JPH06172489A - Thermoplastic resin composition - Google Patents

Abstract

PURPOSE:To provide the subject composition excellent in compatibility and mechanical characteristics by compounding a carboxyl group-containing polyphenylene sulfide resin and an epoxy group-containing polyphenylene ether resin with an epoxy curing-accelerating catalyst in a specific ratio. CONSTITUTION:The objective composition comprises 100 pts.wt. of a resin comprising (A) 10-90wt.% of a carboxyl group-containing polyphenylene sulfide resin produced by modifying polyphenylene sulfide with a modifying agent selected from compounds each having a carboxyl group and a mercapto group or disulfide group in the molecule and (B) 90-10wt.% of an epoxy group- containing polyphenylene ether resin produced by reacting polyphenylene ether with a functionating agent in the presence of a basic catalyst at 50-200 deg.C, (C) 0.01-10 pts.wt. of an epoxy curing-accelerating catalyst, and further preferably (D) 2-4 pts.wt. of a thermoplastic elastomer.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION The present invention relates to an engineering plastics industrial material having excellent mechanical strength, heat resistance rigidity and appearance of a molded product, such as polyphenylene sulfide which provides a connector, an ignition manifold, a gear, a bumper, a coil sealing material and the like. The present invention relates to a contained plastic resin composition.

[0002]

2. Description of the Related Art Polyphenylene sulfide has a fluidity,
It is known as a high-melting-point heat-resistant resin having excellent organic solvent resistance, electrical characteristics, flame retardancy, and the like. However, when it is used as a molding material, it has a drawback that it has a low degree of polymerization and is inferior in extrusion molding stability and injection molding stability. Moreover, since the glass transition temperature is not so high as about 90 ° C., the rigidity of the molded product is greatly reduced at high temperatures. Therefore, performance improvement has been carried out by compounding with inorganic fillers such as glass fiber, carbon fiber, talc, silica, etc., but in this case, the appearance of the molded product is deteriorated and warpage is likely to occur in the molded product. There is a problem.

On the other hand, polyphenylene ether is recognized as an engineering plastic having excellent heat resistance, dimensional stability, non-hygroscopicity, electrical characteristics, etc., but its melt flowability is poor and molding processing is difficult, and ,
It has the drawback of poor oil resistance and impact resistance. Therefore, various compositions have been proposed for the purpose of providing a molding material that complements the drawbacks without impairing the advantages of both.

For example, a technique for improving the molding processability of polyphenylene ether by blending polyphenylene ether with polyphenylene sulfide has been disclosed (Japanese Patent Publication No. 56-34032). However, although the molding processability is improved, the polyphenylene ether and the polyphenylene sulfide are inherently poor in compatibility, and in such a simple blend system, the affinity at the interface is poor, phase separation occurs during molding, and mechanical strength is low. No excellent molded body can be obtained.

As a technique capable of improving the compatibility of the two, Japanese Patent Application Laid-Open No. 1-259060 discloses a modified polyphenylene ether (A) having a functional group introduced therein, specifically maleic anhydride and 2-hydroxyethyl acrylate. ,
An acid-modified polyphenylene ether, a hydroxyl group-modified polyphenylene ether or an epoxy group-modified polyphenylene ether obtained by melt-modifying a functional monomer such as glycidyl methacrylate and polyphenylene ether, and a polyphenylene sulfide (B) modified with a similar functional group. It is disclosed that a composition that gives a molded article having excellent mechanical strength can be obtained by the combination of

Further, JP-A-4-227636 discloses a composition of polyphenylene sulfide (A) containing an amino group, an alcoholic hydroxyl group or a carboxyl group and a polyphenylene ether (B) containing an epoxy group. There is. However, by any of these methods, the miscibility of polyphenylene ether and polyphenylene sulfide is not sufficient, and only molded products having inferior impact strength and appearance can be obtained.

[0007]

DISCLOSURE OF THE INVENTION The present invention provides a thermoplastic resin composition having extremely excellent miscibility of polyphenylene sulfide and polyphenylene ether, excellent appearance of molded articles, mechanical strength, solvent resistance, and excellent moldability. The purpose is to provide.

[0008]

The present invention provides a component (a) containing a carboxyl group obtained by modifying polyphenylene sulfide with a modifier selected from compounds having a carboxyl group and a mercapto group or a disulfide group in the molecule. Polyphenylene sulfide resin component (b) Epoxy group-containing polyphenylene ether resin component (c) Epoxy curing accelerator catalyst Component (a) 10 to 90% by weight and component (b) 90 to 1
The present invention provides a thermoplastic resin composition in which the component (c) is blended in a proportion of 0.01 to 10 parts by weight with respect to 100 parts by weight of a resin composed of 0% by weight.

The second aspect of the present invention is to provide a carboxyl group-containing polyphenylene sulfide obtained by modifying polyphenylene sulfide with a modifier selected from compounds having a carboxyl group and a mercapto group or a disulfide group in the molecule of component (a). Resin component (b) Epoxy group-containing polyphenylene ether resin Component (c) Epoxy curing acceleration catalyst Component (d) Thermoplastic elastomer The above component (a) 10 to 90% by weight and component (b) 90 to 1
The component (c) is 0.01 to 10 parts by weight and the component (d) is 2 to 4 with respect to 100 parts by weight of the resin composed of 0% by weight.
The present invention provides a thermoplastic resin composition blended in a proportion of 0 part by weight.

[0010]

In the presence of the curing-accelerating catalyst of component (c), the carboxyl group of the resin of component (a) and the epoxy group of the resin of component (b) react to give a polymer alloy having excellent compatibility. Hereinafter, the present invention will be described in more detail.

(A) Carboxyl group-containing polyphenylene
The carboxyl group-containing polyphenylene sulfide resin of the sulfide resin component (a) has a carboxyl group obtained by reacting polyphenylene sulfide with a modifier selected from compounds having a carboxyl group and a mercapto group or a disulfide group in the molecule. The modified polyphenylene sulfide resin can be produced, for example, by reacting the polyphenylene sulfide and the modifier with the polyphenylene sulfide in a molten state or in an organic solvent.

(I) Polyphenylene sulfide The raw material polyphenylene sulfide used for modification has the general formula (1)

[0013]

[Chemical 1]

A crystalline resin containing a repeating unit represented by as a main constituent element. In the present invention, those having the above repeating unit as a main constituent element, that is, a homopolymer comprising the above repeating unit, or a main constituent component thereof (80 mol% or more, more preferably 90 mol% or more)
For example, a copolymer having one or two or more repeating units such as (II) to (VIII) below in a proportion of 20 mol% or less can be used.

