominated compounds such as hexabromobenzene and brominated polystyrene; nitrogen-containing compounds such as melamine derivatives; nitrogen-containing phosphorus compounds such as cyclic phosphazene compounds and phosphazene polymers. Flame retardant aids may be used, examples include antimony, boron, zinc or iron compounds. Further, other additives include stabilizers such as sterically hindered phenols and phosphite compounds; ultraviolet absorbers such as oxalate diamide compounds and sterically hindered amine compounds.

Furthermore, pigments such as titanium oxide, zinc sulfide, and zinc oxide; glass beads, wollastonite, mica, talc, clay, charcoal, magnesium hydroxide, silica, diatomaceous earth, graphite, and carbon Random, mineral fillers exemplified by molybdenum disulfide; glass fibers, milled fibers, boron fibers, silicon carbide fibers, carbon whiskers, asbestos fibers, asbestos, rock wool, potassium titanate fibers, brass, aluminum, zinc, etc. Examples include inorganic fibers such as metal fibers; organic fibers such as carbon fibers and aramid fibers; and flakes of aluminum and zinc. The filler is preferably used in an amount of 1 to 50% by weight of the entire composition.

[0056] The preferred filler has an average particle size of 4.5 to 50μ.
m glass beads; average length 1.5-50 mm, average diameter 6-20 μm glass fibers; average length 30-300 μm
The filler is exemplified by milled fiber, etc., and a mixture of these fillers may also be used.

[0057]

[Operations and effects of the present invention] The resin composition of the present invention has excellent heat resistance, melt flowability, and mechanical strength. This is thought to be because the resin precursor and polyphenylene sulfide resin were copolymerized by the chemical action of the compound (C).

The resin composition of the present invention will be explained in more detail below with reference to Examples, Reference Examples, and Comparative Examples.

[0059]

[Reference Example 1] (Production of polyamideimide resin precursor) Metaphenylenediamine 432.6g and tritylamine 4
45.3 g was dissolved in a mixed solvent of 12.8 liters of acetone and 5.4 liters of water, and while stirring vigorously in a 50 liter reactor equipped with an agitator, 842.0 g of trimellitic anhydride monochloride was added. Acetone 5.2
1 of the solution was added at once, and stirring was continued for 20 minutes to carry out polymerization. After completion of the polymerization, the precipitated polymer was filtered off under suction, further dispersed in methanol, thoroughly washed, separated, and dried under reduced pressure at 50°C to obtain a polyamide-imide resin precursor. Dimethylformamide solution (concentration 1
．． The reduced viscosity of this product at 30°C was measured to be 0.32 dl/g. By infrared method, 1780 (1/cm) imide groups and 1525 (1/cm)
When we investigated the ratio of amic acid bonds and imide bonds using the absorption of the amide group of cm), we found that 10% of the amic acid bonds closed and changed to imide rings, but the remaining 90% were amic acid bonds. there were.

[0060]

[Reference Example 2] (Production of polyamideimide resin precursor) Reference Example 1 was repeated except that 432.6 g of metaphenylene diamine was changed to 793.1 g of 4,4'-diaminodiphenylmethane. The reduced viscosity of a dimethylformamide solution (concentration 1.0 g/dl) of the obtained precursor at 30°C was 0.39 dl/g, and the residual rate of amic acid bonds measured by infrared method was 90%. .

[0061]

[Reference Example 3] (Production of polyamide-imide resin precursor) Reference Example 1 was repeated except that 432.6 g of meta-phenylene diamine was changed to 488.7 g of meta-tolylene diamine. The reduced viscosity of a dimethylformamide solution (concentration 1.0 g/dl) of the obtained precursor at 30°C is 0.
At 34 dl/g, the residual rate of amic acid bonds measured by infrared method was 95%.

[0062]

[Reference Example 4] (Production of polyamide-imide resin precursor) 432.6 g of meta-phenylene diamine was mixed with 216.3 g of meta-phenylene diamine and 396 g of diaminodiphenylmethane.
．． Reference Example 1 was repeated except that 5 g of the mixture was used. The reduced viscosity of the obtained precursor in dimethylformamide solution (concentration 1.0 g/dl) at 30°C is 0.36.
The residual rate of amic acid bonds measured by infrared method was 90% in dl/g.

