JP3160978B2 - Thermoplastic resin composition - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a polyarylene sulfide resin composition which can be melt-molded and has excellent mechanical properties and processability.

[0002] Polyarylene sulfide resin is a member of electric and electronic equipment, taking advantage of its excellent heat resistance and chemical resistance.
It is attracting attention as a component of automobile equipment. Further, it can be molded into various molded parts, films, sheets, fibers and the like by injection molding, extrusion molding and the like, and is widely used in fields requiring heat resistance and chemical resistance.

[0003]

2. Description of the Related Art Since polyarylene sulfide resin alone has insufficient mechanical strength and thermal properties, its properties are improved by blending inorganic reinforcing materials such as glass fibers and inorganic fillers. ing.

[0004] However, these improvements with inorganic fillers reduce the formability and impair the appearance. Therefore, in order to improve the moldability, a composition with a liquid crystal resin which can be melt-molded has been studied (for example, Japanese Patent Application Laid-Open No. 57-5 / 1982).
1739, JP-A-62-141064, etc.).
However, since the compatibility between the polyarylene sulfide resin and the liquid crystal resin is not sufficient, there have been problems such that the mechanical properties of the obtained molded product are insufficient, and the molded product surface is peeled off.

Japanese Patent Application Laid-Open No. Sho 62-549 discloses that the addition of an epoxy compound to a composition comprising polyphenylene sulfide, a liquid crystalline aromatic polyester and silica improves the strength. Sufficient effects have not been obtained.

[0006]

SUMMARY OF THE INVENTION An object of the present invention is to provide a novel polyarylene sulfide resin composition which is melt-moldable and has excellent mechanical properties and workability.

Another object of the present invention is to provide a polyarylene sulfide resin composition which is excellent in mechanical properties such as tensile strength, flexural modulus, impact strength and the like and which has good heat resistance.

Still another object of the present invention is to provide a polyarylene sulfide resin composition which can be molded into various molded articles by ordinary injection molding or extrusion molding based on its excellent melt moldability. It is in.

[0009]

Means for Solving the Problems The inventors of the present invention have made intensive studies to solve the above-mentioned problems, and as a result, have found that an amino group-containing polyarylene sulfide resin and a melt-moldable liquid crystalline resin are By blending a di- and / or polyepoxy compound, it has been found that the compatibility of both resins is remarkably improved, a good melt moldability is exhibited, and a heat-resistant molded article having excellent mechanical properties is provided. The present invention has been reached.

That is, the present invention relates to a resin composition 10 comprising 10 to 95% by weight of an amino group-containing polyarylene sulfide resin and 90 to 5% by weight of a melt-moldable liquid crystalline resin.
The thermoplastic resin composition comprises 0.05 to 15 parts by weight of an epoxy compound having two or more epoxy groups per 0 parts by weight.

Hereinafter, the present invention will be described specifically.

The amino group-containing polyarylene sulfide resin used in the present invention is described, for example, in Japanese Patent Publication No. Sho 45-3.
No. 368, it can be obtained in the same manner. Specifically, the following general formula

[0013]

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[0014]

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[0015]

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[0016]

Embedded image (X is a halogen, R is a hydrocarbon group having 1 to 12 carbon atoms, l
Is an integer of 0 to 4, m is an integer of 0 to 3, n is 1 or 2, l + n is 5 or less, and m + n is 4 or less), for example, m-chloroaniline , P-chloroaniline, 3-chloro-m-phenylenediamine, 2-amino-4-chlorotoluene, 2-
Reaction of one or more compounds selected from amino-6-chlorotoluene, 4-amino-2-chlorotoluene, 3,5-dichloroaniline and the like with an alkali metal sulfide and dihalobenzene in an organic amide solvent Can be obtained. At this time, 0.001 to 0.1 mol, preferably 0.003 to 1 mol of dihalobenzene
It is manufactured by adding about 0.05 mol. The amino group-containing aromatic halide may be added to the polymerization system after the dehydration of the alkali metal sulfide in the organic amide has been completed, or may be added together with the dihalobenzene. Further, it may be added to the system after the polymerization of the alkali metal sulfide and the dihalobenzene has started.

As the alkali metal sulfide, lithium sulfide, sodium sulfide, potassium sulfide, rubidium sulfide,
Cesium sulfide or mixtures thereof may be used, and these may be used in the form of hydrates. These alkali metal sulfides include hydrogen sulfide and alkali metal base,
It is obtained by reacting hydrogen sulfide with an alkali metal salt, and may be prepared in situ prior to addition of the dihalobenzene into the polymerization system, or may be prepared outside the system. Also preferred for use in the alkali metal sulfides is sodium sulfide.