[0015]

[Chemical 2]

(Wherein R is an alkyl group, a phenyl group or an alkoxy group) This polyphenylene sulfide is
Those having a substantially linear structure are preferable from the viewpoint of physical properties of the molded product. As long as the physical properties are not substantially reduced, for example, a polymerized cross-linked product obtained by using an effective amount of a cross-linking agent (for example, trihalobenzene) at the time of polymerization, or a polymer obtained by heat treatment in the presence of oxygen to cross-link the heat. Crosslinked products can also be used.

This polyphenylene sulfide is 300
Melt viscosity at 100 ° C and shear rate of 10 ³ sec ^-1 is 100-
100,000 poise, preferably 500 to 50,0
00 poise, more preferably 500 to 30,000
Those in the poise range are preferred. If the melt viscosity is less than 100 poise, the fluidity is too high and molding is difficult, which is not preferable. Further, even if the melt viscosity exceeds 100,000 poise, the fluidity is too low, and molding is difficult.

This polyphenylene sulfide can be produced by any method, for example, Japanese Patent Publication No.
A method for producing a polymer having a relatively small molecular weight as disclosed in JP-A-5-3368, a method for producing a linear polymer having a relatively high molecular weight as disclosed in JP-B-52-12240, or a low method. It can be produced according to a method of heating a molecular weight polymer in the presence of oxygen to obtain a crosslinked product, or by making necessary modifications thereto.

(Ii) Carboxyl Group-Containing Polyphenylene Sulfide Resin The carboxyl group-containing polyphenylene sulfide resin obtained by reacting a functionalizing agent with polyphenylene sulfide can be produced, for example, by the following method. That is, polyphenylene sulfide, and general formula (IX) and general formula (X)

HS-R ¹ -COOR ² (IX)

R ² OOC-R ¹ -S-S-R ¹ -COOR ² (X)

(Here, R ¹ represents an aliphatic or alicyclic residue having 1 to 10 carbon atoms or an aromatic residue having 6 to 12 carbon atoms. R ² represents a hydrogen atom or 1 carbon atom. 10 represents a hydrocarbon or an alkali metal atom of 10), and is a mercapto compound or a disulfide compound represented by a modifying agent.

Specific examples of the modifier include thiomalic acid, mercaptobenzoic acid, and 5,5'-dithiobis (2-
Nitrobenzoic acid), 4,4'-dithiodi (n-butyric acid), dithiodiacetic acid, 2,2'-dithiodipropionic acid, 3,3'-dithiodipropionic acid, mercaptoacetic acid, 2-mercaptopropionic acid, Mercaptovaleric acid,
Examples include dithiodibenzoic acid, thiosalicylic acid, 3- (p-mercaptophenyl) propionic acid and their alkyl esters, and alkali metal salts. Particularly preferred are thiomalic acid, 4,4′-dithiodi (n-butyric acid), dithiodibenzoic acid and their carboxyl group derivatives.

The carboxyl group-containing polyphenylene sulfide resin is a polyphenylene sulfide and a modifying agent in an organic solvent in which the polyphenylene sulfide is soluble or partially soluble. Parts, preferably 1 to 20 parts by weight) and 170 ° C to 300
It can be easily produced by heating and reacting at ℃.

The organic solvent used here is preferably capable of dissolving polyphenylene sulfide as a raw material, but an organic solvent capable of partially swelling polyphenylene sulfide can also be used. In particular,
Aromatic solvents such as diphenyl, toluene, xylene, halogenated aromatic solvents such as chlorobenzene, dichlorobenzene, chloronaphthalene, N-methyl-2-pyrrolidone,
Examples include aprotic polar solvents such as dimethylimidazolidinone, dimethylacetamide, and sulfolane.

Further, the carboxyl group-containing polyphenylene sulfide resin of the present invention is extruded after mixing the polyphenylene sulfide with a modifier in an amount of 0.01 to 20 parts by weight, preferably 0.1 to 10 parts by weight, based on the polyphenylene sulfide. Machine, kneading machine using 150-350
It can also be produced by reacting by melting and kneading in a temperature range of ℃, preferably 280 to 340 ℃.

(B) Epoxy Group-Containing Polyphenylene A
The epoxy group-containing polyphenylene ether resin of the ter resin component (b) is a modified polyphenylene ether resin obtained by adding an epoxy group to the terminal phenolic hydroxyl group of polyphenylene ether or the main chain of polyphenylene ether by a functionalizing agent, and specifically, The polyphenylene ether and the functionalizing agent in the presence or absence of an organic solvent capable of dissolving the polyphenylene ether, with or without a basic catalyst.
It can be obtained by reacting at a temperature of 0 to 200 ° C.

(I) Polyphenylene ether The raw material polyphenylene ether has the general formula (XI)

[0029]

[Chemical 5]

(Wherein Q¹Are a halogen atom and a primary
Secondary or secondary alkyl groups, aryl groups, amino groups
Kill group, halo hydrocarbon group, hydrocarbon oxy group, or halo
Represents a hydrocarbon oxy group, Q²Are hydrogen atom and halogen
Atom, primary or secondary alkyl group, halohydrocarbon
It represents an elementary group or a halohydrocarbonoxy group. )
It is a homopolymer or a copolymer having a structure. Q¹Oh
And Q²Preferable examples of the primary alkyl group of
Chill, n-propyl, n-butyl, n-amyl, isoam
Mill, 2-methylbutyl, 2,3-dimethylbutyl, 2
-, 3- or 4-methylpentyl, or heptyl
is there. Examples of secondary alkyl groups are isopropyl, sec-
Butyl or 1-ethylpropyl. Often Q
¹Is an alkyl group or a phenyl group, especially an alkyl group having 1 to 4 carbon atoms.
It is a rukyll group, and Q²Is a hydrogen atom.

Specifically, poly (2,6-dimethyl-
1,4-phenylene) ether, poly (2,6-diethyl-1,4-phenylene) ether, poly (2,6-dipropyl-1,4-phenylene) ether, poly (2-
Methyl-6-ethyl-1,4-phenylene) ether,
Poly (2-methyl-6-propyl-1,4-phenylene) ether, poly (2-ethyl-6-propyl-1,
4-phenylene) ether, 2,6-dimethylphenol / 2,3,6-trimethylphenol copolymer, 2,
6-dimethylphenol / 2,3,6-triethylphenol copolymer, 2,6-diethylphenol / 2,
Graft polymerization of styrene to 3,6-trimethylphenol copolymer, 2,6-dipropylphenol / 2,3,6-trimethylphenol copolymer, poly (2,6-dimethyl-1,4-phenylene) ether And the graft copolymer obtained by graft-polymerizing styrene to the 2,6-dimethylphenol / 2,3,6-trimethylphenol copolymer.

