JP2570720B2 - Method for producing thermoplastic resin composition - Google Patents

Description

The present invention relates to polyphenylene sulfide (hereinafter abbreviated as PPS) and / or a block copolymer comprising a PPS portion and a polyphenylene sulfide sulfone portion (hereinafter, referred to as PPS portion).
Abbreviated as block copolymer) and a thermoplastic resin composition obtained by using a maleimide compound in combination to improve the compatibility with other thermoplastic resins. The thermoplastic resin composition has excellent appearance and improved mechanical properties. It produces molded articles and can be used for injection molding and extrusion molding materials in various fields.

(Problems to be Solved by Conventional Techniques and Inventions) PPS is known as a high-performance engineering plastic excellent in heat resistance, chemical resistance and flame retardancy. Therefore, PPS has low elongation, is brittle, and has a glass transition point of about 90 ° C., and thus has a drawback such as a sudden decrease in elastic modulus above the glass transition point. Many attempts have been made to improve such disadvantages by blending with various thermoplastic resins.

In addition, many studies have been made on blending PPS as an attempt to improve the heat resistance, chemical resistance, flame retardancy, moldability, etc. of other thermoplastic resins.

However, such a blend is poor in compatibility and has a problem that the surface state of the molded article is deteriorated and the mechanical properties are deteriorated.

(Means and Actions for Solving the Problems) As a result of intensive studies, the present inventors have found a maleimide compound as a component for improving the compatibility between the PPS and / or the block copolymer and another thermoplastic resin, It has become possible to provide a highly practical molding material that exhibits the characteristics of each of the polymer components.

That is, the present invention provides: (A) 99 to 1 parts by weight of a block copolymer composed of polyphenylene sulfide and / or a polyphenylene sulfide portion and a polyphenylene sulfide sulfone portion; (B) 1 to 99 parts by weight of another thermoplastic resin (C The present invention provides a thermoplastic resin composition obtained by melt-kneading 0.1 to 20 parts by weight of a maleimide compound (based on 100 parts by weight in total of (A) and (B)).

The PPS in the present invention can be obtained by various known methods. For example, its production method includes a method of polymerizing p-dichlorobenzene in the presence of sulfur and sodium carbonate, sodium sulfide or sodium hydrosulfide and sodium hydroxide or hydrogen sulfide and sodium hydroxide or sodium amino acid in a polar solvent. A method of polymerizing in the presence of an alkanoate, a self-condensation of p-chlorothiophenol, and the like can be mentioned. A method of reacting dichlorobenzene is common. At this time, in order to adjust the degree of polymerization, an alkali metal salt of carboxylic acid or sulfonic acid may be added, or an alkali hydroxide may be added. If the copolymer component is less than 30 mol%, a meta bond Ortho bond Ether bond Sulfone bond Biphenyl bond Carbonyl bond Substituted phenyl sulfide bond R represents an alkyl group, a nitro group, a phenyl group, an alkoxy group, a carboxylic acid group or a metal base of a carboxylic acid. Even if it has the same, it does not matter as long as it does not significantly affect the crystallinity of the polymer. When a phenyl, biphenyl, naphthyl sulfide bond or the like having three or more functionalities is selected for the copolymerization, it is preferably at most 3 mol%, more preferably at most 1 mol%.

As a specific method for producing such PPS, for example, (1)
Reaction of halogen-substituted aromatic compounds with alkali sulfide (US Pat. No. 2513188, JP-B-44-27671 and JP-B-45
-3368), and (2) a condensation reaction of thiophenols in the presence of an alkali catalyst or a copper salt (U.S. Pat.
74165 and British Patent No. 1160660), (3) Condensation reaction of an aromatic compound with sulfur chloride in the presence of a Lewis acid catalyst (JP-B-46-27255 and Belgian Patent No. 29439)
(4) Production method of high molecular weight PPS (Japanese Patent Publication No. 52-1)
2240, JP-B-54-8719, JP-B-53-25588, JP-B-57-3
34, JP-A-55-43139, USP4350810, USP4324886) and the like.