Before the polymerization by adding dihalobenzene, the water in the system is preferably removed by distillation or the like to make the amount of the water less than about 4 mol per mol of alkali metal sulfide.
It is also possible to change the amount of water in the system during the polymerization. Examples of the dihalobenzene include p-dichlorobenzene, p-dibromobenzene, p-diiodobenzene, m
-Dichlorobenzene, m-dibromobenzene, m-diiodobenzene, 1-chloro-4-bromobenzene and the like, and preferable examples thereof include p-dihalobenzene such as p-dichlorobenzene.

If it is less than 30 mol% with respect to p-dihalobenzene, it may be m-dihalobenzene such as m-dichlorobenzene, o-dihalobenzene such as o-dichlorobenzene, dichloronaphthalene, dibromonaphthalene, dichlorodiphenyl. Dihalo aromatic compounds such as sulfone, dichlorobenzophenone, dichlorodiphenylether, dichlorodiphenylsulfide, dichlorodiphenyl, dibromodiphenyl, and dichlorodiphenylsulfoxide may be copolymerized.

It is also possible to copolymerize a polyhalo aromatic compound containing three or more halogens per molecule, for example, trichlorobenzene, tribromobenzene, triiodobenzene, tetrachlorobenzene, trichloronaphthalene, tetrachloronaphthalene and the like. It is.

As the polymerization solvent, a polar solvent is preferable.
Particularly preferred are organic amides which are aprotic and stable to alkali at high temperatures. Some examples of organic amides include N, N-dimethylacetamide, N, N-dimethylformamide, hexamethylphosphoramide, N-
Examples thereof include methyl-ε-caprolactam, N-ethyl-2-pyrrolidone, N-methyl-2-pyrrolidone, 1,3-dimethylimidazolidinone, dimethyl sulfoxide, sulfolane, tetramethyl urea, and the like, and mixtures thereof.

The polymerization is carried out at 200 to 300 ° C., preferably at 22 ° C.
0.5-30 hours at 0-280 ° C, preferably 1-1
Performed with stirring for 5 hours.

The charged amounts of the alkali metal sulfide and the dihalobenzene can be obtained by molarization (alkali metal sulfide):
(Dihalobenzene) = 1.00: 0.90 to 1.10.

The amount of the polymerization solvent used is such that the amount of the polymer formed by the polymerization is 3 to 60% by weight, preferably 7 to 60% by weight.
It can be used in the range of ４０40% by weight.

The recovery of the polyarylene sulfide from the reaction mixture thus obtained may be carried out by a conventional technique. For example, a method in which the solvent is recovered by distillation, flushing, etc., and then the polymer is washed with water and recovered. And a method in which the reaction mixture is filtered to collect the solvent, and then the polymer is washed with water and collected.

The polyarylene sulfide has, as constituent units, p-phenylene sulfide unit, m-phenylene sulfide unit, o-phenylene sulfide unit, phenylene sulfide sulfone unit, phenylene sulfide ketone unit, phenylene sulfide ether unit, diphenylene sulfide unit and the like. May contain one or two or more different units.

The structure of the melt-moldable liquid crystalline resin that can be used in the composition of the present invention is not particularly limited as long as it exhibits melt anisotropy. Those exhibiting liquid crystallinity in a possible temperature range are preferable. Examples of such a liquid crystalline resin include, for example, British Patent No. 1,507,207, US Patent No. 3,778,410, and US Patent No. 4,067,8.
No. 52, U.S. Pat. No. 4,083,829, U.S. Pat. No. 4,130,545 or U.S. Pat. No. 4,161,47; No. 4,048,148, aromatic polyester amides described in EP 391,276, other aromatic polyester-polycarbonates, aromatic polyester-polyimides, Aromatic polyisocyanate and the like can be mentioned, and a polyester or polyesteramide-based liquid crystal resin is particularly preferable.

Specific examples of the melt-moldable liquid crystal resin used in the present invention include, for example, a polyester-based liquid crystal resin having a unit constituting a hydroxycarboxylic acid compound, a diol compound or a dicarboxylic acid compound. No.

Among these, the hydroxycarboxylic acid compound is composed of an aromatic hydroxycarboxylic acid or a derivative thereof, and one hydrogen atom on the aromatic ring is further substituted by an alkyl group, an alkoxy group, a phenyl group or a halogen. The above may be substituted. See p
-Hydroxybenzoic acid, 4-hydroxy-3-methylbenzoic acid, 4-hydroxy-2-phenylbenzoic acid, 2-
Chlor-4-hydroxybenzoic acid, 3-chloro-4-hydroxybenzoic acid, 3-hydroxybenzoic acid, 2-hydroxy-6-naphthoic acid, 4,4′-diphenylhydroxycarboxylic acid and the like can be mentioned.