Suitable homopolymers of polyphenylene ether are, for example, those having a unit structure of 2,6-dimethyl-1,4-phenylene ether. A preferred copolymer is a random copolymer of 2,6-dimethyl-1,4-phenylene ether and 2,3,6-trimethyl-1,4-phenylene ether. Many suitable homo- or random copolymers are described in the patents and literature (USP 3422062, 33).
06874, 3257358). Also suitable are polyphenylene ethers containing molecular structure moieties that improve properties such as, for example, molecular weight, melt viscosity and / or impact strength.

The molecular weight of polyphenylene ether is usually 0.2 to 0.8 dl in chloroform at 30 ° C.
/ G. Polyphenylene ether is usually produced by oxidative coupling of the above-mentioned monomers. Numerous catalyst systems are known for the oxidative coupling polymerization of polyphenylene ethers. There is no particular limitation on the selection of the catalyst, and any known catalyst can be used. For example, those containing at least one heavy metal compound such as copper, manganese, and cobalt, usually in combination with various other substances, and the like.

(Ii) Method for Producing Epoxy Group-Containing Polyphenylene Ether Resin The epoxy group-containing polyphenylene ether is produced by reacting a functionalizing agent with polyphenylene ether. For example, it can be manufactured by the methods shown in the following (A) to (C).

(A) The terminal epoxidized polyphenylene ether in which the epoxy group of the modifying agent is added to the terminal phenolic hydroxyl group of the polyphenylene ether by contacting the polyphenylene ether and the substance having the epoxy group (modifying agent) with heating. A resin can be produced (Japanese Patent Laid-Open No. 63-
No. 125525). Specifically, as long as the substance having an epoxy group is liquid at the reaction temperature and the polyphenylene ether can be made into a solution, the substance having an epoxy group can be used as a solvent / reactant. Further, when the substance having an epoxy group is solid at the reaction temperature, or when the substance having an epoxy group does not dissolve the polyphenylene ether, it is a good solvent for both the substance having an epoxy group and the polyphenylene ether,
In addition, the reaction is performed by adding a solvent that does not participate in the reaction, for example, an aromatic hydrocarbon compound such as benzene or toluene, a halogenated hydrocarbon compound such as chloroform, a halogenated aromatic hydrocarbon compound such as chlorobenzene or dichlorobenzene. Make it easy.

As the substance having an epoxy group, an epoxy compound having a halide at one end or an epoxidation at both ends is preferable. Examples of the epoxy compound having one end include epichlorohydrin, epibromohydrin, 2- Methylepichlorohydrin is preferably used as the epoxy compound at both ends thereof, glycidyl ether of 2,2-bis (4-glycidylphenyl ether) propane or bisphenol, and glycidyl ether of novolac resin.

The amount ratio between the substance having an epoxy group and the polyphenylene ether is 1 mol or more, preferably 2 to 5 mol, based on 1 mol of the terminal phenolic hydroxyl group of the polyphenylene ether. Regarding the basic compound used to accelerate the reaction,
Although the type is not particularly limited, alkali metal hydroxides such as sodium hydroxide and potassium hydroxide, and alcoholates such as sodium methoxide and sodium ethoxide are preferable. The amount added is 1.0 equivalent or more, preferably 1.2 to 3 equivalents or more, and particularly preferably 1.5 to 2 equivalents, relative to 1 equivalent of the epoxy group of the epoxy compound.

The reaction temperature is preferably about 80 to 120 ° C., and the reaction time is usually about 1 to 8 hours. After the reaction, the system is cooled and the reaction mixture is poured into a poor solvent for polyphenylene ether such as methanol to form a precipitate, and a polyphenylene ether resin having an epoxidized terminal is obtained.

After the reaction, the precipitate is filtered and then washed with water and methanol to remove unreacted epoxy compound and alkaline compound. After washing, the precipitate is filtered off and the temperature is 80 ° C to 1
After drying under reduced pressure or normal pressure at 10 ° C., terminal-epoxidized polyphenylene ether is obtained. (B) The polyphenylene ether resin having an epoxy group in the main chain is, for example, a compound represented by the general formula

[0040]

[Chemical 6]

(In the formula, R ⁶ represents a hydrogen atom or a methyl group.) An acrylate or methacrylate, specifically glycidyl methacrylate or glycidyl acrylate, is subjected to a solution or melt graft reaction with polyphenylene ether to give a compound of the general formula

[0042]

[Chemical 7]

(In the formula, R ⁶ is the same as the above formula (XII))
An epoxy group-containing polyphenylene ether resin in which the main chain of the polyphenylene ether is modified with the structural unit shown by is produced (JP-A-1-259060). (C)
Polyphenylene ethers containing epoxy groups in the main chain also have the general formula

[0044]

[Chemical 8]

(Wherein R ⁷ represents a hydrogen atom or a methyl group, Ar represents an aryl group having 6 to 10 carbon atoms and having at least one glycidyloxy group), for example, an acrylate or a methacrylate. , N-
[4- (2,3-epoxypropoxy) -3,5-dimethylphenylmethyl] acrylamide is reacted with polyphenylene ether by a solution or melt graft reaction to give a compound of the general formula

[0046]

[Chemical 9]

(In the formula, R ⁷ and Ar are the same as those in the formula (XI
Same as V). An epoxy group-containing polyphenylene ether resin in which the main chain of the polyphenylene ether is modified with the structural unit represented by the formula (1) is produced. The epoxy group-containing polyphenylene ether resin as the component (b) may be a single resin or a mixture of an epoxy group-containing polyphenylene ether resin and an unmodified polyphenylene ether. The mixing ratio of the epoxy group-containing polyphenylene ether resin and the unmodified polyphenylene ether is set by the mixing ratio of the polyphenylene sulfide. Usually, up to 80% by weight of the epoxy group-containing polyphenylene ether resin can be replaced by unmodified polyphenylene ether.

(C) Epoxy Curing Accelerating Catalyst As the epoxy curing promoting catalyst, a catalyst usually used in the curing reaction between the epoxy resin and the curing agent can be used.
Specifically, tertiary amines such as benzyldimethylamine, tributylamine, tris (dimethylamino) methylphenol, p- (dimethylamino) pyridine, triphenylamine and the like;

