JP2008101200A - Thermoplastic resin composition - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a thermoplastic resin composition having well-balanced heat resistance, chemical resistance and electrical properties, and also to provide a molded article from the resin composition. <P>SOLUTION: The thermoplastic resin composition comprises a polyphenylene ether resin and a polyaryl ketone resin. Preferably, the whole or a part of the polyphenylene ether resin is modified with an epoxy group-containing compound. <P>COPYRIGHT: (C)2008,JPO&INPIT

Description

  The present invention relates to a thermoplastic resin composition and a molded article excellent in a balance between heat resistance, chemical resistance and electrical characteristics.

Polyphenylene ether is used in a wide range of applications because it has excellent mechanical properties, electrical properties, and heat resistance, and also has excellent dimensional stability, but it is inferior in molding processability by itself. It is widely known to blend polystyrene. However, there is a problem that heat resistance and chemical resistance are lowered.
As a technique for improving the fluidity of polyphenylene ether while maintaining heat resistance, a technique for blending liquid crystal polyester (for example, see Patent Document 1) has been proposed, but it is sufficient in terms of impact resistance and chemical resistance. It wasn't.
On the other hand, polyaryl ketones typified by polyetheretherketone are very expensive and have a high melting point, but since the glass transition temperature of the resin itself is relatively low, improvements such as heat resistance have been studied. It was.

Moreover, in blending layered silicate with polyetheretherketone, a composition is disclosed that is blended in the form of a masterbatch composed of polyphenylene ether and layered silicate in order to improve dispersibility (see Patent Document 2). However, this is not intended to be an alloy of polyphenylene ether and polyetheretherketone, and electrical properties are not sufficient.
Therefore, the present situation is that a resin composition having an excellent balance between heat resistance, chemical resistance, and electrical characteristics is desired.
JP 56-115357 A JP 2003-335867 A

  The object of the present invention is suitable for precision molded products such as electric and electronic parts, and has not been able to be achieved by the above-described technology, and has a thermoplastic resin composition having an excellent balance of heat resistance, chemical resistance, and electrical characteristics, and The object is to provide a molded article comprising the resin composition.

As a result of intensive studies to solve the above-mentioned problems, the present inventors have found that a thermoplastic resin composition comprising a polyphenylene ether resin and a polyaryl ketone resin is excellent in these properties. The present invention has been found out that it is effective for obtaining a product and a molded body.
Next, in order to facilitate understanding of the present invention, basic features and preferred embodiments of the present invention will be listed.
(1) A thermoplastic resin composition comprising (A) a polyphenylene ether resin and (B) a polyaryl ketone resin.
(2) The thermoplastic resin composition according to the above (1), wherein (A) part or all of the polyphenylene ether resin is a polyphenylene ether resin modified with an epoxy group-containing compound.
(3) The thermoplastic resin according to (1) or (2), further comprising (C) an epoxy compound in an amount of 0.1 to 10 parts by mass with respect to 100 parts by mass in total of the components (A) and (B). Composition.
(4) The thermoplastic resin composition according to the above (2) or (3), wherein the polyphenylene ether resin modified with the epoxy group-containing compound (A) has a modification rate of 0.1 to 50%.

(5) The thermoplastic resin according to any one of (2) to (4) above, wherein the polyphenylene ether resin modified with the epoxy group-containing compound (A) is modified at a temperature lower than the glass transition temperature of the polyphenylene ether resin. Resin composition.
(6) The thermoplastic resin composition according to any one of (1) to (5), wherein the component (A) is 1 to 49 parts by mass and the component (B) is 51 to 99 parts by mass.
(7) The thermoplastic resin composition according to any one of (1) to (6), wherein the component (A) forms a dispersed phase and the component (B) forms a continuous phase.
(8) The thermoplastic resin composition according to any one of (1) to (7), wherein the component (B) is a polyetheretherketone resin.
(9) The thermoplastic resin composition according to any one of (3) to (8), wherein (C) the epoxy compound is a copolymer of an unsaturated monomer having a glycidyl group and a monomer having styrene as a main component. object.

(10) The thermoplastic resin composition according to the above (1) to (9), which comprises (D) an elastomer.
(11) The above (1) to (10), wherein the component (D) is a hydrogenated product of a block copolymer comprising a polymer block mainly composed of an aromatic vinyl compound and a polymer block mainly composed of a conjugated diene compound. ). The thermoplastic resin composition according to any one of
(12) The thermoplastic resin composition according to any one of the above (1) to (11), comprising (E) an inorganic filler.
(13) The thermoplastic resin composition according to any one of (1) to (12), which comprises a flame retardant (F).
(14) An injection-molded article comprising the thermoplastic resin composition according to any one of (1) to (13).
(15) A sheet comprising the thermoplastic resin composition according to any one of (1) to (13).

  ADVANTAGE OF THE INVENTION According to this invention, the thermoplastic resin composition excellent in the balance of heat resistance, chemical resistance, and an electrical property and the molded object which consists of this resin composition can be provided.

Next, each component that can be used in the present invention will be described in detail.
The polyphenylene ether resin of component (A) that can be used in the present invention is a homopolymer and / or copolymer comprising the structural unit of the formula (1).

