JPH0733973A - Thermoplastic resin composition - Google Patents

Abstract

PURPOSE:To obtain the title composition which gives a molding excellent in mechanical strength, high-temp. rigidity, solvent resistance, and appearance by blending a specific poly(phenylene ether) and a specific poly(phenylene sulfide) in a given proportion. CONSTITUTION:The composition comprises 10-90wt.% functional poly(phenylene ether) obtained by reacting 100 pts.wt. poly(phenylene ether) represented by formula I wherein Q<1> is a halogen, a primary or secondary alkyl, an aryl, an aminoalkyl, a halohydrocarbon, or a (halo)hydrocarbonoxy; Q<2> is H, a halogen, a primary or secondary alkyl, or a halohydrocarbon(oxy); and m is 20-450 with 0.1-10 pts.wt. alkylene carbonate represented by formula II wherein R<1> is a (hydroxyalkylated) 1-8C aliphatic group and 90-10wt.% carboxylated poly(phenylene sulfide) obtained by modifying poly(phenylene sulfide) with a modifier selected from compounds each having both a COOH group and an SH or disulfide group in the molecule.

Description

Detailed Description of the Invention

[0001]

The present invention relates to a functionalized polyphenylene ether having a hydroxyalkyl group as a functional group,
The present invention relates to a thermoplastic resin composition containing a carboxyl group-containing polyphenylene sulfide. This composition is useful as a material for engineering plastics industrial materials excellent in mechanical strength, heat resistance rigidity and appearance of molded articles, such as connectors, ignition manifolds, gears, bumpers, coil sealing materials and the like.

[0002]

2. Description of the Related Art Polyphenylene ether is a very useful thermoplastic resin having excellent heat resistance, mechanical properties, electrical properties, water resistance, acid resistance, alkali resistance, and self-extinguishing properties, and is an engineering plastic material. , Many applications are being developed. However, since this resin has a high glass transition temperature, it has a high melt viscosity, is poor in moldability, and has poor impact resistance as an engineering plastic.

Polyphenylene sulfide is a heat-resistant crystalline resin having a high melting point, which is excellent in fluidity, resistance to organic solvents, electrical characteristics, flame retardancy and the like. However, when it is used as a molding material for a sliding member, an optical disk carriage, etc., it has a drawback that the polymerization degree is low and the extrusion molding stability and the injection molding stability are poor. Further, since the glass transition temperature is not so high as about 90 ° C., the rigidity of the molded product is greatly reduced when it is used at high temperature. Therefore, the rigidity is improved by compounding with an inorganic filler such as glass fiber, carbon fiber, talc, and silk (USP 4,737,539, USP 4,000).
However, in this case, there are problems that the appearance of the molded product is deteriorated and warpage is likely to occur in the molded product.

Therefore, various compositions have been proposed for the purpose of providing a molding material which complements the drawbacks without impairing the advantages of both. For example, a technique for improving the moldability of polyphenylene ether by blending polyphenylene ether with polyphenylene sulfide has been disclosed (Japanese Patent Publication No. 56-34032). This one is
Although molding processability is improved, polyphenylene ether and polyphenylene sulfide originally have poor compatibility.In such a simple blend system, the affinity at the interface is poor and phase separation occurs during molding, resulting in excellent mechanical strength. No molded body can be obtained.

Therefore, some techniques have been proposed which can improve the compatibility of the two. For example, JP-A-1-259
JP-A No. 060 gazette discloses a modified polyphenylene ether (a) having a functional group introduced therein, specifically maleic anhydride, 2-hydroxyethyl acrylate, glycidyl methacrylate and the like, and an acid-modified polyphenylene ether obtained by melt modification of polyphenylene ether, It is disclosed that a composition having excellent mechanical strength can be obtained by combining a hydroxyl group-modified polyphenylene ether or an epoxy group-modified polyphenylene ether and a polyphenylene sulfide (b) modified with the same functional group.