Quaternary ammonium compounds, eg
Tetra-n-butylammonium fluoride, tetraethylammonium fluoride, alkyl (C8
~ 18) dimethylbenzylammonium chloride, benzylcetyldimethylethylammonium chloride,
Benzyldimethylalkyl (C8-18) ammonium chloride, benzyldimethylstearylammonium chloride, benzyltri-n-butylammonium chloride, (3-chloro-2-hydroxy-n-propyl) trimethylammonium chloride, n-decyltrimethylammonium chloride , Diallyldimethylammonium chloride, dimethylbenzylphenylammonium chloride, distearyldimethylammonium chloride, dodecyltrimethylammonium chloride, n-hexadecyltrimethylammonium chloride, (2-methoxyethoxymethyl) triethylammonium chloride, n-octyltrimethylammonium chloride, phenyl Triethylammonium chloride, Lil trimethyl ammonium chloride, tetradecyl dimethyl benzyl ammonium chloride, tetra -n- amyl chloride,
Tetra-n-butylammonium chloride, n-tetradecyltrimethylammonium chloride, tetraethylammonium chloride, tetramethylammonium chloride, triethylbenzylammonium chloride, trimethylbenzylammonium chloride, trioctylmethylammonium chloride, benzyltri-n-butylammonium bromide, cetyl Dimethylammonium bromide, n-decyltrimethylammonium bromide, dilauryldimethylammonium bromide, distearyl dimethylammonium bromide, n-hexadecyltrimethylammonium bromide, n-hexyltrimethylammonium bromide, n-octyltrimethylammonium bromide,
Phenyltrimethylammonium bromide, stearyltrimethylammonium bromide, tetra-n-butylammonium bromide, tetra-n-decylammonium bromide, n-tetradecyltrimethylammonium bromide, tetraethylammonium bromide, tetramethylammonium bromide, tetra-
n-propylammonium bromide, tetraethylbenzylammonium bromide, ethyltrimethylammonium iodide, ethyltri-n-propylammonium iodide, phenyltriethylammonium iodide, phenyltrimethylammonium iodide, tetra-n-amylammonium iodide, tetra-n -Butylammonium iodide, tetraethylammonium ammonium iodide, tetra-n-octylammonium iodide, tetra-n-propylammonium iodide, triethylbenzylammonium iodide, etc .;

Phosphonium compounds such as allyltriphenylphosphonium bromide, allyltriphenylphosphonium chloride, n-amyltriphenylphosphonium bromide, benzyltriphenylphosphonium chloride, bromomethyltriphenylphosphonium bromide, 3-bromopropylyltriphenylphosphonium. Bromide, n-butyltriphenylphosphonium bromide, 4-carboxybutyltriphenylphosphonium bromide, chloromethyltriphenylphosphonium chloride, cinnamyltriphenylphosphonium bromide, 2-dimethylaminoethyltriphenylphosphonium bromide, 2- (1,3- Dioxan-2-yl) ethyltriphenylphosphonium bromide, 2- (1,3 Dioxolan-2-yl) ethyltriphenylphosphonium bromide, 4-ethoxy-benzyl triphenylphosphonium bromide, ethoxymethyl carboxylmethyl (triphenyl) phosphonium bromide, ethyl triphenyl phosphonium bromide,
(Formylmethyl) triphenylphosphonium chloride, n-heptyltriphenylphosphonium bromide, n-hexyltriphenylphosphonium bromide, (methoxymethyl) triphenylphosphonium chloride, methyltriphenylphosphonium iodide, methyltriphenylphosphonium bromide, μ-
Oxo-bis [tris (dimethylamino) phosphonium] bis (tetrafluoroborate), phenacyltriphenylphosphonium bromide, tetra-n-butylphosphonium bromide, tetraethylphosphonium bromide, tetrakis (hydroxymethyl) phosphonium sulfate, tetrakis (hydroxy) Methyl) phosphonium chloride, tetraphenylphosphonium bromide, tetraphenylphosphonium chloride, tetraphenylphosphonium iodide, tetraphenylphosphonium tetraphenylborate, 2- (trimethylsilyl) ethoxymethyltriphenylphosphonium chloride;

Pyridinium compounds such as 1-acetonylpyridinium chloride, 1- (aminoformylmethyl) pyridinium chloride, 1-pyridinium iodide, 2-bromo-1-ethylpyridinium tetrafluoroborate, 4-bromopyridine hyde Roborate, 4-bromopyridine hydrochloride, N-
n-butylpyridinium chloride, 3-carbamyl-
1-methylpyridinium chloride, 2- (chloromethyl) pyridine hydrochloride, 3- (chloromethyl) pyridine hydrochloride, 4- (chloromethyl) pyridine hydrochloride, 2-chloro-1-methylpyridinium iodide, 2-chloro -1-Methylpyridinium p-toluenesulfonate, 4-chloropyridine hydrochloride, cetylpyridinium chloride monohydrate, 1- (cyanomethyl) pyridinium chloride, N, N'-dibenzyl-4,4 '
-Bipyridinium dichloride, 1,1'-di-n-heptyl-4,4'-bipyridinium dibromide, 2,
6-dihydroxypyridine hydrochloride, 4-dimethylamino-1-neopentylpyridinium chloride, 4-dimethylaminopyridinium bromide perbromide, 1,1′-dimethyl-4,4′-dipyridinium dichloride, 2,6-dimethylpyridinium p-
Toluene sulfonate, N, N'-di-octyl-
4,4'-bipyridinium dibromide, 2,6-diphenyl-4-pyridinio) phenolate, dodecylpyridinium chloride, 1- (ethoxycarbonylmethyl) pyridinium chloride, 1-ethyl-4-methoxycarbonylpyridinium iodide, 1- Ethylpyridinium bromide, 2-fluoro-1-methylpyridinium p-toluene sulfonate, hexadecylpyridinium bromide, hexadecylpyridinium chloride, isonicotinoyl chloride hydrochloride, 1-methyl-4- [4- (4-aminonaphthyl) Azo) phenylazo] pyridinium iodide, 1-methyl-4- (4-diethylaminophenylazo) pyridinium iodide, N-methylpyridinium-2-aldoxime-chlora , 1- (4-nitrobenzyl) -4- (4-diethylaminophenylazo) pyridinium bromide, 1-octadecyl-4- (4-phenyl-1,3-butadienyl) pyridinium bromide, N- (10,12- Pentacosadinyl) pyridinium bromide, 1-phenacylpyridinium bromide, N-phenylnicotinamide hydrochloride,
Picolinic acid hydrochloride, picolinoyl chloride hydrochloride, pyridine polyfluoride hydrofluoride, pyridinium chlorochromate, pyridinium dichromate, pyridinium fluorochromate, pyridinium hydrobromide perbromide, pyridinium m-nitrobenzene sulfonate, pyridinium p-toluene Sulfonate, pyridoxamine dihydrochloride, pyridooxyhydrochloride, 2-pyridylacetic acid hydrochloride, 3-pyridylacetic acid hydrochloride, 1- (4-pyridyl) -pyridinium chloride hydrochloride, tetrakis ( 1-methylpyridinium-4-yl) porphine p-toluenesulfonate, 2 4,6-trimethyl pyridinium p
-Toluene sulfonate, etc .;