The block copolymer in the present invention is mainly PSS part with repeating unit, and mainly Is a block copolymer of a polyphenylene sulfide sulfone (hereinafter abbreviated as PPSS) portion having
It is used as an uncrosslinked product or a crosslinked product or a mixture thereof.

As disclosed in Japanese Patent Application No. 252857/1985, a block copolymer can be produced, for example, by reacting a terminal group of PPSS with a terminal group of PPS. In this case, the terminal group of PPS needs to be a reactive group such as a sodium sulfide group (structural formula: NaS—). As a method for obtaining such PPS, there is a method in which the amount of the sodium sulfide component of the monomer is previously reacted in the polymerization reaction in an excess of 1 to 20 mol% with respect to the p-dichlorobenzene component.

On the other hand, PPSS constituting the block copolymer of the present invention is Is defined as a polymer having a repeating unit of The molecular weight of this polymer is the logarithmic viscosity ηinh (where ηinh is 0.
Phenol / 1, at a polymer concentration of 5/100 ml of solution
30 in a 1,2,2-tetrachloroethane (3: 2 weight ratio) mixed solvent
It is a value measured at ℃ and calculated according to the following formula: ηinh = ln (relative viscosity) / polymer concentration. ) Is preferably in the range of 0.05 to 1.0. As a method for polymerizing this polymer, for example, a method of reacting a dihalo aromatic sulfone with an alkali metal sulfide in an organic amide solvent (see US Pat. No. 4,102,875) can be mentioned.

PPSS used in synthesizing the block copolymer of the present invention
Is, for example, at the polymer end As a method for obtaining this, a method of reacting the amount of the dihaloaromatic sulfone at the time of the polymer synthesis reaction in an excess of, for example, 5 mol% with respect to the amount of the alkali metal sulfide (US Pat. No. 4,301,274) Reference).

In carrying out the copolymerization reaction between PPSS and PPS in the method of the present invention, a method of adding a binder such as dihalo aromatic sulfone or sodium sulfide as the third component may be used. Further, a method of polymerizing the other monomer component in the presence of any one of PPS and PPSS, and finally obtaining a copolymer, without departing from the object of the present invention, which is a block copolymer, is used. You can also.

In the copolymerization reaction, it is most preferable to make the number of terminal reactive groups of PPS and PPSS the same, since a block copolymer can be obtained with high yield. On the other hand, when the number of terminal groups of one of the components is excessive, after the reaction is completed, only the unreacted homopolymer component is separated or extracted and removed to recover only the block copolymer.

The maleimide compound in the present invention is usually a compound represented by the following general formula (1).

The maleimide compound represented by the above formula can be produced by a known method in which maleimide acid is adjusted by reacting maleic acid with a monoamine or polyamine, and then the maleamic acid is dehydrated and cyclized. The amines used are preferably aromatic amines from the viewpoint of heat resistance of the final composition, but if flexibility or the like is desired, alicyclic amines and aliphatic amines may be used. Examples of preferred maleimide compounds include phenylmaleimide, N, N '-(methylene di-p-phenylene) dimaleimide, N, N'-(oxydi-p-phenylene) dimaleimide, N, N'-m-phenylenedimaleimide , N, N'-p-phenylenedimaleimide, N, N'-m
-Xylene dimaleimide, N, N'-p-xylene dimaleimide, N, N'-hexamethylene dimaleimide, and compounds represented by the following general formula (2).

Further, polyaminobismaleimide, which is an addition reaction product of N, N '-(methylene di-p-phenylene) dimaleimide and diaminodiphenylmethane, can be used.

The other thermoplastic resin is selected from polyester, polyarylate, polycarbonate, polyphenylene oxide, polyamide, polyimide, polysulfone, polyether ketone, polyamide type elastomer, polyester type elastomer, α-olefin (co) polymer or a modified product thereof. At least one.

For example, in order to improve the elastic modulus above the glass transition point, which is a drawback of PPS and block copolymers of PPS and PPSS, a combination of polyarylate, polyphenylene oxide, polyimide, polysulfone, polyetherketone, etc. is selected. In order to improve the toughness, a combination of an α-olefin (co) polymer or a modified product thereof, a polyamide elastomer, a polyester elastomer, polycarbonate, polyester, polyamide and the like is selected.