[Wherein, O is an oxygen atom, R _{1 to} R ₄ are each independently hydrogen, halogen, primary or secondary lower alkyl, phenyl, haloalkyl, aminoalkyl, hydrocarbonoxy, or halocarbon. Represents hydrogenoxy, provided that at least two carbon atoms separate the halogen and oxygen atoms. ]

  Specific examples of the polyphenylene ether resin of the present invention include, for example, poly (2,6-dimethyl-1,4-phenylene ether), poly (2-methyl-6-ethyl-1,4-phenylene ether), Poly (2-methyl-6-phenyl-1,4-phenylene ether), poly (2,6-dichloro-1,4-phenylene ether) and the like, and 2,6-dimethylphenol and other phenols (For example, a copolymer with 2,3,6-trimethylphenol or a copolymer with 2-methyl-6-butylphenol as described in JP-B-52-17880) Polyphenylene ether copolymers are also included. When using a copolymer of 2,6-dimethylphenol and 2,3,6-trimethylphenol as polyphenylene ether, the ratio of each monomer unit is based on the total amount of polyphenylene ether copolymer being 100% by mass. Particularly preferred is a copolymer comprising about 60 to about 90% by weight of 2,6-dimethylphenol and about 10 to about 40% by weight of 2,3,6-trimethylphenol.

Among these, particularly preferred polyphenylene ether resins include poly (2,6-dimethyl-1,4-phenylene ether), a copolymer of 2,6-dimethylphenol and 2,3,6-trimethylphenol, or these It is a mixture of
The method for producing the polyphenylene ether resin used in the present invention is not particularly limited as long as it can be obtained by a known method. For example, U.S. Pat. Nos. 3,306,874, 3,306,875, and 3,257,357. Examples thereof include the production methods described in the specification and the specification of Japanese Patent No. 3257358, JP-A-50-51197, JP-B-52-17880, and 63-152628.

The reduced viscosity (η _{sp / c} : 0.5 g / dl, chloroform solution, measured at 30 ° C.) of the polyphenylene ether resin that can be used in the present invention is in the range of 0.15 to 0.70 dl / g. More preferably, it is the range of 0.20-0.60 dl / g, More preferably, it is the range of 0.40-0.55 dl / g.
In the present invention, two or more polyphenylene ether resins having different reduced viscosities may be blended. For example, a mixture of a polyphenylene ether having a reduced viscosity of 0.45 dl / g or less and a polyphenylene ether having a reduced viscosity of 0.50 dl / g or more, a low molecular weight polyphenylene ether having a reduced viscosity of 0.40 dl / g or less, and a reduced viscosity of 0.50 dl / g or more. A mixture of polyphenylene ether resins is not limited to these.

Furthermore, although the polyphenylene ether resin has a phenolic hydroxyl group at the molecular chain end, the position may be one end, both ends, or a mixture thereof.
In addition, the polyphenylene ether resin that can be used in the present invention may be partly or entirely modified with an epoxy group-containing compound.
The method for producing the modified polyphenylene ether includes (1) an epoxy group without melting the polyphenylene ether at a temperature in the range of 80 ° C. or higher in the presence or absence of a radical initiator and lower than the glass transition temperature of the polyphenylene ether. (2) a method of reacting a polyphenylene ether and an epoxy group-containing compound in a solution at a temperature lower than the glass transition temperature of the polyphenylene ether in the presence or absence of a radical initiator, and (3) In the presence or absence of a radical initiator, a method of melting and kneading and reacting with an epoxy group-containing compound at a temperature in the range of the glass transition temperature of polyphenylene ether to 360 ° C. may be used, and any of these methods may be used. . Especially, the method of making it react below the glass transition temperature of polyphenylene ether is preferable, and the method of making it react in a solution is more preferable.

  Examples of the epoxy group-containing compound that can be used for modifying the polyphenylene ether resin include epoxy resin, allyl glycidyl ether, glycidyl acrylate, glycidyl methacrylate, epoxidized natural oil and fat, and the like. Epoxy resins include bisphenol A type epoxy resin, bisphenol F type epoxy resin, bisphenol S type epoxy resin, hindered-in type epoxy resin, biphenyl type epoxy resin, bisphenol-novolak type epoxy resin, alicyclic epoxy resin, triphenylmethane type Examples thereof include epoxy resins, phenol novolac type epoxy resins, orthocresol novolac type epoxy resins, and halogenated compounds thereof. Moreover, what mixed these 1 or 2 or more types can also be used for these epoxy resins. In the present invention, among the various epoxy resins described above, a bisphenol A type epoxy resin or an orthocresol novolac type epoxy resin is particularly preferable from the viewpoints of reactivity and handleability. The epoxy group-containing compound may be the same as or different from the epoxy compound described later.

The amount of the epoxy group-containing compound added in the production of the modified polyphenylene ether is preferably 1 to 100 parts by mass, more preferably 3 to 50 parts by mass with respect to 100 parts by mass of the polyphenylene ether resin.
A preferable amount of the radical initiator in producing the polyphenylene ether modified with the radical initiator is 0.001 to 2 parts by mass with respect to 100 parts by mass of the polyphenylene ether.
The addition rate of the epoxy group-containing compound in the modified polyphenylene ether is preferably 0.1 to 50%. More preferably, it is 1 to 40%.

In the modified polyphenylene ether, an unreacted epoxy group-containing compound and / or a polymer of the epoxy group-containing compound may remain.
(A) The modification rate of the polyphenylene ether resin modified with the epoxy group-containing compound is preferably 0.1 to 50%, more preferably 1 to 40%, and still more preferably 3 from the viewpoint of sheet formability. ~ 30%.
Also, various stabilizers known for stabilizing the polyphenylene ether can be suitably used. Examples of the stabilizer are organic stabilizers such as a hindered phenol stabilizer and a hindered amine stabilizer, and the preferred blending amount thereof is less than 5 parts by mass with respect to 100 parts by mass of the polyphenylene ether resin.