Imidazoles such as imidazole, 2-methylimidazole, 2-phenylimidazole, 2-undecylimidazole, 2-heptadecylimidazole, 1-benzyl-2-methylimidazole,
2-phenyl-4-methylimidazole, 1-cyanoethyl-2-methylimidazole, 1-cyanoethyl-2
-Phenylimidazole, 1-cyanoethyl-2-ethyl-4-methylimidazole, 1-aminoethyl-2-
Methylimidazole, 1- (cyanoethylaminoethyl) -2-methylimidazole, N- (2-methylimidazolyl-1-ethyl) -urea, 1-cyanoethyl-
2-undecylimidazole, 1-cyanoethyl-2-
Methylimidazole trimellitate, 1-cyanoethyl-2-phenylimidazole trimellitate, 1-cyanoethyl-2-ethyl-4 (5) -ethylimidazole, 1-cyanoethyl-2-ethyl-4-methylimidazole trimellitate, 1-Cyanoethyl-2-undecyl-imidazole trimellitate, 2,4-diamino-6- [2'-methylimidazolyl- (1 ')]-ethyl-S-triazine, 2,4-diamino-6- [2 ′-
Undecylimidazolyl- (1 ')]-ethyl-S-triazine, 2,4-diamino-6- [2'-ethyl-
4 ′ Methylimidazolyl- (1 ′)] ethyl-S-triazine, 1-dodecyl-2-methyl-3-benzylimidazolium chloride, N, N′-bis- (2-methylimidazolyl-1-ethyl) -urea , N, N '-[2
-Methylimidazolyl- (1) -ethyl] -adipoyldiamide, 2,4-dialkylimidazole-5-dithiocarboxylic acid, 1,3-dibenzyl-2-
Methylimidazolium chloride, 2-phenyl-4,
5-dihydroxymethylimidazole, 1-cyanoethyl-2-phenyl-4,5-di (cyanoethoxymethyl) imidazole, 1-isobutyl-2-methylimidazole, 2-ethyl-4 (5) -methylimidazole,
2-methylimidazole azine and the like;

Examples of the phosphines include triphenylphosphine, tricyclophosphine, tributylphosphine, allyldiphenylphosphine, tribenzylphosphine and tritolylphosphine.

Preferably, n-amyltriphenylphosphonium bromide, benzyltriphenylphosphonium bromide, bromomethyltriphenylphosphonium bromide, n-butyltriphenylphosphonium bromide, ethyltriphenylphosphonium bromide,
n-heptyltriphenylphosphonium bromide, n
-Hexyltriphenylphosphonium bromide, methyltriphenylphosphonium iodide, methyltriphenylphosphonium bromide, tetra-n-butylphosphonium bromide, tetraethylphosphonium bromide, tetraphenylphosphonium bromide, tetraphenylphosphonium chloride, tetraphenylphosphonium iodide, tetraphenyl Phosphonium tetraphenylborate phosphonium compounds; 1-
Acetonylpyridinium chloride, 1- (aminoformylmethyl) pyridinium chloride, Nn-butylpyridinium chloride, 3-carbamyl-1-methylpyridinium chloride, 1- (cyanomethyl) pyridinium chloride, N, N'-dibenzyl-4, 4'-
Bipyridinium dichloride, 1,1'-di-n-heptyl-4,4'-bipyridinium dibromide, 4-dimethylamino-1-neopentylpyridinium chloride, 1,1'-dimethyl-4,4'-dipyridinium dichloride , N, N'-di-octyl-4,4'-bipyridinium dibromide, 1- (ethoxycarbonylmethyl) pyridinium chloride, 1-ethyl-4-methoxycarbonylpyridinium iodide, 1-ethylpyridinium bromide, 2-fluoro -1-Methylpyridinium p-toluenesulfonate, 1-octadecyl-4- (4-phenyl-1,3-butadienyl) pyridinium bromide, 1-phenacylpyridinium bromide pyridinium compound; 2-ethyl-4 (5)
-Methylimidazole, 1-cyanoethyl-2-ethyl-4 (5) -ethylimidazole imidazoles; and triphenylphosphine and tributylphosphine phosphines.

More preferably, tetra-n-butylphosphonium bromide, tetraphenylphosphonium bromide, tetraphenylphosphonium tetraphenylborate, Nn-butylpyridinium chloride, 1
-(Cyanomethyl-1-methylpyridinium chloride, N, N'-dibenzyl-4,4'-bipyridinium dichloride, 4-dimethylamino-1-neopentylpyridinium chloride, 1-ethylpyridinium bromide, 1-phenacylpyridinium bromide, Is mentioned.

(D) Thermoplastic Elastomer The thermoplastic elastomer of the component (d) of the present invention is a polymer having an elastic modulus at room temperature of 10 ⁸ (dyn / cm ² ) or less, and examples thereof include a polyolefin-based elastomer and a diene-based elastomer. Elastomer, polystyrene elastomer, polyamide elastomer, polyester elastomer,
Polyurethane elastomer, fluorine elastomer,
Known materials such as silicone-based elastomers can be used. Preferable examples include polyolefin-based elastomers, diene-based elastomers, and polystyrene-based elastomers.

As the polyolefin-based elastomer,
For example, polyisobutylene, ethylene-propylene copolymer, ethylene-propylene-non-conjugated diene copolymer,
Ethylene-butene-1 copolymer, ethylene-propylene-butene-1 copolymer, ethylene-hexene-1 copolymer, ethylene-vinyl acetate copolymer, ethylene-acrylic acid, ethylene-methacrylic acid copolymer, Examples thereof include an ethylene-glycidyl acrylate copolymer, an ethylene-glycidyl methacrylate copolymer, an ethylene-vinyl acetate-glycidyl methacrylate copolymer, an ethylene-maleic acid copolymer, and an ethylene-maleic anhydride copolymer.

Examples of the diene elastomer include:
Examples thereof include polybutadiene and its hydride, polyisoprene and its hydride, butadiene-styrene random copolymer and its hydride. Examples of the polystyrene-based elastomer include a block copolymer of a vinyl aromatic compound and a conjugated diene compound or a hydrogenated product of this block copolymer (hereinafter, abbreviated as hydrogenated block copolymer), and specifically, A block copolymer comprising at least one vinyl aromatic compound-based polymer block and at least one conjugated diene compound-based polymer block, and this block copolymer are hydrogenated. It is a hydrogenated block copolymer obtained by hydrogenating at least 80% of an aliphatic double bond based on a conjugated diene compound in the block copolymer.

Examples of the vinyl aromatic compound constituting the block copolymer include styrene, α-methylstyrene, vinyltoluene, p-tert-butylstyrene,
One or two or more kinds can be selected from 1,1-diphenylethylene and the like, and styrene is preferable. Examples of the conjugated diene compound include butadiene, isoprene, 1,3-pentadiene, 2,3-dimethyl-1,3.
One or more selected from butadiene and the like,
Of these, butadiene, isoprene and combinations thereof are preferable. In the polymer block mainly composed of the conjugated diene compound, the microstructure in the block can be arbitrarily selected. For example, in the polybutadiene block, the 1,2-vinyl bond structure is 5 to 65%, preferably 10 to 10. It is preferably 50%.