When PPS is blended with other thermoplastic resins except polyetherketone, chemical resistance etc. are improved and PPS is added to polyarylate, polyphenylene oxide, polyimide, polyamideimide, polyetherimide, polysulfone, polyethersulfone, polyetherketone. Has effects such as an improvement in fluidity and an improvement in moldability.

Even if PPS is blended with another thermoplastic resin, the compatibility is poor, and there is a problem that the surface state of the molded article is deteriorated and the mechanical properties are deteriorated. When a maleimide compound is added as a third component to PPS and another thermoplastic resin, the compatibility is surprisingly improved, the appearance of a molded article is improved, and the problems of reduced mechanical properties are eliminated.
Although the reason is not clear, it is considered that the unsaturated group of the maleimide compound causes some reaction to occur in both the PPS and the other thermoplastic resin and improves the compatibility while increasing the viscosity.

Polyester is a polymer or copolymer obtained by a condensation reaction containing a dicarboxylic acid and a diol as main components.

Examples of the polyester used in the present invention include terephthalic acid, isophthalic acid, orthophthalic acid, naphthalenedicarboxylic acid, 4,4'-diphenyldicarboxylic acid, diphenylether dicarboxylic acid, α, β-bis (4-carboxyphenoxy) ethane, adipic acid, Sebacic acid, azelaic acid, decanedicarboxylic acid, dodecanedicarboxylic acid,
Dicarboxylic acids such as cyclohexanedicarboxylic acid and dimer acid or ester-forming derivatives thereof and ethylene glycol, propylene glycol, butanediol, pentanediol, neopentyl glycol, hexanediol, octanediol, decanediol, cyclohexanedimethanol, hydroquinone, bisphenol A ,
Polyesters obtained from glycols such as 2,2-bis (4'-hydroxyethoxyphenyl) propane, xylene glycol, polyethylene ether glycol, polytetramethylene ether glycol, and aliphatic polyester oligomers having hydroxyl groups at both ends. Yes,
Usually, the intrinsic viscosity [η] measured at 30 ° C. in a mixed solvent of phenol and ethane tetrachloride in a weight ratio of 6 to 4 is 0.3 to 0.3.
1.5 dl / g range is used. It may contain a polyfunctional ester-forming component such as tromethylolpropane, trimethylolethane, glycerin, pentaerythritol, trimellitic acid, trimesic acid and pyromellitic acid as long as the thermoplasticity can be maintained.

Particularly preferred polyesters include polyethylene terephthalate, polybutylene terephthalate, polyhexamethylene terephthalate, poly (ethylene / butylene terephthalate), poly (cyclohexane dimethylene terephthalate), and 2,2-bis (β-hydroxyethoxytetrabromophenyl) propane. Polymerized polybutylene terephthalate and the like can be mentioned.

As the polyester used in the present invention, a liquid crystalline polyester may be used. About liquid crystalline polyester
An aromatic polyester capable of forming an anisotropic melt phase at a temperature of 400 ° C. or less. Examples of the essential components include those composed of the following repeating parts I and II.

At least one component selected from the group consisting of: (However, R is methyl, chloro, bromo or a mixture thereof and is a group substituted with hydrogen existing on an aromatic ring.) The aromatic polyester has an anisotropic melt phase formation temperature of about
Below 400 ° C, 260-350 ° C is preferred, especially 280-330 ° C
Is preferred.