Further, Japanese Patent Laid-Open No. 3-79661 discloses that
By adding a coupling agent to a blend of polyphenylene ether and polyphenylene sulfide,
Attempts have been made to improve mechanical strength. Further, JP-A-3-54251 attempts to improve mechanical strength in the same manner by blending a blending agent of polyphenylene ether and polyphenylene sulfide with a coupling agent and maleic anhydride. 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 molded product appearance can be obtained.

[0007]

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

[0008]

According to the present invention, the following component (a) is 10 to 90% by weight and component (b) is 90 to 1% by weight.
The present invention provides a thermoplastic resin composition containing 0% by weight. Component (a): general formula (I)

[0009]

[Chemical 3]

(Wherein Q ¹ represents a halogen atom, a primary or secondary alkyl group, an aryl group, an aminoalkyl group, a halohydrocarbon group, a hydrocarbonoxy group or a halohydrocarbonoxy group, and Q 1 ² represents a hydrogen atom, a halogen atom, a primary or secondary alkyl group, a halohydrocarbon group or a halohydrocarbonoxy group, and m is an integer representing the degree of polymerization and is 20 to 450). For 100 parts by weight of the indicated polyphenylene ether, the general formula (II)

[0011]

[Chemical 4]

[0012] (In the formula, R ¹ has a carbon number represents .R ¹ may include a hydroxyalkyl group. 1-8 aliphatic group) 0.1 alkylene carbonate represented by
A functionalized polyphenylene ether containing a hydroxyalkyl group obtained as a part of a substituent obtained by reacting at a ratio of 10 parts by weight.

Component (b): a carboxyl group in the molecule,
A carboxyl group-containing polyphenylene sulfide obtained by modifying polyphenylene sulfide with a modifier selected from compounds having both a mercapto group and a disulfide group.

[0014]

DETAILED DESCRIPTION OF THE INVENTION The present invention will be specifically described below. (A) Hydroxyalkyl group-containing polyphenylene ether
Le hydroxyalkyl group containing polyphenylene ether of component (a), with respect to the polyphenylene ether 100 parts by weight, the alkylene carbonate in proportions of 0.1 to 10 parts by weight, obtained this by melt modification, polyphenylene ether and It is a functionalized polyphenylene ether containing as a substituent a hydroxyalkyl group consisting of the reaction product of alkylene carbonate. (Polyphenylene ether) The polyphenylene ether used in the reaction with the modifier has the general formula (I)

[0015]

[Chemical 5]

(Wherein Q ¹ represents a halogen atom, a primary or secondary alkyl group, an aryl group, an aminoalkyl group, a halohydrocarbon group, a hydrocarbonoxy group or a halohydrocarbonoxy group, and Q 1 ² represents a hydrogen atom, a halogen atom, a primary or secondary alkyl group, a halohydrocarbon group or a halohydrocarbonoxy group, and m is an integer representing the degree of polymerization and is 20 to 450). It is a homopolymer or a copolymer having the structure shown.

Preferred examples of the primary alkyl group for Q ¹ and Q ² include methyl, ethyl, n-propyl, n-butyl,
n-amyl, isoamyl, 2-methylbutyl, 2,3-
Dimethylbutyl, 2-, 3- or 4-methylpentyl or heptyl. Examples of secondary alkyl groups are isopropyl, sec-butyl or 1-ethylpropyl. In many cases, Q ¹ is an alkyl group or a phenyl group, especially an alkyl group having 1 to 4 carbon atoms, and Q ² is 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 / 2,3,
Grafting of 6-trimethylphenol copolymer, 2,6-dipropylphenol / 2,3,6-trimethylphenol copolymer, poly (2,6-dimethyl-1,4-phenylene ether) with styrene Examples thereof include a copolymer and a graft copolymer obtained by graft-polymerizing styrene to a 2,6-dimethylphenol / 2,3,6-trimethylphenol copolymer.