The molecular structure of the block copolymer is linear,
It may be branched, radial, or any combination thereof. As the method for producing these block copolymers, any structural method may be used as long as it has the above-mentioned structure. For example,
A vinyl aromatic compound-conjugated diene compound block copolymer can be synthesized in an inert solvent using a lithium catalyst by the method described in JP-B-40-23798.

The hydrogenated block copolymer is obtained by hydrogenating the above vinyl aromatic compound-conjugated diene compound block copolymer. Examples of the method for producing the hydrogenated block copolymer include, for example, JP-B-42-8704 and JP-B-43-66.
It can also be obtained by the method described in Japanese Patent No. 36. In particular, a hydrogenated block copolymer synthesized using a titanium-based hydrogenation catalyst that exhibits excellent heat resistance and heat deterioration resistance of the obtained hydrogenated block copolymer is most preferable. 59-133203, JP-A-60-7.
The block copolymer having the above structure can be obtained by hydrogenation in the presence of a titanium-based hydrogenation catalyst in an inert solvent by the method described in Japanese Patent Publication No. 9005. At that time, at least 80% of the aliphatic double bond based on the conjugated diene compound of the vinyl aromatic compound-conjugated diene compound block copolymer was hydrogenated, and the polymer block mainly composed of the conjugated diene compound was morphologically modified with olefin. It is necessary to convert it into a polymerizable compound polymer. The amount of non-hydrogenated aliphatic double bonds contained in this hydrogenated block copolymer is
It can be easily known by a Fourier transform infrared spectrophotometer, a nuclear magnetic resonance apparatus, or the like.

Further, a polyolefin elastomer,
0.01 to 10 parts by weight of one or more of α, β-unsaturated carboxylic acid and its derivative or acrylamide and its derivative is added to 100 parts by weight of the diene elastomer or styrene elastomer as a radical initiator. Examples thereof include modified products reacted in the presence or absence of.

Specific examples of the α, β-unsaturated carboxylic acid and its derivative include maleic acid, maleic anhydride, fumaric acid, itaconic acid, acrylic acid, glycidyl acrylate, 2-hydroxyethyl acrylate, methacrylic acid and glycidyl methacrylate. , 2-hydroxyethyl methacrylate, crotonic acid, cis-4-cyclohexene-1,2-dicarboxylic acid, and their anhydrides, endo-cis-bicyclo [2.2.1] -5-heptene-2,
3-dicarboxylic acid, its anhydride, a maleimide compound, etc. are mentioned. Further, specific examples of acrylamide and its derivatives include acrylamide, methacrylamide, and N- [4- (2,3-epoxypropoxy).
-3,5-dimethylphenylmethyl] acrylamide,
N-methylol acrylamide etc. are mentioned.

Known radical initiators can be used as necessary in this modification, and examples thereof include dicumyl peroxide, di-tert-butyl peroxide, tert-butylcumyl peroxide, and , 5-Dimethyl-2,5-di (tert-butylperoxy) hexane, 2,5-dimethyl-2,5-di (tert-butylperoxy) hexyne-3, n-butyl-4,4-bis (Tert-Butylperoxy) parellate, 1,1-bis (tert-butylperoxy) 3,3,5-trimethylcyclohexane, tert
-Butylperoxytriphenylsilane and tert
-Butylperoxytrimethylsilane and the like can be mentioned, and one or more kinds can be suitably selected from these. In addition, as other radical initiators of organic peroxide,
-Dimethyl-2,3-diphenylbutane, 2,3-diethyl-2,3-diphenylbutane, 2,3-dimethyl-
The modification reaction may be carried out using a compound such as 2,3-di (p-methylphenyl) butane or 2,3-dimethyl-2,3-di (bromophenyl) butane.

The amount of the radical initiator used is usually 0.01 to 10 parts by weight, preferably 0.05 to 5 parts by weight, based on 100 parts by weight of the polyolefin elastomer, diene elastomer or polystyrene elastomer. The modified polyolefin-based elastomer, modified diene-based elastomer or modified styrene-based elastomer can be produced by melt-kneading modification or solution-mixing modification.

Specific examples of suitable polyolefin elastomers include, for example, ethylene-acrylic acid copolymer, ethylene-methacrylic acid copolymer, ethylene-glycidyl acrylate copolymer, ethylene-glycidyl methacrylate copolymer, As the ethylene-vinyl acetate copolymer, the ethylene-maleic anhydride copolymer, and the modified product, ethylene-propylene-5-ethylidene-2
-Norbornene copolymer, ethylene-propylene-dicyclopentadiene copolymer, ethylene-propylene copolymer, ethylene-butene-1 copolymer and the like maleic anhydride graft modified product, graft methacrylate graft modified product and N- [ 4- (2,3-epoxypropoxy) -2,5-dimethylphenylmethyl] acrylamide modified product and the like can be mentioned.

Specific examples of suitable diene elastomers include polybutadiene containing a carboxyl group or an epoxy group, hydrogenated polybutadiene and hydrogenated polyisoprene, which are modified with maleic anhydride, modified with glycidyl methacrylate, and N. -[4-
(2,3-epoxypropoxy) -2,5-dimethylphenylmethyl] acrylamide modified product and the like can be mentioned.

Specific examples of suitable polystyrene-based elastomers include styrene-butadiene block copolymers and hydrogenated block copolymers thereof, styrene-isoprene block copolymers and hydrogenated block copolymers thereof, and modified Examples of the compound include a styrene-butadiene hydrogenated block copolymer and a styrene-isoprene hydrogenated block copolymer modified with maleic anhydride, glycidyl methacrylate modified with N- [4- (2,
3-epoxypropoxy) -2,5-dimethylphenylmethyl] acrylamide modified product and the like. As the thermoplastic elastomer, not only one kind of the other thermoplastic elastomers but also two or more kinds thereof may be used in combination.

Additive Ingredients If necessary, other additive ingredients may be added to the resin composition to the extent that the properties of the resin composition of the present invention are not impaired. it can. For example,
As inorganic fillers, metal oxides (silicon oxide, titanium oxide, zinc oxide, iron oxide, magnesium oxide, alumina, etc.), silicates (kaolin, clay, mica, pentonite, silica, talc, wollastonite, montmorillonite, etc.) ), Iron hydroxide, hydrotalcite, calcium carbonate, magnesium carbonate, barium sulfate, calcium sulfate, boron nitride, silicon carbide, glass beads, glass fiber, alumina fiber, silica-alumina fiber, zirconia fiber, silicon nitride fiber, nitride Boron fiber, asbestos fiber, silicon carbide fiber, calcium silicate fiber, gypsum fiber, polyamide fiber, phenol fiber, silicon carbide whisker, potassium titanate whisker, carbon fiber,
To 100 parts by weight of the sum of the components (a), (b) and (d), 40 parts by weight or less, and 2 flame retardants are added.
0 parts by weight or less, crystallization accelerator (nucleating agent), silane coupling agent such as mercaptosilane, vinylsilane, aminosilane, and epoxysilane, antioxidant, heat stabilizer, ultraviolet absorber, hindered amine light stabilizer, coloring Agent 5
Less than or equal to parts by weight can be added. For the purpose of the degree of crosslinking of polyphenylene sulfide, up to 5 parts by weight of a metal salt of thiophosphinic acid as a crosslinking accelerator, a dialkyltin dicarboxylate as a crosslinking inhibitor, aminotriazole and the like can be added.