Furthermore, you may add the well-known additive etc. which can be added to polyphenylene ether resin in the quantity of less than 10 mass parts with respect to 100 mass parts of polyphenylene ether resin.
The polyaryl ketone of the component (B) of the present invention is a thermoplastic resin containing an aromatic nucleus bond, an ether bond and a ketone bond in its structural unit, and representative examples thereof include polyether ketone, polyether ether ketone, There are polyether ketone ketones and the like, and they may contain other monomer units capable of copolymerization such as biphenyl structure and sulfonyl group within the range not exceeding the gist of the present invention. In the present invention, polyetheretherketone having a repeating unit represented by the formula (2) is preferably used.

Polyether ether ketone having this repeating unit is commercially available under the trade names “PEEK90G”, “PEEK151G”, “PEEK381G”, “PEEK450G”, etc., manufactured by VICTREX. In addition, polyaryl ketone can be used individually by 1 type or in combination of 2 or more types.
In the present invention, the amount ratio of the polyphenylene ether resin to the polyaryl ketone is not particularly limited, but from the viewpoint of heat resistance, the polyphenylene ether resin is 1 to 49 parts by mass and the polyaryl ketone is 51 to 99 parts by mass. preferable. More preferably, they are 5-40 mass parts of polyphenylene ether resins, 60-95 mass parts of polyaryl ketones, More preferably, 20-40 mass parts of polyphenylene ether resins, 60-80 mass parts of polyaryl ketones.

In the present invention, it is preferable that the polyphenylene ether resin forms a dispersed phase and the polyaryl ketone forms a continuous phase. Since the polyaryl ketone forms a continuous phase, the chemical resistance is excellent. About these morphology, it can judge easily by observing, for example using a transmission electron microscope.
The (C) epoxy compound in the present invention includes an epoxy resin, a precursor thereof, and an epoxy group-containing copolymer. For example, the epoxy resin and the epoxy resin precursor include bisphenol A type epoxy resin, orthocresol novolac type epoxy resin, glycidylamine type epoxy resin, trifunctional type epoxy resin, tetrafunctional type epoxy resin, and precursors thereof. The epoxy compound may be the same as or different from the epoxy group-containing compound described above.

In addition, examples of the epoxy group-containing copolymer include a copolymer of an unsaturated monomer having a glycidyl group and a monomer having styrene as a main component. The monomer having styrene as the main component here is 100% by weight of the styrene component, but when there is another monomer copolymerizable with styrene, the copolymer chain is the component (A). In order to maintain the miscibility with the polyphenylene ether resin, it is preferable to contain at least 65% by weight of styrene monomer, more preferably 75 to 98% by weight.
Specific examples of the unsaturated monomer having a glycidyl group constituting these copolymers include allyl glycidyl ether, glycidyl acrylate, glycidyl methacrylate, epoxidized natural oil and fat, among which glycidyl acrylate and glycidyl methacrylate are used. preferable. Content of the unsaturated monomer which has these glycidyl groups is 0.3-20 weight% in the copolymer of (C) component, Preferably it is 1-15 weight%, More preferably, it is 2-10 weight%.

  In addition, a vinyl cyanide monomer such as ethylene or acrylonitrile, vinyl acetate, acrylic acid ester, methacrylic acid ester, or the like may be copolymerized as a copolymerization component. Examples of these copolymers include styrene-glycidyl methacrylate copolymers, styrene-glycidyl methacrylate-methyl methacrylate copolymers, styrene-glycidyl methacrylate-acrylonitrile copolymers, and ethylene copolymers. For example, a graft copolymer obtained by grafting a styrene monomer onto an ethylene-glycidyl methacrylate copolymer, or a styrene monomer and acrylonitrile on an ethylene-glycidyl methacrylate copolymer. Examples thereof include grafted graft copolymers.

(C) The compounding quantity in the case of mix | blending an epoxy compound is 0.1 mass part or more from a heat resistant and a flame-resistant viewpoint with respect to a total of 100 mass parts of said (A) component and (B) component. Less than heavy part. Preferably they are 0.15 mass part or more and 9 heavy parts or less, More preferably, they are 0.2 mass part or more and 8 mass parts or less, More preferably, they are 0.3 mass part or more and 5 mass parts or less.
The thermoplastic resin composition of the present invention can contain polyarylate. Polyarylate, also called polyaryl ester, is a polymer containing an aromatic ring and an ester group in the main chain. These polymers are preferably polymers comprising bisphenol A, terephthalic acid and isophthalic acid. Polyarylate having a repeating unit represented by the formula (3) is preferably used.

The content of polyarylate is preferably 0.5 to 45 parts by mass with respect to 100 parts by mass in total of the component (A) and the component (B). More preferably, it is 1-40 mass parts, More preferably, it is 2-30 mass parts, Most preferably, it is 3-20 mass parts, Especially preferably, it is 4-10 mass parts. The content of this polyarylate is preferably 0.5 parts by mass or more from the viewpoint of suppressing interphase peeling of the resin composition, and is preferably 45 parts by mass or less from the viewpoint of heat resistance.
Furthermore, in the present invention, a styrene polymer may be included. Examples of the styrenic polymer in the present invention include homopolystyrene, rubber-modified polystyrene (HIPS), styrene-acrylonitrile copolymer (AS resin), styrene-rubber polymer-acrylonitrile copolymer (ABS resin), and the like. It is done. By including the styrenic polymer, in addition to achieving the object of the present invention, fluidity can be improved. A preferable blending amount of the styrene polymer is an amount of less than 50 parts by mass with respect to 100 parts by mass in total of the polyphenylene ether and the polyaryl ketone. Although there is no restriction | limiting in particular in the addition method of these styrene-type polymers, It is preferable to add simultaneously with a polyphenylene ether component.