Suitable polyphenylene ether homopolymers include, for example, poly (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. The molecular weight of polyphenylene ether is usually such that the intrinsic viscosity at 30 ° C. in chloroform is about 0.2 to 0.8 dl / 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.

(Alkylene Carbonate) The alkylene carbonate which introduces a hydroxyalkyl group into polyphenylene ether is a carbonic acid ester of 1,2-alkanediol and is represented by the following general formula (II).

[0022]

[Chemical 6]

[0023] (In the formula, R ^1, .R ¹ to carbon atoms represent a 1-8 aliphatic group may contain a hydroxyalkyl group.) And preferred examples of the alkylene carbonate, ethylene carbonate, Examples include propylene carbonate. (Production of Hydroxyalkyl Group-Containing Polyphenylene Ether) A functionalized polyphenylene ether containing a hydroxyalkyl group as a part of a substituent has a polyphenylene ether and an alkylene carbonate at 200 to 350 ° C. in the presence or absence of a radical initiator. 20 at temperature
It can be easily produced by melt-kneading for a time of from seconds to 30 minutes, preferably from 40 seconds to 5 minutes.

As a melt-kneading method for obtaining the hydroxyalkyl group-containing polyphenylene ether of the present invention, a kneading method generally used for thermoplastic resins can be applied. For example, powdery, granular, or liquid components are uniformly mixed with a radical initiator, if necessary, by a Henschel mixer, ribbon blender, V-type blender, etc., and then uniaxial or multiaxial kneading extruder, roll, Banbury. It can be kneaded with a mixer or the like.

The mixing ratio of the polyphenylene ether and the modifier alkylene carbonate is 0.1 to 10 parts by weight, preferably 1 to 5 parts by weight, relative to 100 parts by weight of the polyphenylene ether. In addition, examples of the radical initiator used as necessary during this modification include dicumyl peroxide, di-tert-butyl peroxide, tert-butyl cumyl peroxide, and 2,5-dimethyl-2,5-. Di (tert-butylperoxy) hexane, 2,5-dimethyl-2,5-
Di (tert-butylperoxy) hexyne-3, n-
Butyl-4,4-bis (tert-butylperoxy)
Valerate, 1,1-bis (tert-butylperoxy) 3,3,5-trimethylcyclohexane, tert
-Butylperoxytriphenylsilane and tert
-Organic peroxides such as butylperoxytrimethylsilane, 2,3-dimethyl-2,3-diphenylbutane,
2,3-diethyl-2,3-diphenylbutane, 2,3
-Dimethyl-2,3-di (p-methylphenyl) butane, 2,3-dimethyl-2,3-di (bromophenyl)
A compound such as butane can be used. These may be used alone or in combination of two or more.

The amount of the radical initiator used is usually 0.01 to 1 with respect to 100 parts by weight of polyphenylene ether.
It is 0 part by weight, preferably 0.05 to 5 parts by weight. Further, if necessary, a catalyst that promotes functionalization, for example, a basic compound (sodium hydroxide, an alkali metal hydroxide such as potassium hydroxide, sodium carbonate, an alkali metal carbonate such as potassium carbonate, sodium methoxide, Alkali metal alcoholates such as sodium ethoxide) may be added in less than 5 parts by weight to 100 parts by weight of polyphenylene ether.

This hydroxylalkyl group-containing polyphenylene ether is, for example, an alcoholic hydroxyl group-containing polyphenylene ether represented by the following general formula (III),

[0028]

[Chemical 7]

(Wherein Q ¹ , Q ² , R ¹ and m are the same as those in the above formula (I).) A functionalized polyphenylene ether having the following structural units (IV), (V) and (VI). .

[0030]

[Chemical 8]

[0031]

[Chemical 9]

[0032]

[Chemical 10]

(In the formula, R ¹ is the same as the above formula (I).) The amount of the modifier added in the hydroxyalkyl group-containing polyphenylene ether is 0.05 to 8% by weight, preferably 0.5 to 5% by weight. %.