Polyarylates are polyesters synthesized from bisphenols or derivatives thereof and dibasic acids or derivatives thereof. Examples of bisphenols include 2,2-bis- (4-hydroxyphenyl) -propane, 4,4'-
Dihydroxy-diphenyl ether, 4,4'-dihydroxy-3,3'-dimethyldiphenyl ether, 4,4'-dihydroxy-3,3'-dichlorodiphenyl ether,
4'-dihydroxy-diphenyl sulfide, 4,4'-dihydroxy-diphenyl sulfone, 4,4'-dihydroxy-diphenyl ketone, bis- (4-hydroxyphenyl) -methane, 1,1-bis- (4-hydroxyphenyl ) -Ethane, 1,1-bis- (4-hydroxyphenyl) -n-butane, di- (4-hydroxyphenyl)-
Cyclohexyl-methane, 1,1-bis- (4-hydroxyphenyl) -2,2,2-trichloroethane, 2,2-bis-
(4-Hydroxy-3,5-dibromophenyl) -propane, 2,2-bis- (4-hydroxy-3,5-dichlorophenyl) -propane, and the like, and particularly preferred is 2,2-bis -(4-hydroxyphenyl) -propane, that is, bisphenol A.

Examples of dibasic acids include aromatic dicarboxylic acids such as phthalic acid, isophthalic acid, terephthalic acid, bis- (4-carboxy) -diphenyl, bis- (4-carboxyphenyl) -ether, bis- (4-carboxyphenyl) )
-Sulfone, bis- (4-carboxyphenyl) -carbonyl, bis- (4-carboxyphenyl) -methane,
Bis- (4-carboxyphenyl) -dichloromethane,
1,2- and 1,1-bis- (4-carboxyphenyl)-
Ethane, 1,2- and 2,2-bis- (4-carboxyphenyl) -propane, 1,2- and 2,2-bis- (3-carboxyphenyl) -propane, 2,2-bis- (4 -Carboxyphenyl) -1,1-dimethylpropane, 1,1- and 2,2-bis- (4-carboxyphenyl) -butane,
1,1- and 2,2-bis- (4-carboxyphenyl)-
Pentane, 3,3-bis- (4-carboxyphenyl)-
Heptane, 2,2-bis- (4-carboxyphenyl)-
Heptane and aliphatic acids such as oxalic acid, adipic acid, succinic acid, malonic acid, sebacic acid, glutaric acid, azelaic acid, suberic acid, etc., are preferred, with isophthalic acid and terephthalic acid or mixtures of these derivatives being preferred.

The polycarbonate of the present invention (hereinafter abbreviated as PC) is a homogeneous PC
Also, for example, PC copolymers based on one or more of the following bisphenols can be used. Hydroquinone, resorcin, dihydroxydiphenyl, bis- (hydroxyphenyl) -alkane, bis- (hydroxyphenyl)
-Cycloalkane, bis- (hydroxyphenyl) -sulfide, bis- (hydroxyphenyl) -ketone,
Bis- (hydroxyphenyl) -ether, bis- (hydroxyphenyl) -sulfoxide, bis- (hydroxyphenyl) -sulfone and α, α′-bis- (hydroxyphenyl) -diisopropylbenzene and alkyl or halogen substituted nuclei Those compounds.

Specific examples of preferred bisphenols among these include 4,4-dihydroxydiphenyl, 2,2-bis-
(4-hydroxyphenyl) -propane, 2,4-bis-
(4-hydroxyphenyl) -2-methylbutane, 1,1
-Bis- (4-hydroxyphenyl) -cyclohexane, α, α'-bis- (4-hydroxyphenyl) -p
-Diisopropylbenzene, 2,2-bis- (3-methyl-4-hydroxyphenyl) -propane, 2,2-bis-
(3-chloro-4-hydroxyphenyl) -propane,
Bis- (3,5-dimethyl-4-hydroxyphenyl)-
Methane, 2,2-bis- (3,5-dimethyl-4-hydroxyphenyl) -propane, bis- (3,5-dimethyl-4-
(Hydroxyphenyl) -sulfone, 2,4-bis- (3,5
-Dimethyl-4-hydroxyphenyl) -2-mercaptan, 1,1-bis- (3,5-dimethyl-4-hydroxyphenyl) -cyclohexane, α, α'-bis- (3,5-
Dimethyl-4-hydroxyphenyl) -p-diisopropylbenzene, 2,2-bis- (3,5-dichloro-4-hydroxyphenyl) -propane and 2,2-bis- (3,5-dibromo-4-hydroxy Phenyl) -propane and the like, preferably 2,2-bis- (4-hydroxyphenyl) -propane, 2,2-bis- (3,5-dimethyl-4-hydroxyphenyl) -propane, 2,2 -Bis- (3,5-dichloro-4-hydroxyphenyl) -propane, 2,2-
Bis- (3,5-dibromo-4-hydroxyphenyl)-
Propane and 1,1-bis- (4-hydroxyphenyl)
-Cyclohexane.