The diol compound is composed of an aliphatic diol or an aromatic diol, and one or more hydrogen atoms on the aromatic ring may be further substituted with an alkyl group, an alkoxy group, a phenyl group or a halogen. Specifically, ethylene glycol, butanediol, 4,
4'-biphenol, hydroquinone, resorcinol, 4,4'-dihydroxydiphenyl ether, 4,
Examples include 4'-dihydroxydiphenylsulfone, 4,4'-dihydroxydiphenylpropane, 4,4'-dihydroxybenzophenone, chloro-substituted hydroquinone, phenyl-substituted hydroquinone, and 2,6-naphthalenediol.

Further, the dicarboxylic acid compound is composed of an aliphatic dicarboxylic acid or an aromatic dicarboxylic acid, and one or more hydrogen atoms on the aromatic ring are further substituted by an alkyl group, an alkoxy group, a phenyl group or a halogen. Is also good. Specific examples include adipic acid, terephthalic acid, isophthalic acid, 4,4′-diphenyldicarboxylic acid, and 2,6-naphthalenedicarboxylic acid.

In the polyesteramide-based liquid crystalline resin, p-phenylenediamine, m-phenylenediamine, 4,4'-diaminodiphenyl ether, 4,4'-diaminodiphenylmethane, 4,4 Diamino compounds such as' -diaminodiphenyl sulfone; p-aminophenol; aminohydroxy compounds such as m-aminophenol; p-aminobenzoic acid; m
-Contains an aminocarboxylic acid compound such as aminobenzoic acid as a constituent component.

The liquid crystalline resin in the present invention can be produced by various condensation reactions using the above monomers alone or in combination of two or more. For example, the structural unit is subjected to an active esterification reaction at 50 to 200 ° C. for 1 to 5 hours, preferably at 140 to 180 ° C. for 2 to 4 hours in the presence of a lower acid anhydride, and thereafter, by-products are distilled off. Reaction temperature 240 ~ 3
It is manufactured by gradually increasing the temperature to 50 ° C., preferably 280 to 350 ° C. over 1 to 10 hours, and performing polymerization.
Further, this polymerization may be performed under reduced pressure atmosphere in order to increase the reaction rate. In some cases, the obtained product can be subjected to solid-state polymerization at a temperature of 200 to 350 ° C. to increase the degree of polymerization.

Examples of these melt-moldable liquid crystal resins include VECTRA manufactured by Hoechst Celanese, USA.
XYDAR manufactured by Amoco, USA, Econol manufactured by Sumitomo Chemical Co., Ltd., etc. are commercially available. In particular, the terminal of the liquid crystal resin has a functional group having reactivity with an epoxy group, for example, a carboxyl group, a hydroxyl group, an amino group, and the like. It is preferable to use a resin.

The mixing ratio between the amino group-containing polyarylene sulfide resin and the melt-moldable liquid crystalline resin is 95/5 to 10/90 by weight, preferably 90/10 to 40/90.
60, particularly preferably in the range of 85/15 to 60/40. If the proportion of polyarylene sulfide exceeds 95% by weight, the moldability is insufficient, and if it is less than 10% by weight, the weld strength is undesirably reduced.

The epoxy compounds having two or more epoxy groups that can be used in the composition of the present invention include:
Generally, bisphenol compounds, phenol novolaks, aromatic diols and dicarboxylic acid compounds, ethylene glycol, polyethylene glycol, propylene glycol, polypropylene glycol, polytetramethylene glycol, and polymers obtained by condensing epihalohydrin with a polymer having these as the basic structural unit. Diglycidyl ether compound, furthermore, a heterocyclic epoxy compound such as a hydantoin type compound, an alicyclic epoxy compound and the like. In particular, aromatic diepoxy compounds such as bisphenol A diglycidyl ether, bisphenol S diglycidyl ether, resorcin diglycidyl ether, hydroquinone diglycidyl ether, and terephthalic acid diglycidyl ether are preferred.

The amount of the epoxy compound is 0.05 to 15 parts by weight, preferably 0.07 to 100 parts by weight of the composition of the polyarylene sulfide resin and the liquid crystalline resin.
10 to 10 parts by weight, particularly preferably 0.1 to 5 parts by weight. When the amount is less than 0.05 part by weight, the effect of improving the compatibility is small, and the mechanical properties are insufficient. When the amount exceeds 15 parts by weight, the moldability and thermal stability are deteriorated, so that it is preferable. Absent.

The production of the resin composition of the present invention can be carried out in accordance with a method known per se, but it is particularly preferable to melt-knead, for example, in a kneader, a Banbury mixer, heat or an extruder.