(B) Polyphenylene sulfide containing carboxyl group The functionalized polyphenylene sulfide of the component (b) is obtained by modifying polyphenylene sulfide with a modifier selected from compounds having both a carboxyl group and a mercapto group or a disulfide group in the molecule. It is the obtained carboxyl group-containing polyphenylene sulfide. The polyphenylene sulfide used to react with the (polyphenylene sulfide) modifier has the general formula (VII)

[0035]

[Chemical 11]

It is a crystalline resin containing a repeating unit represented by as a main constituent element. In the present invention, those comprising the above-mentioned repeating unit or those containing the same as the main component, preferably 80 mol% or more, more preferably 90 mol% or more, are preferable from the viewpoint of physical properties such as heat resistance.

When substantially all the constituents of the polyphenylene sulfide do not consist of the above-mentioned repeating unit, the rest (20 mol% or less) is copolymerizable,
For example, it can be satisfied with a component consisting of the following repeating units.

[0038]

[Chemical 12]

(In the formula, Y represents an alkyl group, a phenyl group, or an alkoxy group.) The polyphenylene sulfide preferably has a substantially linear structure from the viewpoint of the 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 a cross-linking agent (for example, trihalobenzene) in a polymerization effective amount, or polyphenylene sulfide is heat-treated in the presence of oxygen to cross-link it. A thermally crosslinked product can also be used.

The polyphenylene sulfide has a melt viscosity at 300 ° C. of 100 to 100,000 poises, preferably 500 to 50,000 poises, and more preferably
It is preferably in the range of 500 to 20,000 poise.
If the melt viscosity is less than 100 poise, the fluidity is too high and molding becomes difficult. Even if the melt viscosity exceeds 100,000 poise, the fluidity is too low, and molding becomes difficult.

The polyphenylene sulfide is, for example, a method for producing a polymer having a relatively small molecular weight as disclosed in Japanese Patent Publication No. 45-3368, and a linear relatively high polymer as disclosed in Japanese Patent Publication No. 52-12240. It can be produced according to a method for producing a polymer having a molecular weight or a method for heating a low molecular weight polymer in the presence of oxygen to obtain a crosslinked product, or by making necessary modifications thereto.

(Modifier) A modifier having a carboxyl group and a mercapto group or a disulfide group in the molecule is
For example, it is represented by the following formula (VIII) or (IX).

[0043]

[Chemical 13]

[0044]

[Chemical 14]

(Here, R ² represents an aliphatic or alicyclic residue having 1 to 10 carbon atoms or an aromatic residue having 6 to 12 carbon atoms. R ³ represents a hydrogen atom or 1 to 10 carbon atoms. 10 hydrocarbons or alkali metal atoms are shown.) Specific examples of the modifier include thiomalic acid, mercaptobenzoic acid, 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, dithiodibenzoic acid,
Thiosalicylic acid, 3- (p-mercaptophenyl) propionic acid and their alkyl esters, alkali metal salts and the like. Particularly preferably, thiomalic acid and 4,4 '
-Dithiodi (n-butyric acid), dithiodibenzoic acid and their carboxyl group derivatives. (Production of polyphenylene sulfide containing carboxyl group)

The carboxyl group-containing polyphenylene sulfide as the component (b) is prepared by dissolving the polyphenylene sulfide and the modifier in an organic solvent in which the polyphenylene sulfide can be partially or partially dissolved, and the polyphenylene sulfide and the modifier (0.1% relative to the polyphenylene sulfide). ~ 100
Parts by weight, preferably 1 to 20 parts by weight) 170 ° C to 30
It can be easily produced by heating and reacting at 0 ° C (Japanese Patent Application No. 3-342586).

The organic solvent used here is preferably capable of dissolving the starting material polyphenylene sulfide, but an organic solvent capable of partially swelling the polyphenylene sulfide can also be used. Specifically, aromatic solvents such as diphenyl, toluene and xylene, halogenated aromatic solvents such as chlorobenzene, dichlorobenzene and chloronaphthalene, N-methyl-2-pyrrolidone, dimethylimidazolidinone, dimethylacetamide, sulfolane and the like. An aprotic polar solvent may be mentioned.