Preferred PCs are based on the preferred bisphenols described above. Particularly preferred PC copolymers are 2,2-bis-
It is a copolymer of (4-hydroxyphenyl) -propane and one of the above particularly preferred other bisphenols.

Other particularly suitable PCs are 2,2-bis- (4-hydroxyphenyl) -propane or 2,2-bis- (3,5-dimethyl-
4-hydroxyphenyl) -propane only.

Incidentally, PC can be produced by a known method, for example, a method of melt transesterification of bisphenol and diphenyl carbonate, a two-phase interfacial polymerization method of bisphenol and phosgene, and the like.

Polyphenylene oxide is also referred to as polyphenylene ether, for example, the general formula [I] (Wherein, R ₁ and R ₂ represent hydrogen, halogen or an alkyl, haloalkyl, alkoxy or allyl derivative having 9 or less carbon atoms or an aralkyl group having 4 or less carbon atoms, n represents the number of repeating units, and an integer of 10 or more) The polymer of 2,6-disubstituted phenol and the polymer of 2,6-disubstituted phenol and polyhydric phenol represented by
No. 24265) and the molecular weight is usually 2,000 or more, preferably 10,000 to 35,000.

Such resins are generally phenols such as phenol, 2,6-dimethylphenol, 2,6-diethylphenol, 2,6-diisopropylphenol, 2-methyl-
It can be obtained by subjecting 6-methoxyphenol or the like to a dehydration reaction with oxygen in the presence of a cocatalyst such as a metal / amine or a metal chelate / basic organic compound. Any production method can be used. Specific examples include 2,6-dimethylphenylene oxide polymer, 2,6
A dimethylphenol / bisphenol A (former / latter = 95/5 molar ratio) copolymer, a 2,6-diethylphenylene oxide polymer, and the like. Also, use of styrene-grafted PPO is not a problem.

In the present invention, examples of the polyamide resin used as one of the raw materials include various known polyamide resins. For example, terephthalic acid, isophthalic acid, oxalic acid,
Polymerization condensation of dicarboxylic acids such as adipic acid, sepadic acid and 1,4-cyclohexyldicarboxylic acid with diamines such as ethylenediamine, pentamethylenediamine, hexamethylenediamine, decamethylenediamine, 1,4-cyclohexyldiamine and m-xylylenediamine Polymerization of a cyclic lactam such as caprolactam or laurolactam; obtained by polycondensation of an aminocarboxylic acid such as aminoenanoic acid, aminononanoic acid or aminoundecanoic acid, or copolymerization of the above-mentioned cyclic lactam, dicarboxylic acid and diamine. Available, 6 nylon, 66 nylon, 610 nylon, 612 nylon, 11 nylon, 12 nylon, 66/610
Copolymer nylon, 6/66 copolymer nylon and the like can be mentioned, and particularly preferred are 6 nylon, 66 nylon and 12 nylon. Furthermore, polycondensation with cyclic lactams such as lauryl lactam, aromatic dicarboxylic acids such as terephthalic acid and isophthalic acid, and alicyclic aliphatic diamines such as 4,4'-diamino-3,3'-dimethylcyclohexylmethane; trimethyl Substantially amorphous polyamide resins obtained by polycondensation of an asymmetric diamine such as hexamethylene diamine and an aromatic diamine are also suitable. Polyimide is
General formula [Wherein, R is a tetravalent aromatic or aliphatic group containing at least one carbon 6-membered ring, and R ₁ is a group represented by the formula: Wherein R ₂ is a divalent benzenoid group represented by the formula:
O -, - CH ₂ -, -S -, - SO ₂ -, Wherein R ₃ and R ₄ are selected from the group consisting of alkyl and aryl groups, and n is at least about 20.
It is an integer of 2 or more so that the polymer becomes thermally stable at 0 ° C. A polyimide having a repeating unit represented by the general formula [Where Ra is 10% to 90% of the repeating unit. And in the rest of the repeating unit Where n is an integer greater than or equal to 2 such that the polymer is thermally stable at least at about 200 ° C. A polyimide having a repeating unit represented by the general formula [Wherein, Ar represents a trivalent aromatic group containing at least one carbon 6-membered ring, R represents a divalent aromatic and / or aliphatic residue, and R ′ represents hydrogen, a methyl group or a phenyl group. And n is an integer of 2 or more. A polyamide imide having a repeating unit represented by the general formula: [Wherein Ar is a trivalent aromatic group containing at least one carbon 6-membered ring, and R is a divalent aromatic and / or aliphatic residue. And a polyetherimide having a repeating unit represented by the formula:

Polysulfone is defined as a polyarylene compound in which the arylene units are located randomly or orderly with ether and sulfone linkages, for example,
(Wherein n represents an integer of 10 or more), but preferably has a structure of or.

Polyetherketone is a repeating unit of the formula [1] And / or a repeating unit of the formula [2] Is a tough, crystalline thermoplastic aromatic polyether ketone which contains, alone or together with other repeating units, and has an intrinsic viscosity (IV) of 0.7 or more. As a repeating unit other than the formula [1] and / or the formula [2], a formula [3] [Wherein A is a direct bond, oxygen, sulfur, -SO _2- , -CO-
Or a divalent hydrocarbon group. ] And equation [4] And further, as a copolymerized unit, a compound represented by the formula [5] And equation [6] (Where the subunit is Oxygen atom 'is in the ortho or para position relative to, Q and Q' groups Q or Q are the same or different, -CO- or -SO ₂ - and is, Ar 'is a divalent aromatic radical And n is 0, 1, 2 or 3. ] Is included.

The polyamide elastomer is a block copolymer elastomer having hard segments of nylons 11 and 12 and soft segments of a polyether component or a polyester component. Specific examples of the polyether component include OR _n (R is a C _{2 to} C ₁₂ alkylene group),
Specific examples of the polyester component, polycaprolactone or HO-R-OH (R is an alkylene group of C ₂ -C ₁₂₎
And (R ₁ COOH) _2-3 as a starting component. A typical product name is EMSCHEMIE
It is offered by the company under the trade name "Grilamide". Also, a random copolymer of nylon 6, nylon 66, nylon 610, nylon 11, and nylon 12 can be used.

The polyester elastomer is a block copolymer of a high melting point hard segment mainly composed of an alkylene terephthalate unit and a low melting point soft segment composed of an aliphatic polyester or polyether. Examples of the segment mainly composed of an alkylene terephthalate unit constituting the high melting point segment include terephthalic acid and ethylene glycol, propylene glycol, tetramethylene glycol, pentamethylene glycol, 2,2-dimethyl-trimethylene glycol, hexamethylene glycol, decamethylene glycol. Mainly a unit consisting of an alkylene glycol such as glycol, and optionally a dicarboxylic acid such as isophthalic acid, 1,5-naphthalenedicarboxylic acid,
2,6-naphthalenedicarboxylic acid, dibenzoic acid, bis (p
-Carboxyphenyl) methane, aromatic dicarboxylic acids such as 4,4'-sulfonyldibenzoic acid, aliphatic dicarboxylic acids to be described later, diols such as p-xylylene glycol and cyclohexanedimethanol as glycols, and p-oxy as oxyacids Even if a small amount of benzoic acid, p- (β-hydroxyethoxy) benzoic acid, or the like is contained as a component, it may be acceptable.

Examples of the low melting point soft segment composed of aliphatic polyester or polyether include poly (ethylene oxide) glycol and poly (propylene oxide).
Glycols, polyether glycols such as poly (tetramethylene oxide) glycol, mixtures or copolymers of these polyether glycols, having 2 carbon atoms
Polyesters prepared from aliphatic dicarboxylic acids having up to 12 and aliphatic glycols having 2 to 10 carbon atoms, such as polyethylene adipate, polytetramethylene adipate, polyethylene sebacate, polyneopentyl sebacate,
Polytetramethylene dodecane, polytetramethylene azelate, polyhexamethylene azelate, poly-ε
-Caprolactone and the like, and a polyester polyether copolymer obtained by combining the above aliphatic polyester and an aliphatic polyether.