[0063]

[Reference Example 5] (Production of polyamide-imide resin precursor) 4
, 4'-diaminodiphenyl ether 480.6 g and metaphenylene diamine 173.0 g were used as the diamine component, and trimellitic anhydride monochloride 5
Reference Example 1 was repeated using a mixture of 05.2 g and 324.8 g of isophthalic acid dichloride as the acid component. The reduced viscosity of the obtained precursor in dimethylformamide solution (concentration 1.0 g/dl) at 30°C is 0.35 d.
The residual rate of amic acid bonds measured by infrared method was 90% in l/g.

[0064]

[Examples 1 to 3] The polyamide-imide resin precursor produced in Reference Example 1 and polyphenylene sulfide resin (manufactured by Toprene Co., Ltd., trade name T-4) were blended in the composition shown in Table 1, and then blended using a twin-screw extruder. The mixture was melt-kneaded at 360°C to form pellets. These pellets were blended with 4,4'-diphenylmethane diisocyanate in the amounts shown in Table 1, and melt-kneaded again at 360°C using a twin-screw extruder to form pellets to produce a resin composition. This pellet was injection molded to obtain a 1/8 inch thick dumbbell test piece and a 1/8 inch thick bending test piece. The tensile strength and elastic modulus were determined from the dumbbell test piece, and the heat distortion temperature (18.6Kg) was determined from the bending test piece.
Also, the melt flow value was measured from the pellet at 350°C and 60 kg stress. These results are shown in Table 1.

[0065]

[Comparative Examples 1 to 3] In Examples 1 to 3, 4
, 4'-diphenylmethane diisocyanate was not used. The results are shown in Tables 1 and 2.

[0066]

Examples 4 to 6 Examples 1 to 3 were repeated except that the polyamideimide resin precursor of Reference Example 1 was changed to the polyamideimide resin precursor of Reference Example 2. The results are shown in Table 2.

[0067]

Comparative Examples 4 to 6 Comparative Examples 1 to 3 were repeated except that the polyamide-imide resin precursor of Reference Example 1 was changed to the polyamide-imide resin precursor of Reference Example 2. The results are shown in Tables 2 and 3.

[0068]

Examples 7-8 Examples 1-3 were repeated except that the polyamide-imide resin precursor of Reference Example 1 was changed to the polyamide-imide resin precursor of Reference Example 3. The results are shown in Table 4.

[0069]

[Comparative Examples 7-8] Comparative Examples 1-3 were repeated except that the polyamide-imide resin precursor of Reference Example 1 was changed to the polyamide-imide resin precursor of Reference Example 3. The results are shown in Table 4.

[0070]

Examples 9-10 Examples 1-3 were repeated except that the polyamide-imide resin precursor of Reference Example 1 was changed to the polyamide-imide resin precursor of Reference Example 4. The results are shown in Tables 4 and 5.

[0071]

Comparative Examples 9-10 Comparative Examples 1-3 were repeated except that the polyamide-imide resin precursor of Reference Example 1 was changed to the polyamide-imide resin precursor of Reference Example 4. The results are shown in Table 5.

[0072]

Examples 11-12 Examples 1-3 were repeated except that the polyamide-imide resin precursor of Reference Example 1 was changed to the polyamide-imide resin precursor of Reference Example 5. The results are shown in Table 5.

[0073]

Comparative Examples 11-12 Comparative Examples 1-3 were repeated except that the polyamide-imide resin precursor of Reference Example 1 was changed to the polyamide-imide resin precursor of Reference Example 5. The results are shown in Table 6.

[0074]

[Table 1]

[0075]

[Table 2]

[0076]

[Table 3]

[0077]

[Table 4]

[0078]

[Table 5]

[0079]

[Table 6]

Claims (1)

[Claims] Claim 1: (A) General formula (1) [Formula 1] (wherein Ar is a trivalent aromatic group containing at least one carbon 6-membered ring, R is a divalent aromatic and/or aliphatic group) basis,
R1 represents hydrogen, an alkyl group, or a phenyl group. ) A polyamide-imide resin precursor having the unit represented by (B) as a main structural unit, (B) a polyphenylene sulfide resin, and (C) an organic compound having two or more isocyanate groups in the molecule. resin composition.