Further, the carboxyl group-containing polyphenylene sulfide can also be produced by the following melting reaction. For example, the carboxyl group-containing polyphenylene sulfide is added to 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, and then mixed with an extruder or kneader at 150 to 150 parts by weight. It is manufactured by melt-kneading in a temperature range of 350 ° C., preferably in a temperature range of 280 ° C. to 340 ° C.

Composition In the thermoplastic resin composition of the present invention, the composition ratio of the component (a) hydroxyalkyl group-containing polyphenylene ether to the component (b) carboxyl group-containing polyphenylene sulfide is such that mechanical strength and resistance to organic solvents are high. From the balance, the composition ratio of the polyphenylene ether as the component (a) and the polyphenylene sulfide as the component (b) is 10 by weight.
The range is 90 to 90:10, preferably 20 to 80 to 80:20, more preferably 30 to 70 to 70:30. If the amount of polyphenylene sulfide is less than 10% by weight, the organic solvent resistance is poor, which is not preferable, and if it exceeds 90% by weight, the heat resistance and rigidity are not sufficient. From the viewpoint of rigidity, it is preferable to use the polyphenylene sulfide as the component (b) in an amount of 50% by weight or more.

Even if less than 70% by weight of the functionalized polyphenylene ether of the component (a) is replaced with the unmodified polyphenylene ether and less than 70% by weight of the carboxyl group-containing polyphenylene sulfide of the component (b) is replaced with the unmodified polyphenylene sulfide. Good.

Additional Components Other optional components may be added to the resin composition according to the present invention, if necessary, to the extent that the properties of the resin composition of the present invention are not impaired. be able to. For example, the impact modifier thermoplastic elastomer may be
-40 parts by weight; as an inorganic filler, metal oxides (silicon oxide, titanium oxide, zinc oxide, iron oxide, magnesium oxide, alumina, etc.), silicates (kaolin, clay, mica, pentonite, silica, talc, Wallastonite,
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 , Boron nitride fiber, asbestos fiber, silicon carbide fiber, calcium silicate fiber, gypsum fiber, polyamide fiber, phenol fiber, silicon carbide whisker, potassium titanate whisker,
5 to 40 parts by weight of carbon fiber, 2 to 20 parts by weight of various flame retardants, crystallization accelerator (nucleating agent), silane coupling agent such as mercaptosilane, vinylsilane, aminosilane and epoxysilane, and antioxidant , Heat stabilizer,
An ultraviolet absorber, a hindered amine light stabilizer, and a colorant may be added in an amount of 0.1 to 5 parts by weight. For the purpose of controlling the degree of crosslinking of polyphenylene sulfide, 0.1 to 5 parts by weight of a metal salt of thiophosphinic acid as a crosslinking accelerator and 0.1 to 5 parts by weight of a dialkyltin dicarboxylate or aminotriazole as a crosslinking inhibitor can be added.

Further, in the thermoplastic resin composition of the present invention, in order to accelerate the reaction of each component, tri-n-butylamine, triethylamine, triphenylamine, benzyldimethylamine, tris (dimethylamino) methylphenol, 4 Tertiary amines such as-(N, N-dimethyl) pyridine, quaternary ammonium salts such as triethylbenzylammonium chloride, tetramethylammonium chloride, trioctylmethylammonium chloride, quaternary ammonium salts such as tetrabutylphosphonium bromide and tetraphenylphosphonium bromide Imidazole compounds such as phosphonium salts, 2-ethyl-4-methylimidazole, 2-methylimidazole, 1-cyanoethyl-2-methylimidazole, metal acetates such as zinc acetate and cesium acetate, antitrioxide Transesterification accelerators such as benzene and tetraoctyl titanate, sodium hydroxide, potassium hydroxide, sodium carbonate, potassium carbonate, sodium methoxide, sodium ethoxide, sodium-n-butoxide, potassium-t-butoxide, pyridine and other bases. Sex compounds can be added.