In the polyester type block copolymer of the present invention,
The molecular weight of the low melting point soft segment is preferably from 400 to 6000, and the proportion of the soft segment in the copolymer is preferably from 5 to 80% by weight.

The α-olefin (co) polymer comprises at least 50 mol% of an α-olefin such as ethylene, propylene, butene-1, isobutene, pentene-1, hexene-1,
Contains decene-1,4-methylbutene-1,4-methylpentene-1,4,4-dimethylpentene-1, vinylcyclohexane, styrene, α-methylstyrene, styrene substituted with a lower alkyl substituent or the like Should. Mixtures of the above olefins can also be used. A modified product obtained by grafting an unsaturated carboxylic acid or an unsaturated epoxy compound to the α-olefin (co) polymer can also be suitably used.

As the acid component, citraconic anhydride, 3-methyl-4
-Cyclohexene-1,2-dicarboxylic anhydride (hereinafter referred to as P
MMA), maleic anhydride, (methyl) nadic anhydride, itaconic anhydride, and epoxy components such as glycidyl acrylate and glycidyl methacrylate. The α-olefin (co) polymer 100
0.1 to 2.0 parts by weight, preferably 0.2 to 2.0 parts by weight,
1.5 parts by weight for graft polymerization.

The ratio of PPS to other thermoplastics is 99/1 to 1/99 (weight ratio)
If it is out of the range, each reforming effect will be lost,
If the amount of the maleimide compound is less than 0.1 part by weight with respect to the total of 100 parts by weight of the PPS and the other thermoplastic resin, the effect of improving the compatibility is not obtained. If the amount exceeds 20 parts by weight, molding becomes extremely difficult due to thickening.

The composition of the present invention includes glass fiber, carbon fiber, potassium titanate, asbestos, silicon carbide, ceramic fiber,
Fibrous reinforcing agents such as metal fibers and silicon nitride; barium sulfate, calcium sulfate, kaolin, clay, pyrophyllant, bentonite, sericite, zeolite, mica, mica, nepheline cinite, talc, atalvalgite, wollastonite , PMF, ferrite, calcium silicate, calcium carbonate, magnesium carbonate, dolomite, antimony trioxide, zinc oxide, titanium oxide, magnesium oxide, iron oxide, molybdenum dioxide, graphite, stone, glass beads, glass balloon, quartz powder, etc. Inorganic fillers; organic reinforcing agents such as aramid fibers can be included in the composition up to 80% by weight. When adding these reinforcing agents or fillers, known silane coupling agents can be used.

Further, the composition of the present invention may contain a small amount of an epoxy resin, a releasing agent, a coloring agent, a heat stabilizer, an ultraviolet stabilizer, a foaming agent, a flame retardant, a flame retardant auxiliary, and a flame retardant within a range not departing from the object of the present invention. Rust agents and the like can be included.

The composition of the present invention is prepared by melt-kneading. For example, a method in which the raw materials are uniformly mixed in advance by a mixer such as a tumbler or a Henschel mixer, fed to a single-screw or twin-screw extruder, melt-kneaded at 230 to 400 ° C., and then pelletized is used. it can.

(Effects of the Invention) The present invention provides a molded article having excellent compatibility between PPS and / or a block copolymer of PPS and PPSS, and other thermoplastic resins, and having improved mechanical properties. Composition.

(Examples) Next, the present invention will be specifically described with reference to examples, but the present invention is not limited to these examples.

Reference Example 1 984 g of sodium sulfide (60% purity) and 47 g of sodium hydroxide were added to 3080 g of N-methylpyrrolidone, and the temperature was raised while dehydrating to 205 ° C., followed by 1113 g of paradichlorobenzene.
And 510 g of N-methylpyrrolidone, and the mixture was heated under pressure at 262 ° C. for 5 hours, then cooled, washed with water and dried. The resulting polymer (PPS) was thermally crosslinked at a temperature of 260 ° C. in air for 5 hours. This is designated as polymer (A).