In the present invention, (D) an elastomer can be further added. Preferred elastomers include block copolymers composed of a polymer block mainly composed of at least one aromatic vinyl compound and a polymer block mainly composed of at least one conjugated diene compound.
“Mainly” in the polymer block mainly composed of the aromatic vinyl compound of the present invention means that at least 50% by mass or more of the block is an aromatic vinyl compound unit. More preferably, it is 70 mass% or more, More preferably, it is 80 mass% or more, Most preferably, it is 90 mass% or more. The same applies to “mainly” in a polymer block mainly composed of a conjugated diene compound, which means that at least 50% by mass or more is a conjugated diene compound unit. More preferably, it is 70 mass% or more, More preferably, it is 80 mass% or more, Most preferably, it is 90 mass% or more.

In this case, for example, even in the case of a block in which a small amount of a conjugated diene compound or another compound is randomly bonded in an aromatic vinyl compound block, 50% by mass of the block is formed from aromatic vinyl compound units. If so, it is regarded as a block copolymer mainly composed of an aromatic vinyl compound. The same applies to the case of a conjugated diene compound.
Specific examples of the aromatic vinyl compound include styrene, α-methylstyrene, vinyltoluene and the like, and one or more compounds selected from these are used, and among them, styrene is particularly preferable.
Specific examples of the conjugated diene compound include butadiene, isoprene, piperylene, 1,3-pentadiene and the like, and one or more compounds selected from these are used. Of these, butadiene, isoprene and combinations thereof are preferable. .

The microstructure of the conjugated diene compound block portion of the block copolymer is preferably 1,2-vinyl content or a total amount of 1,2-vinyl content and 3,4-vinyl content of 5-80%, more preferably 10-50% 15 to 40% is most preferable.
In the block copolymer of the present invention, the polymer block [A] mainly composed of an aromatic vinyl compound and the polymer block [B] mainly composed of a conjugated diene compound are AB type and ABA type. A block copolymer having a bond type selected from A-B-A-B type is preferable, and a mixture thereof may be used. Among these, the AB type, the ABA type, or a mixture thereof is more preferable, and the ABA type is most preferable.

The block copolymer of an aromatic vinyl compound and a conjugated diene compound that can be used in the present invention is more preferably a hydrogenated block copolymer. The hydrogenated block copolymer is an aliphatic double bond of a polymer block mainly composed of a conjugated diene compound by subjecting the block copolymer of the aromatic vinyl compound and the conjugated diene compound to a hydrogenation treatment. The hydrogenation rate is controlled in the range of more than 0 to 100%. A preferable hydrogenation rate of the hydrogenated block copolymer is 80% or more, and most preferably 98% or more.
These block copolymers can be used without any problem as a mixture of a non-hydrogenated block copolymer and a hydrogenated block copolymer.

In addition, these aromatic vinyl compound-conjugated diene compound block copolymers are different in bond type, different in aromatic vinyl compound type, different in conjugated diene compound type, unless contrary to the spirit of the present invention, A mixture of 1,2-bonded vinyl content, 1,2-bonded vinyl content and 3,4-bonded vinyl content, or different aromatic vinyl compound component content may be used. .
Further, the block copolymer used in the present invention may be a block copolymer in which all or part of the block copolymer is modified.
The modified block copolymer as used herein refers to at least one carbon-carbon double bond or triple bond and at least one carboxylic acid group, acid anhydride group, amino group, hydroxyl group in the molecular structure. Alternatively, it refers to a block copolymer modified with at least one modifying compound having a glycidyl group.

  The modified block copolymer can be produced by (1) melt-kneading with a modifying compound at a temperature in the range of the softening point of the block copolymer to 250 ° C. in the presence or absence of a radical initiator. A method of reacting, (2) a method of reacting a block copolymer and a modifying compound in a solution at a temperature below the softening point of the block copolymer in the presence or absence of a radical initiator, and (3) radical initiation. In the presence of the agent, in the absence of the block copolymer at a temperature equal to or lower than the softening point of the block copolymer, a method of reacting without melting the block copolymer and the like, and any of these methods may be used, The method (1) is preferable, and the method (1) performed in the presence of a radical initiator is most preferable.

At least one modification having at least one carbon-carbon double bond or triple bond and at least one carboxylic acid group, acid anhydride group, amino group, hydroxyl group, or glycidyl group in the molecular structure referred to herein. As the compound, the same modified compounds as described in the modified polyphenylene ether can be used.
The blending amount of the elastomer in the present invention is preferably less than 50 parts by mass with respect to 100 parts by mass of the total amount of polyphenylene ether and polyaryl ketone. Although there is no restriction | limiting in particular in the addition method of these elastomers, adding simultaneously with polyphenylene ether is preferable.