The catalyst for accelerating the above reaction is the component (a).
Less than 10 parts by weight, more preferably less than 5 parts by weight, can be added to 100 parts by weight of the sum of the resin components consisting of (b) and (b). If the amount of the catalyst that accelerates the reaction is 10 parts by weight or more, gas may be generated during molding, which may deteriorate the appearance of the molded product and may deteriorate the physical properties. The thermoplastic elastomer improves the impact resistance of the resins (a) and (b), and has a three-point bending elastic modulus of 1000 kg / cm ² or less measured according to JIS K 7203 and a glass transition point. It is a polymer having a temperature of -10 ° C or lower.
For example, known elastomers such as polyolefin-based elastomers, diene-based elastomers, polystyrene-based elastomers, polyamide-based elastomers, polyester-based elastomers, polyurethane-based elastomers, fluorine-based elastomers and silicone-based elastomers can be mentioned, but preferably polyolefin-based elastomers and polystyrenes. Examples include 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. 50%. The molecular structure of the block copolymer may be linear, branched, radial, or any combination thereof.

As a method for producing these block copolymers, for example, a vinyl aromatic compound-conjugated diene compound block copolymer in an inert solvent using a lithium catalyst can be prepared by the method described in JP-B-40-23798. Polymers can be synthesized. Further, the hydrogenated block copolymer is obtained by hydrogenating the above vinyl aromatic compound-conjugated diene compound block copolymer, as a method for producing this hydrogenated block copolymer, For example, it can be obtained by the method described in JP-B-42-8704 and JP-B-43-6636. 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. According to the method described in JP-A-59-133203 and JP-A-60-79005, the block copolymer having the above structure is hydrogenated in the presence of a titanium-based hydrogenation catalyst in an inert solvent. Obtainable. 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 can be easily known by a Fourier transform infrared spectrophotometer, nuclear magnetic resonance apparatus or the like. Further, based on 100 parts by weight of the polyolefin-based elastomer, diene-based elastomer or styrene-based elastomer, one or more of α, β-unsaturated carboxylic acid and its derivative or acrylamide and its derivative are 0.01-10 parts by weight. A modified product obtained by reacting a part in the presence or absence of a radical initiator may also be used. 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, glycidyl methacrylate, 2-hydroxyethyl methacrylate, crotonic acid, cis-4-cyclohexene-1,2-dicarboxylic acid, and anhydrides thereof. , Endo-cis-bicyclo [2.2.1] -5-heptene-
2,3-dicarboxylic acid, its anhydride, a maleinimide compound, etc. are mentioned. Specific examples of acrylamide and its derivatives include acrylamide, methacrylamide, N- [4- (2,3-epoxypropoxy) -3,5-dimethylphenylmethyl] acrylamide, N-methylolacrylamide and the like.

Further, the radical initiator used as necessary in this modification is not particularly limited as long as it is known, and for example, dicumyl peroxide,
Di-tert-butyl peroxide, tert-butyl cumyl peroxide, 2,5-dimethyl-2,5-di (tert-butylperoxy) hexane, 2,5-dimethyl-2,5-di (tert- Butylperoxy) hexyne-3, n-butyl-4,4-bis (tert-butylperoxy) valerate, 1,1-bis (tert)
-Butylperoxy) 3,3,5-trimethylcyclohexane, tert-butylperoxytriphenylsilane, tert-butylperoxytrimethylsilane, and the like, and one or more kinds can be suitably selected from these. Further, as other radical initiators of organic peroxides, 2,3-dimethyl-2,3-diphenylbutane, 2,3-diethyl-2,3-diphenylbutane,
2,3-dimethyl-2,3-di (p-methylphenyl)
The modification reaction may be carried out using a compound such as 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, Ethylene-vinyl acetate copolymer, ethylene-maleic anhydride, and modified products of ethylene-propylene-5-ethylidene-2-norbornene copolymer, ethylene-propylene-dicyclopentadiene copolymer, ethylene-propylene copolymer And ethylene-butene-1 copolymer modified with maleic anhydride, modified with glycidyl methacrylate and N- [4- (2,3-epoxypropoxy) -2,
5-dimethylphenylmethyl] acrylamide modified products 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, modified with glycidyl methacrylate and 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.