The resin composition of the present invention is processed by a known molding method such as injection molding, extrusion molding, or hollow molding. In particular, injection molding and stretching at a high speed in which a high shear force is applied to the resin composition. Blow molding to which a force is applied is preferable from the viewpoint of exhibiting excellent strength and elastic modulus.

[0040]

[0041]

[0042]

Other well-known additives, for example, heat stabilizers such as hindered phenols and phosphates,
Weathering improvers such as triazine compounds, coloring agents such as pigments and dyes, impact improvers such as vinyl copolymers and hydrogenated products thereof, modified olefins, lubricants such as paraffin wax and fatty acid esters, silanes, titanates If necessary, a coupling agent such as a system, a crystal nucleating agent, an antistatic agent, and a flame retardant may be added.

[0044]

EXAMPLES The present invention will now be described specifically with reference to examples, but the present invention is not limited by these examples.

The melt viscosity of the obtained polymer was measured by a Koka type flow tester using a dice having a length of 2 mm and a diameter of 0.5 mm.

Reference Example 1 (Synthesis of Polyphenylene Sulfide Containing Amino Group) Na ₂ S · 2.9H ₂ O was placed in a 10-liter autoclave.
36 mol, 9 l of N-methyl-2-pyrrolidone
The mixture was stirred under a nitrogen stream and heated to 200 ° C.
g of a distillate mainly consisting of water was distilled off. Then 150 ° C
3840 g (35.82) of dichlorobenzene.
Mol), 3-chloro-m-phenylenediamine 25.6
7 g (0.18 mol), N-methyl-2-pyrrolidone 1
l, the system is charged under a nitrogen stream, and the temperature is raised to 250 ° C.
For 3 hours. After completion of the polymerization, the slurry cooled to room temperature was poured into a large amount of water to precipitate a polymer, which was separated by filtration, washed with pure water, and then heated and vacuum-dried overnight to isolate the polymer.

Reference Example 2 (Synthesis of Wholly Aromatic Polyester Liquid Crystalline Resin) A reaction vessel equipped with a stirrer, a cooling pipe and a nitrogen introducing pipe was placed in a reaction vessel.
1243 g (9 mol) of hydroxybenzoic acid, 382 g (2.3 mol) of terephthalic acid, 166 g of isophthalic acid
(1.0 mol), 4,4'-dihydroxydiphenyl 5
After 59 g (3 mol) and 1.8 kg of acetic anhydride were added and the atmosphere was replaced with nitrogen, the mixture was refluxed at 150 ° C. for 2 hours. Further 300
The acetic acid produced as a by-product was distilled off while the temperature was raised to 5 ° C. over 5 hours. When the temperature reached 300 ° C., the reaction was further performed for 1 hour, and then the reaction product was cooled and pulverized while solidifying to obtain a polymer. After further pulverizing the obtained polymer,
The temperature was raised from room temperature to 310 ° C. over 12 hours under a nitrogen stream, and solid phase polymerization was performed at 310 ° C. for 5 hours to obtain a liquid crystal resin.

Examples and Comparative Examples Amino group-containing polyphenylene sulfide resin, wholly aromatic polyester-based liquid crystalline resin, and commercially available epoxy compounds A and B (manufactured by Nagase Kasei)

[0049]

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[0050]

Embedded image Was blended with each composition shown in Table 1, and a set temperature of 30 was set using a vented twin-screw extruder (TEX30SS manufactured by Nippon Steel Works).
The mixture was melt-kneaded at 0 ° C. to obtain pellets of each composition. Evaluation of mechanical properties, fluidity, and appearance of the molded product was performed using a 50-ton injection molding machine (IS-50EP manufactured by Toshiba Machine Co., Ltd.) using a test piece molded at a resin temperature of 300 to 320 ° C. Each physical property was measured according to ASTM. The fluidity was evaluated using a 0.5 mm thick spiral flow mold.
Performed at 0 ° C. Table 1 shows the evaluation results.

[0051]

[Table 1]

[0052]

The composition comprising the amino group-containing polyarylene sulfide resin, the melt-moldable liquid crystalline resin, and the epoxy compound having two or more epoxy groups according to the present invention has good resin compatibility and mechanical properties. It has excellent properties and moldability, and is useful for use as an industrial material.

Claims (1)

(57) [Claims] An amino group-containing polyarylene sulfide resin of 10 to 95% by weight and a melt-moldable liquid crystalline resin of 90 to 90%.
With respect to 100 parts by weight of the resin composition consisting of 5% by weight,
A thermoplastic resin composition comprising 0.05 to 15 parts by weight of a compound having two or more epoxy groups.