In the present invention, (E) an inorganic filler can be further added. Examples of the inorganic filler include glass fiber, metal fiber, carbon fiber, wollastonite, talc, kaolin, mica, and zonotlite. Among these, glass fiber, carbon fiber, wollastonite, talc and the like can be suitably used.
In the present invention, (F) a flame retardant may be further added. As a flame retardant, a silicon compound, a cyclic nitrogen compound, and a phosphorus flame retardant are preferable.
Examples of the silicon compound include, for example, silicone, caged silsesquioxane or a partially cleaved structure thereof, silica and the like.

Silicone is an organosiloxane polymer, which may have a linear structure, a crosslinked structure, or a structure constituted by a certain ratio thereof, or may be a single substance or a mixture thereof. From the viewpoint of flame retardancy and fluidity, a straight chain structure is more preferable. From the viewpoint of flame retardancy and impact resistance, those having a functional group as a terminal group or side chain group in the molecule are preferred. The functional group is particularly preferably an epoxy group or an amino group. Specifically, for example, silicone oil, modified silicone oil, silicone powder manufactured by Toray Dow Corning Silicone Co., Ltd., straight silicone oil manufactured by Shin-Etsu Chemical Co., Ltd., reactive silicone oil, non-reactive silicone oil, silicone powder A KMP series or the like can be used. Either liquid or solid can be used. Those of the liquid form, a viscosity at 25 ° C., preferably 10~10,000 ^(mm 2 / s), more preferably ^{100~8,000 (mm 2 / s),} 500~3,000 (mm 2 / s) is particularly more preferred. The solid particles preferably have an average particle size of 0.1 to 100 μm, more preferably 0.5 to 30 μm, and particularly preferably 0.5 to 5 μm. The silicone is contained in an amount of 0.1 parts by mass or more from the viewpoint of flame retardancy and 10 parts by mass from the viewpoint of rigidity reduction with respect to 100 parts by mass of the total of polyphenylene ether and polyaryl ketone. It is preferable, 0.3-5 mass parts is further more preferable, and 0.5-2 mass parts is especially more preferable.

A cyclic nitrogen compound is a cyclic organic compound containing a nitrogen element. Specifically, melamine derivatives, melamine, melem and melon are preferably used. Of these, melem and melon are preferred from the viewpoint of volatility.
Examples of phosphorus-based flame retardants include red phosphorus, phosphate ester compounds, phosphite ester compounds, phosphazene compounds, and phosphinates. Among these, phosphate ester compounds and phosphinates are more preferable.
Examples of the phosphoric ester compound include mono-organic phosphorus compounds and organic phosphorus compound oligomers such as triphenyl phosphate and tricresyl phosphate, and organic phosphorus compound oligomers are particularly preferable.
Particularly preferred examples of the organophosphorus compound oligomer include those selected from the group of compounds represented by the following formula (4).

(In the formula, Q ₁ , Q ₂ , Q ₃ and Q ₄ represent an alkyl group having 1 to 6 carbon atoms or hydrogen, n is an integer of 1 or more, and m ₁ , m ₂ , m ₃ and m ₄ are 0. To X, and X is selected from any of the following formulas (5).)

_{(Wherein, S 1, S 2, S} 3 is _{.n 1, n 2,} n ₃ represents methyl group or hydrogen is an integer from 0 to 2.)
Specifically, CR-741, CR-747, CR-733S manufactured by Daihachi Chemical Co., Ltd. are suitable.
As the phosphinic acid salts, at least one phosphinic acid selected from phosphinic acid salts represented by the following formula (6) and / or diphosphinic acid salts represented by the following formula (7), or condensates thereof: Salts are preferred.

Wherein R ¹ and R ² are the same or different and are linear or branched C ₁ -C ₆ -alkyl and / or aryl or phenyl, and R ³ is linear or branched C ₁ -C ₁₀ -alkylene, C ₆ -C ₁₀ -arylene, C ₆ -C ₁₀ -alkylarylene or C ₆ -C ₁₀ -arylalkylene, M is calcium (ion), magnesium (ion), aluminum ( Ion), zinc (ion), bismuth (ion), manganese (ion), sodium (ion), potassium (ion), and protonated nitrogen base, and m is 2 or 3 , N is 1 to 3, and x is 1 or 2.)

The phosphinates may be mixed in any composition as long as the effects of the present invention are not impaired. From the viewpoint of flame retardancy and suppression of mold deposit, the phosphine represented by the above (4) It is preferable to contain 90% by mass or more, more preferably 95% by mass or more, and most preferably 98% by mass or more of the acid salt.
Specific examples of phosphinic acid that can be preferably used in the present invention include dimethylphosphinic acid, ethylmethylphosphinic acid, diethylphosphinic acid, methyl-n-propylphosphinic acid, methandi (methylphosphinic acid), benzene-1,4- (Dimethylphosphinic acid), methylphenylphosphinic acid, diphenylphosphinic acid, and mixtures thereof.
The metal component that can be preferably used is at least one selected from calcium ions, magnesium ions, aluminum ions, zinc ions, bismuth ions, manganese ions, sodium ions, potassium ions) and / or protonated nitrogen bases. More preferably, it is at least one selected from calcium ions, magnesium ions, aluminum ions, and zinc ions.