Preparation of Thermoplastic Resin Composition As the 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, powdery, granular or liquid components are uniformly mixed with the additives described in the section of additional components, if necessary, with a Henschel mixer, ribbon blender, V-type blender, etc., and then uniaxially or It can be kneaded with a multi-screw kneading extruder, roll, Banbury mixer or the like. The temperature of melt-kneading is 150 to 3
70 degreeC, Preferably it is 250-350 degreeC. 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, injection molding, blow molding, extrusion molding, sheet molding, thermoforming, compression. A molding method such as molding can be applied.

[0065]

EXAMPLES The present invention will be described in detail below with reference to examples. The components used are as follows. Polyphenylene sulfide: Polyphenylene sulfide manufactured by Topren Co., Ltd. (trade name: Topren T-7) was used. (Indicated by PPS in the table.) Polyphenylene ether: Poly (2,6-dimethyl-1,4-phenylene ether) manufactured by Nippon Polyether Co., Ltd. was used. [Intrinsic viscosity measured in chloroform at 30 ° C. is 0.4 dl / g, polystyrene-equivalent molecular weight: Mn 15,200, Mw 45,800. In the table, indicated by PPE. ] Hydrogenated styrene-butadiene-styrene block copolymer: Kraton G1651 (trade name) of Shell Chemistry was used. (Indicated by SEBS in the table.) Confirmation of the hydroxyalkyl group substituted on the polyphenylene ether was carried out according to the following.

0.5 g of the melt-modified functionalized polyphenylene ether was dissolved in 25 ml of chloroform, and the filtrate obtained by filtering the insoluble matter was poured into 150 ml of methanol to reprecipitate the functionalized polyphenylene ether. After filtering and drying this functionalized polyphenylene ether, 2.0% by weight
The carbon disulfide solution was prepared and the infrared absorption spectrum was measured using a quartz cell having an optical path length of 10 mm.

Production Example 1 Carboxyl group-containing polyphenylene sulfide (functionalized PPS-1) Polyphenylene sulfide (Toprene T-7) 100
After 3 parts by weight of thiomalic acid was added to 1 part by weight and uniformly mixed, the mixture was melt-kneaded at a temperature of 310 ° C. by a twin-screw extruder, extruded in a strand form from a die, 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 was added to 20 m of 1-chloronaphthalene.
It was dissolved in 1 l at 220 ° C., and after cooling, 30 ml of acetone was added to cause precipitation, and the obtained polymer was separated by filtration and dried, and then a press sheet was prepared, and FT-IR was measured. As a result, absorption attributed to the ketone of the carboxyl group was observed at 1730 cm ^-1 . By comparing the peak of polyphenylene sulfide at 1910 cm ^-1 with the calibration curve of FT-IR prepared by the peak ratio in advance, the binding amount of the modifier to the polyphenylene sulfide was found to be about 2% by weight. Admitted.

Production Example 2 Functionalized polyphenylene ether (functionalized PPE-1) After 100 parts by weight of polyphenylene ether and 3 parts by weight of ethylene carbonate were dry blended, a Labo Plastomill manufactured by Toyo Seiki Co., Ltd. was used and the temperature was 270 ° C. The rotor was rotated at 180 rpm and kneaded in a nitrogen atmosphere for 5 minutes. After the kneading was completed, it was crushed by a crusher into particles.