Composition Ratio of Constituent Components In the thermoplastic resin composition of the present invention, the composition ratio of the carboxyl group-containing polyphenylene sulfide resin of the component (a) and the epoxy group-containing polyphenylene ether resin of the component (b) is such that mechanical strength and resistance are high. From the balance of organic solvent properties,
The composition ratio of the carboxyl group-containing polyphenylene sulfide resin and the epoxy group-containing polyphenylene ether resin is in the range of 10:90 to 90:10, preferably 2 by weight.
0:80 to 80:20, more preferably 30:70
From 70 to 30. If the carboxyl group-containing polyphenylene sulfide resin is less than 10% by weight, the organic solvent resistance is poor, and if it exceeds 90% by weight, the heat resistance and rigidity are not sufficient.

The epoxy curing accelerating catalyst of the component (c) is 0.01 to 10 parts by weight, more preferably 0.1 to 100 parts by weight of the resin composition comprising the components (a) and (b).
05 to 5 parts by weight. Epoxy curing accelerator is 0.01
If it is less than 10 parts by weight, the effect of improving impact resistance cannot be expected, and if it exceeds 10 parts by weight, gas is generated during molding, and the appearance of the molded product is deteriorated. The thermoplastic elastomer of component (d) is
From 100 parts by weight of the resin composition comprising the components (a) and (b), the amount is 2 to 40 parts by weight, and more preferably 5 to 30 parts by weight, from the viewpoint of improving impact resistance and moldability.

Preparation and Molding Method of Resin Composition As a melt-kneading method for obtaining the thermoplastic resin composition of the present invention, a kneading method generally used for thermoplastic resins can be applied. For example, a powdery or granular component, if necessary, together with the additives and the like described in the section of additional components, a Henschel mixer, a ribbon blender, a V
After uniform mixing with a mold blender or the like, the mixture can be kneaded with a uniaxial or multiaxial kneading extruder, roll, Banbury mixer, or the like. The molding method of the thermoplastic resin composition of the present invention is not particularly limited, and molding methods generally used for thermoplastic resins, that is, molding methods such as injection molding, blow molding, extrusion molding, press molding, etc. Applicable.

[0073]

EXAMPLES The present invention will be described in detail below with reference to examples. High temperature GPC measurement of polyphenylene sulfide
Using Senshu Science VHT-GPC 7000,
The column temperature was 210 ° C., and the mobile phase was 1-chloronaphthalene.

The components used are as follows. Polyphenylene sulfide: Polyphenylene sulfide (trade name: Toprene P-7) manufactured by Topren Co., Ltd. was used. Polyphenylene ether: Poly (2,6-dimethyl-1,4-phenyleneethyl) manufactured by Nippon Polyether Co., Ltd.
(Intrinsic viscosity 0.4 dl / g measured in chloroform at 30 ° C.) was used. SEBS (Partially Hydrogenated Styrene-Butadiene Block Copolymer): Shell Chemical Co., Ltd. (Brand Name: Kraton G165
1) was used. EVG (ethylene-vinyl acetate-glycidyl methacrylate copolymer): Sumitomo Chemical Co., Ltd. (trade name: Bondfast BF-E) was used. M-EPR (maleic anhydride-modified ethylene-propylene copolymer): manufactured by Nippon Synthetic Rubber Co., Ltd. (trade name: T-7771)
Y) was used.

[Production Example 1] Carboxyl group-containing polyphenylene sulfide resin-1 Polyphenylene sulfide (Toprene T-7) 100
To 3 parts by weight of thiomalic acid was added and mixed uniformly, and then melt-kneaded at a temperature of 310 ° C. with a twin-screw extruder, extruded into strands, and cut to obtain pellets. Almost no increase in the melt flow value was observed. As a result of GPC measurement, almost no decrease in the molecular weight of polyphenylene sulfide before and after modification was observed.

0.5 g of the obtained carboxyl group-containing polyphenylene sulfide resin pellets was dissolved in 20 ml of 1-chloronaphthalene at 220 ° C., and after cooling, 30 ml of acetone was added to cause precipitation, and the obtained polymer was separated by filtration,
After drying, this polymer powder was compression-molded at 260 ° C. to form a press sheet having a thickness of 2 mm, which was measured by a Fourier transform infrared spectrophotometer. As a result, 1730c
The absorption attributed to the ketone of the carboxyl group was observed at m ⁻¹ .

Production Example 2 Carboxyl Group-Containing Polyphenylene Sulfide Resin-2 As a modifier, dithiodi (n- was used instead of thiomalic acid.
(Butyric acid) was used, and the same procedure as in Production Example 1 was performed. The obtained carboxyl group-containing polyphenylene sulfide resin had a Fourier transform infrared spectrophotometer of 1
Absorption attributed to the ketone of the carboxyl group was observed at 735 cm ^-1 .

Production Example 3 Carboxyl Group-Containing Polyphenylene Sulfide Resin-3 The same procedure as in Production Example 1 was carried out except that 2,2′-dithiodibenzoic acid was used instead of thiomalic acid as the modifier. The obtained carboxyl group-containing polyphenylene sulfide resin had a Fourier transform infrared spectrophotometer of 1
At 700 cm ⁻¹ , absorption attributed to the carboxyl group ketone was observed.

Production Example 4 Carboxyl Group-Containing Polyphenylene Sulfide Resin-4 The procedure of Production Example 1 was repeated except that methacrylic acid was used instead of thiomalic acid as the modifier. In the obtained carboxyl group-containing polyphenylene sulfide resin, absorption attributed to the ketone of the carboxyl group was observed at 1740 cm ⁻¹ in a Fourier transform infrared spectrophotometer.

Production Example 5 Epoxy Group-Containing Polyphenylene Ether Resin-1 To 350 g of polyphenylene ether, 5 liters of epichlorohydrin was added and dissolved under nitrogen atmosphere by stirring at 100 ° C. Sodium ethoxide 70 in this solution
g and 300 ml of methanol were added over 20 minutes. Furthermore, stirring was continued at 100 ° C. for 4 hours.