  Specific examples of phosphinates that can be preferably used include calcium dimethylphosphinate, magnesium dimethylphosphinate, aluminum dimethylphosphinate, zinc dimethylphosphinate, calcium ethylmethylphosphinate, magnesium ethylmethylphosphinate, aluminum ethylmethylphosphinate , Zinc ethylmethylphosphinate, calcium diethylphosphinate, magnesium diethylphosphinate, aluminum diethylphosphinate, zinc diethylphosphinate, calcium methyl-n-propylphosphinate, magnesium methyl-n-propylphosphinate, methyl-n-propyl Aluminum phosphinate, zinc methyl-n-propylphosphinate, calcium methanedi (methylphosphinate), meta Di (methylphosphinic acid) magnesium, methanedi (methylphosphinic acid) aluminum, methanedi (methylphosphinic acid) zinc, benzene-1,4- (dimethylphosphinic acid) calcium, benzene-1,4- (dimethylphosphinic acid) magnesium, Benzene-1,4- (dimethylphosphinic acid) aluminum, benzene-1,4- (dimethylphosphinic acid) zinc, calcium methylphenylphosphinate, magnesium methylphenylphosphinate, aluminum methylphenylphosphinate, zinc methylphenylphosphinate, Examples include calcium diphenylphosphinate, magnesium diphenylphosphinate, aluminum diphenylphosphinate, and zinc diphenylphosphinate.

Calcium dimethylphosphinate, aluminum dimethylphosphinate, zinc dimethylphosphinate, calcium ethylmethylphosphinate, aluminum ethylmethylphosphinate, zinc ethylmethylphosphinate, calcium diethylphosphinate especially from the viewpoint of flame retardancy and mold deposit control Aluminum diethylphosphinate and zinc diethylphosphinate are preferred. Of these, aluminum diethylphosphinate is particularly preferable.
In consideration of the mechanical strength and the appearance of the molded product obtained by molding the resin composition of the present invention, the preferred lower limit of the average particle diameter of phosphinates is 0.5 μm. A more preferred lower limit is 1.0 μm, and a most preferred lower limit is 2 μm. The upper limit of the average particle diameter of phosphinic acid salts is preferably 40 μm, more preferably 20 μm, still more preferably 15 μm, and most preferably 10 μm.

By setting the number average particle diameter of the phosphinates to 0.5 μm or more, handling properties and biting into an extruder are improved during processing such as melt kneading. Moreover, it is preferable that the average particle diameter is 40 μm or less because the mechanical strength of the resin composition is easily developed and the good surface appearance of the molded product is improved.
The average particle size of the phosphinates can be measured and analyzed by dispersing the phosphinates in water using a laser diffraction particle size distribution analyzer (for example, trade name: SALD-2000, manufactured by Shimadzu Corporation). The method for dispersing water in phosphinates can be achieved by adding water and phosphinates to an ultrasonic diffuser and / or a stirrer equipped with a stirrer. This dispersion is sent to a measurement cell of a laser diffraction particle size distribution meter via a pump, and the particle diameter is measured by laser diffraction. The number average particle size can be calculated from the frequency distribution of the particle size and the number of particles obtained by measurement.

In the phosphinic acid salts in the present invention, unreacted products or by-products may remain as long as the effects of the present invention are not impaired.
The compounding amount of these phosphorus-based flame retardants is 0.1 parts by mass or more from the viewpoint of flame retardancy and 10 parts by mass from the viewpoint of heat resistance with respect to 100 parts by mass in total of polyphenylene ether and polyaryl ketone. It is preferably contained in a proportion of not more than 1 part, more preferably 1 to 8 parts by mass, particularly preferably 3 to 5 parts by mass.
In the present invention, in addition to the above-described components, additional components may be added as necessary within a range not impairing the effects of the present invention.

Examples of additional components are listed below.
Conductivity imparting materials (conductive carbon black, carbon nanotubes, etc.), plasticizers (oil, low molecular weight polyolefin, polyethylene glycol, fatty acid esters, etc.), antistatic agents, various peroxides, zinc sulfide, antioxidants, UV absorbers, light stabilizers, colorants and the like.
Specific processing machines for obtaining the composition of the present invention include, for example, a single screw extruder, a twin screw extruder, a roll, a kneader, a Brabender plastograph, a Banbury mixer, etc. Machine is preferred.

A preferable production method of the present invention includes a method of using a twin screw extruder equipped with an upstream supply port, supplying polyphenylene ether and polyaryl ketone from the upstream supply port, and melt-kneading. Is not to be done.
In this invention, the preferable temperature for manufacturing a resin composition can be arbitrarily selected from the range of 345-380 degreeC. Among these, a range of 350 to 370 ° C. is more preferable.
The composition of the present invention thus obtained can be molded as a molded body of various parts by various conventionally known methods such as injection molding.
These various parts include, for example, internal parts of hard disks used in digital home appliances such as personal computers, hard disk DVD drive recorders, digital video cameras, portable digital music players, mobile phones, and various computers and peripheral devices. Suitable for parts, IC tray materials, chassis for various disc players, electrical / electronic parts such as cabinets, electrical parts for motorcycles and automobiles represented by relay block materials, etc., heat-resistant parts for automobiles or heat-resistant parts for office equipment . Among them, it is suitably used as an internal part of a hard disk that requires precision molding.

Examples of the internal parts of the hard disk include a bracket, a latch, a comb, a spoiler, a bush, a mount plate, and a hook.
Automotive heat-resistant parts include, for example, alternator terminals, alternator connectors, IC regulators, light meter potentiometer bases, various valves such as exhaust gas valves, engine coolant joints, carburetor main bodies, carburetor spacers, exhaust gas sensors, coolant sensors, Oil temperature sensor, brake pad wear sensor, throttle position sensor, crankshaft position sensor, air flow meter, brake butt wear sensor, thermostat base for air conditioner, heating hot air flow control valve, brush holder for radiator motor, water pump impeller, turbine Bain, wiper motor related parts, distributor, starter switch, switch Motor relays, transmission wire harnesses, window washer nozzles, air conditioner panel switch boards, coils for fuel-related electromagnetic valves, fuse connectors, horn terminals, electrical component insulation plates, step motor rotors, brake pistons, solenoid bobbins, ignition device cases, etc. Parts, wheel caps, lamp sockets, lamp housings, lamp extensions, lamp reflectors and the like are suitable.