The melt flow rate of the polymer (A) was 316 ° C. and 250 at a load of 5 kg.

Reference Example 2 984 g of sodium sulfide (60% purity), sodium hydroxide
47 g and 765 g of lithium acetate dihydrate were added to N-methylpyrrolidone 3
080 g, and after raising the temperature while dehydrating to 205 ° C, p
-Dichlorobenzene 1113 g, N-methylpyrrolidone 510 g
The mixture was heated under pressure at 230 ° C. for 2 hours and at 260 ° C. for 3 hours, cooled, washed with water and dried. Let the obtained PPS be a polymer (B).

The melt flow rate of the polymer (B) was 130 at 316 ° C. under a load of 5 kg.

Reference Example 3 Reaction was carried out as in Reference Example 1 to obtain a chlorophenyl-terminated PPS (logarithmic viscosity ηinh 0.22). (Ηinh is 0.5g / 10
Measured at 30 ° C in a mixed solvent of phenol / 1,1,2,2-tetrachloroethane (weight ratio of 3: 2) at the polymer concentration of 0 ml of the solution, the formula: ηinh = ln (relative viscosity) / polymer concentration Calculated by Also, 3100 g of N-methylpyrrolidone and 2.7 g of sodium sulfide
1009 g of water salt and 3.5 g of sodium hydroxide were charged, and the temperature was raised to 200 ° C. under a nitrogen atmosphere. Terminal chlorophenyl group type
Got PPSS.

Next, 2370 g of the above-mentioned PPS, 300 g of the above-mentioned PPSS, and 1200 g of N-methylpyrrolidone were added and reacted at 220 ° C. under a nitrogen atmosphere to obtain 486 g of a block copolymer. Such a block copolymer contains 46% by weight of PPSS and has a logarithmic viscosity (0.4 g / 100 ml).
(Measured in α-chloronaphthalene at 206 ° C.) was 0.19.

Examples 1 to 3 and Comparative Examples 1 to 5 70 parts by weight of the polymer A (PPS) obtained in Reference Example 1, 30 parts by weight of polysulfone and 2 parts by weight of bismaleimide were uniformly premixed, and then the vent was heated to 330 ° C. The mixture was kneaded with a 40 mm extruder and pelletized. Using these pellets, test pieces were prepared with an injection molding machine. The appearance of the test piece was light brown with excellent compatibility and excellent uniformity.

Test pieces of other examples were prepared in the same manner as in Example 1 with the composition shown in Table 1. Table 1 shows the characteristics.

Examples 4 to 12 and Comparative Examples 6 to 14 Extruded and kneaded at 330 ° C into pellets with the composition shown in Table-2. A test piece was prepared using the pellet. Table 2 shows each characteristic.

Examples 13 to 30 and Comparative Examples 15 to 32 Each test piece was prepared by extruding and kneading at 290 ° C into pellets with the composition shown in Tables 3, 4, 5, and 6. Table for each characteristic
Shown in 3,4,5,6.

Claims (2)

(57) [Claims] (A) a polyphenylene sulfide and / or a block copolymer comprising a polyphenylene sulfide portion and a polyphenylene sulfide sulfone portion in an amount of 99 to 1 part by weight (B) another thermoplastic resin in an amount of 1 to 99 parts by weight (C) A method for producing a thermoplastic composition, wherein 0.1 to 20 parts by weight of a maleimide compound (based on a total of 100 parts by weight of (A) and (B)) is melt-kneaded. 2. The method according to claim 1, wherein the other thermoplastic resin is polyester, polyarylate, polycarbonate, polyphenylene oxide, polyamide, polyimide, polysulfone, polyether ketone, polyamide-type elastomer, polyester-type elastomer, α-olefin (co) polymer or a copolymer thereof. The production method according to claim 1, wherein the production method is at least one type of thermoplastic resin selected from a modified product.