After cooling the reaction mixture to room temperature, 10 liters of methanol was added thereto to precipitate the terminal epoxidized polyphenylene ether resin. The product is filtered, washed with 10 liters of methanol, and further purified water 1
It was washed twice with 0 liter and again with 10 liter of methanol. When the obtained epoxidized polyphenylene ether resin was dried by heating under reduced pressure at 80 ° C., 351 g
Of solid was obtained.

When the terminal group of this product was quantified, it was found to be 9% of the terminal phenolic hydroxyl group of the raw material polyphenylene ether.
It turned out that 9% had reacted. The reaction rate of the terminal phenolic hydroxyl group of polyphenylene ether is as shown in Journal of Applied Polymer Science:
Applied Polymer Symposium (Junal
of Applied Polymer Science
e: Applied Polymer Symposi
Um), 34, (1987), pages 103 to 117, and the terminal phenolic hydroxyl groups before and after the reaction were quantified and calculated.

Production Example 6 Epoxy Group-Containing Polyphenylene Ether Resin-2 3 parts by weight of glycidyl methacrylate was added to 100 parts by weight of polyphenylene ether and uniformly mixed, and then melt-kneaded at a temperature of 260 ° C. with a twin-screw extruder. Extruded into strands and cut to obtain pellets. The pellet of the epoxy group-containing polyphenylene ether resin showed absorption attributed to a carbonyl group near 1720 cm ^{−1 in} its infrared absorption spectrum.

[Production Example 7] Epoxy group-containing polyphenylene ether resin-3 100 parts by weight of polyphenylene ether was added with N- [4-
After adding 3 parts by weight of (2,3-epoxypropoxy) -3,5-dimethylphenylmethyl] acrylamide and uniformly mixing, the mixture was melt-kneaded at a temperature of 260 ° C. in a twin-screw extruder and extruded into a strand. The pellet was obtained by cutting. The pellet of the epoxy group-containing polyphenylene ether resin has an infrared absorption spectrum of 16
Absorption attributed to a carbonyl group was exhibited near 85 cm ^-1 .

[Production Example 8] Polyphenylene ether resin containing epoxy group-4 400 g of polyphenylene ether was dissolved in 2.5 liter of toluene, 19 ml of 10% sodium hydroxide aqueous solution was added to this solution, and then, in a small amount of methylene chloride. 20 g of 2-chloro-4- (2,4,6-trimethylphenoxy) -6-glycidoxy-1,3,5-triazine dissolved in and commercially available with 8 to 10 carbon atoms in the alkyl group 48 g of a 10% solution of available methyltrialkylammonium chloride in toluene was added.

The mixture was vigorously stirred for 30 minutes, after which the product was precipitated with methanol, quickly filtered, washed with methanol and dried under vacuum. This product was found by nuclear magnetic resonance to contain about 1.5 wt% epoxytriazine molecular moieties.

<Example 1> 70 parts by weight of carboxyl group-containing polyphenylene sulfide resin-1, 30 parts by weight of epoxy group-containing polyphenylene ether resin-1, SE
After dry blending 9 parts by weight of BSΔ and 0.5 parts by weight of tetra-n-butylphosphonium bromide, the mixture was kneaded for 5 minutes at a temperature of 310 ° C. and a rotor rotation speed of 180 rpm using a Labo Plastomill manufactured by Toyo Seiki Co., Ltd. After the kneading was completed, it was crushed by a crusher into particles. Using a compression molding machine manufactured by Toyo Seiki Co., Ltd., the granular sample was molded into a sheet having a thickness of 2 mm at a temperature of 310 ° C. This sheet was heated in a hot air drier at 120 ° C. for 4 hours to sufficiently crystallize the polyphenylene sulfide resin. A test piece for physical property evaluation was cut from this sheet.

When kneading and molding, polyphenylene sulfide was used which had been previously vacuum dried at 100 ° C. for 24 hours. Also, the test piece for physical property evaluation is for 2 days,
Evaluation was carried out after storage in a desiccator. The rigidity is JIS-
A bending stiffness test was performed at 23 ° C. according to K-7106. The impact strength was measured with an Izod impact tester by stacking three 2 mm-thick test pieces in accordance with JIS-K-7110. For the dispersed form, cut out a part of the sheet,
Using a scanning electron microscope S-2400 manufactured by Hitachi, Ltd., observation was performed at a magnification of 1000 times and 5000 times. From the observed morphological photograph, SPICC manufactured by Nippon Avionics Co., Ltd.
The number average dispersed particle diameter Dn was determined by the following equation using an AII type image analyzer.

Dn = Σnidi / Σni: Good appearance was evaluated as ◯, worse than this but not practically problematic, and sparse surface practically problematic. The results are shown in Table 1.

<Examples 2 to 21> Dry blending was carried out in the formulations shown in Tables 1 to 3 and the same procedure as in Example 1 was carried out. The results are shown in Tables 1 to 3.

<Comparative Examples 1 to 10> Dry blending was carried out according to the formulations shown in Tables 1 to 3 and the same procedure as in Example 1 was carried out. The results are shown in Tables 1-5.

[0092]

[Table 1]

[0093]

[Table 2]

[0094]

[Table 3]

[0095]

[Table 4]

[0096]

[Table 5]

[0097]

The compatibility of polyphenylene sulfide and polyphenylene ether can be made extremely good by using a carboxyl group-containing polyphenylene sulfide resin, an epoxy group-containing polyphenylene ether resin, and an epoxy effect promoting catalyst. And the impact strength was remarkably improved.

Claims (2)

[Claims] 1. A component (a), a carboxyl group in the molecule,
Carboxyl group-containing polyphenylene sulfide resin component (b) obtained by modifying polyphenylene sulfide with a modifier selected from compounds having a mercapto group or disulfide group Component (b) Epoxy group-containing polyphenylene ether resin component (c) Epoxy curing accelerating catalyst Above component ( a) 10 to 90% by weight and component (b) 90 to 1
A thermoplastic resin composition in which the component (c) is blended in a proportion of 0.01 to 10 parts by weight with respect to 100 parts by weight of a resin composed of 0% by weight. 2. A component (a), a carboxyl group in the molecule,
Carboxyl group-containing polyphenylene sulfide resin component (b) obtained by modifying polyphenylene sulfide with a modifier selected from compounds having a mercapto group or disulfide group Component (c) Epoxy group-containing polyphenylene ether resin component (c) Epoxy curing accelerator component (d) ) Thermoplastic elastomer 10 to 90% by weight of the above component (a) and 90 to 1 of the component (b)
The component (c) is 0.01 to 10 parts by weight and the component (d) is 2 to 4 with respect to 100 parts by weight of the resin composed of 0% by weight.
A thermoplastic resin composition blended in a proportion of 0 parts by weight.