Heat-resistant parts for office equipment include, for example, homes such as air conditioner parts, typewriter parts, word processor parts, office electrical product parts, office computer-related parts, telephone-related parts, facsimile-related parts, copier-related parts, etc. It is suitable for.
Further, the composition of the present invention can be formed into a sheet by, for example, extrusion sheet forming. The sheet referred to here is one having a thickness of 0.001 to 2.0 mm, and examples of a method for producing these sheets include an extruded tubular method (sometimes called an inflation method), a T-die extrusion method, and the like. Is mentioned.
The sheet thus obtained can be suitably used for applications requiring flame retardancy and electrical characteristics, such as printed circuit board materials, printed circuit board peripheral parts, printed circuit board release films, semiconductor packages, data-based magnetic tapes, APS photographic film, film capacitors, insulation materials such as motors and transformers, speaker diaphragms, automotive sheet sensors, wire cable insulation tape, TAB tape, generator slot liner interlayer insulation materials, toner agitators, lithium ion batteries, etc. Suitable for washer and the like.

EXAMPLES Hereinafter, although an Example and a comparative example demonstrate this invention further in detail, this invention is not limited to what was shown by this Example.
(Raw materials used)
(1) Polyphenylene ether (hereinafter abbreviated as PPE-1)
Poly (2,6-dimethyl-1,4-phenylene ether)
Reduced viscosity: 0.42 dl / g, (0.5 g / dl, chloroform solution, measured at 30 ° C.)
(2) Polyphenylene ether modified with an epoxy group-containing compound Obtained by the method described later.
(3) Polyaryl ketone (3-1) Product name: VICTREX PEEK 151G (registered trademark) (manufactured by Victrex) (hereinafter abbreviated as PAK-1)
(3-2) Product name: VICTREX PEEK 90G (registered trademark) (manufactured by Victrex) (hereinafter abbreviated as PAK-2)
(4) Epoxy compound (4-1) Novolak type epoxy resin (hereinafter abbreviated as EP-1)
Product name: EPICLON N-695 (registered trademark) (Dainippon Ink Co., Ltd.)
(4-2) Styrene / glycidyl methacrylate copolymer (hereinafter abbreviated as EP-2)
Product name: Marble G-1005S (registered trademark) (manufactured by NOF Corporation)

(5) Flame retardant Aluminum diethylphosphinate (hereinafter abbreviated as DEP) was produced with reference to the production methods described in Examples of JP-A-2005-179362.
The DEP mass was wet-ground in water and classified to obtain DEP having an average particle size of 3.3 μm.
(Reference Example-1: Production method of polyphenylene ether resins [E-PPE-1] and [E-PPE-2] modified with an epoxy group compound)
450 g of the above-mentioned [PPE-1] is dissolved in 1300 g of toluene, and the solution is put into a 10 L container having a cooling pipe on the top and heated with oil set at 120 ° C. In advance, 200 g of the above-mentioned [EP-1] is dissolved in 500 g of toluene and added to the toluene solution of [PPE-1] with stirring. After reacting for 2 hours with stirring, the temperature was lowered to 50 ° C., 5400 g of methanol was gradually added, the precipitate was filtered through a filter, dispersed in 1000 g of methanol, and washed and filtered at 50 ° C. for 30 minutes. After being repeated, it was dried under reduced pressure at 140 ° C. for 8 hours to obtain [E-PPE-1]. When the modification rate of the obtained [E-PPE-1] was measured by the following method, it was 30%.

Here, the modification rate is the ratio of the epoxy-modified hydroxyl group in the molecular chain terminal phenolic hydroxyl group of [PPE-1], for example, the average molecular chain terminal phenolic per molecule of [PPE-1]. From the number of hydroxyl groups (Np (number / polyphenylene ether single molecular chain)) and the average number of terminal phenolic hydroxyl groups (Nq (number / polyphenylene ether single molecular chain)) per molecule of [E-PPE-1], It can be obtained by the following mathematical formula.
(Modification rate) = [(Np−Nq) / Np] × 100 (%)
Np and Nq are a collection of polymer papers, vol. 51, no. 7 (1994), according to the method described on page 480, the methylene chloride solution adjusted so that [PPE-1] is 0.2 g / L and the [E-PPE-1] is adjusted to 0.2 g / L. It calculates from the value which measured the absorbance change in 318 nm when a 10 wt% tetramethylammonium hydroxide solution was added to the methylene chloride solution, respectively, and the value of the number average molecular weight of (A) polyphenylene ether. be able to.

In the same manner, the reaction time was 5 hours to obtain [E-PPE-2]. The modification rate was 58%.
(Reference Example-2: Production method of polyphenylene ether resin [E-PPE-3] modified with an epoxy group compound)
A twin screw extruder having an upstream supply port in the first barrel from the upstream side of the extruder and having L / D (extruder cylinder length / extruder cylinder diameter) = 44 (number of barrels: 11) [ ZSK-25: manufactured by Coperion (Germany)], the upstream feed port to the die is set to 320 ° C., the screw rotation speed is 300 rpm, the discharge rate is 12 kg / h, and [PPE-1] and [EP- 1] was supplied from the upstream supply port so as to be a ratio of 10: 1, and melt kneaded to prepare [E-PPE-3]. Since the obtained pellet had 7% insoluble matter in methylene chloride, the modification rate could not be measured accurately.