From the infrared absorption spectrum of the functionalized polyphenylene ether (PPE-1) purified by reprecipitation, absorption attributed to the hydroxyalkyl group was observed at around 3,550 cm ^-1 . The results of GPC molecular weight measurement were Mn 20,700 and Mw 67,900.

Example 1 70 parts by weight of a carboxyl group-containing polyphenylene sulfide (functionalized PPS-1), 30 parts by weight of a functionalized polyphenylene ether (functionalized PPE-1), and 9 parts by weight of S.
After uniformly dry blending EBS and 0.5 part by weight of sodium ethoxide, using a Labo Plastomill manufactured by Toyo Seiki Co., Ltd., a temperature of 310 ° C., a rotor rotation speed of 180 r
The mixture was kneaded at pm for 5 minutes. 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 in a hot air dryer at 120 ° C,
It was heated for 4 hours to sufficiently crystallize the polyphenylene sulfide. A test piece for physical property evaluation was cut from this sheet.

The test pieces for evaluation of physical properties were evaluated after being stored in a desiccator for 2 days. Flexural rigidity is JIS-K-71
A bending rigidity test was carried out at 23 ° C. according to 06.
The impact strength was measured with an Izod impact tester by stacking three 2 mm-thick test pieces in accordance with JIS-K-7110. The dispersion form was obtained by cutting a part of the sheet and using a scanning electron microscope S-2400 manufactured by Hitachi, Ltd. at a magnification of 1
It was observed at 000 and 5,000 times. From the observed morphological photographs, the number average dispersed particle diameter Dn was determined by the following equation using a SPICCA II type image analyzer manufactured by Nippon Avionics Co., Ltd.

[0073]

## EQU1 ## Dn = Σnidi / Σni

A good appearance was evaluated as ◯, a worse appearance but no practical problem was evaluated as Δ, and a sparse surface having practical problem was evaluated as x. The results are shown in Table 1. <Examples 2 to 6, Comparative Examples 1 to 6> A resin composition was prepared by dry blending with the composition shown in Table 1 or Table 2, and the same procedure as in Example 1 was carried out to obtain a test piece. These results are shown in Table 1.
Or shown in Table 2.

[0075]

[Table 1]

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[Table 2]

[0077]

EFFECT OF THE INVENTION The resin composition of the present invention has extremely good compatibility, and thus gives a molded article excellent in appearance and impact strength.

[Brief description of drawings]

FIG. 1 shows an infrared absorption spectrum of a hydroxyalkylated polyphenylene ether (cast film prepared from a chloroform solution) obtained in Production Example 2.

FIG. 2 shows an infrared absorption spectrum of a hydroxylalkylated polyphenylene ether obtained in Production Example 2 in a carbon disulfide solution. Absorption attributed to the hydroxy group was observed near 3,550 cm ^-1 .

Claims (1)

[Claims] 1. Component (a): general formula (I): (In the formula, Q ¹ represents a halogen atom, a primary or secondary alkyl group, an aryl group, an aminoalkyl group, a halohydrocarbon group, a hydrocarbonoxy group or a halohydrocarbonoxy group, and Q ² represents each Represents a hydrogen atom, a halogen atom, a primary or secondary alkyl group, a halohydrocarbon group or a halohydrocarbonoxy group, m is an integer representing the degree of polymerization, and 20
~ 450. ) To 100 parts by weight of the polyphenylene ether represented by the general formula (II) (In the formula, R ¹ represents an aliphatic group having 1 to 8 carbon atoms. R
¹ may contain a hydroxyalkyl group. ) A functionalized polyphenylene ether containing a hydroxyalkyl group obtained by reacting 0.1 to 10 parts by weight of an alkylene carbonate as a part of the substituent (b): a carboxyl group and a mercapto group or disulfide in the molecule. Carboxyl group-containing polyphenylene sulfide obtained by modifying polyphenylene sulfide with a modifier selected from compounds having both groups. Containing 10 to 90% by weight of the above component (a) and 90 to 10% by weight of the component (b). A thermoplastic resin composition.