(Evaluation methods)
The evaluation method is described below.
<Heat resistance: deflection temperature under load>
The resin composition pellets obtained in Examples and Comparative Examples were dried at 100 ° C. for 3 hours using a dryer, and an injection speed of 700 mm / second was used using an injection molding machine [IS-80EPN: manufactured by Toshiba Machine Co., Ltd.]. A holding pressure of 60 MPa, an injection + holding time of 10 seconds, and a cooling time of 15 seconds were set, and a 127 × 13 × 3.2 mm molded piece was formed under the temperature setting conditions described in Table 1. Based on ASTM D648, the deflection temperature under load was measured at 1.82 MPa using the obtained test piece.

<Chemical resistance 1: Critical strain>
Using the molded piece, the critical strain value for crack generation with respect to linoleic acid was measured under the conditions of 23 ° C. and 72 hours by the bending foam method.
<Chemical resistance 2: Crack generation>
The molded piece was fixed using a bending die with a strain of 1%, immersed in cyclohexane, and the occurrence of cracks under conditions of 23 ° C. and 72 hours was evaluated.
<Chemical resistance 3: Weight change rate>
The resin composition pellets obtained in Examples and Comparative Examples were dried at 100 ° C. for 3 hours using a dryer, and an injection speed of 700 mm / second was used using an injection molding machine [IS-80EPN: manufactured by Toshiba Machine Co., Ltd.]. The holding pressure was set to 60 MPa, the injection + holding time was 10 seconds, and the cooling time was 15 seconds. Under the temperature setting conditions shown in Table 1, a 90 × 50 × 2 mm molded piece was formed. Four sides of the obtained test piece were cut to cut out 20 × 20 × 2 mm. This cut piece was immersed in 20 ml of chloroform for 24 hours, and the weight change before and after immersion was measured. The weight change rate was calculated according to the following formula.
(Weight change rate) = {(weight before immersion) − (weight after immersion)} / weight before immersion × 100

<Electrical characteristics>
The resin composition pellets obtained in the examples and comparative examples were dried at 100 ° C. for 3 hours using a dryer, and manufactured by Technobel, T-die film forming machine with a 15 mm 2-axis co-rotating extruder (KZW15TW). The dry pellets are supplied from the first supply port, and while blowing nitrogen, the cylinder set temperature from the first supply port side to the T die is set to 320/360/360 ° C., and the T die is set. The temperature was set to 360 ° C., the cast roll temperature was set to 170 ° C., and the supply amount and the take-up speed were adjusted while drawing a vacuum vent to obtain a film having a thickness of about 100 μm.
The obtained film having a thickness of 100 μm was cut into a 5 cm × 9 cm square, and this was used to test the dielectric constant (hereinafter abbreviated as “ε”) and dielectric using a test method (a method of bonding aluminum foil) in accordance with JIS-K6911. The tangent (hereinafter abbreviated as “tan δ”) was measured. The measuring device used was 4284A manufactured by Agilent. The measurement atmosphere temperature was 22 ° C. and the measurement frequency was 1 MHz.

<Flame retardance>
The resin composition pellets obtained in the examples were dried at 100 ° C. for 3 hours using a dryer, and an injection speed of 700 mm / second, pressure holding using an injection molding machine [IS-80EPN: manufactured by Toshiba Machine Co., Ltd.] A molded piece of 127 × 13 × 1.6 mm was molded at 100 MPa, injection + pressure holding time 10 seconds, cooling time 15 seconds, mold temperature 170 ° C., molten resin temperature 370 ° C. Using the obtained test piece, based on UL-94 (American Underwriters Laboratory Standard), each of the five test pieces was flame contacted twice, and a total of 10 burning times were measured and judged. .

[Examples 1 and 2, Comparative Example 1]
A twin screw extruder having an upstream supply port in the first barrel from the upstream side of the extruder and having L / D (extruder cylinder length / extruder cylinder diameter) = 44 (number of barrels: 11) [ ZSK-25: manufactured by Coperion (Germany)], from the upstream supply port to the die is set to 360 ° C., the screw rotation speed is 300 rpm, the discharge rate is 12 kg / h, and the ratio described in Table 1 is obtained. The raw material was supplied from the upstream supply port and melt kneaded to prepare resin composition pellets. The obtained resin composition was evaluated for deflection temperature under load and chemical resistance (critical strain). The physical property values are shown together with the composition in Table 1. In Examples 1 and 2, polyphenylene ether was a continuous phase and polyether ether ketone was a dispersed phase.

[Examples 3 to 9, Comparative Example 2]
A twin screw extruder having an upstream supply port in the first barrel from the upstream side of the extruder and having L / D (extruder cylinder length / extruder cylinder diameter) = 44 (number of barrels: 11) [ ZSK-25: manufactured by Coperion (Germany)], from the upstream supply port to the die is set to 360 ° C., the screw rotation speed is 300 rpm, the discharge rate is 12 kg / h, and the ratio shown in Table 2 is obtained. The raw material was supplied from the upstream supply port and melt kneaded to prepare resin composition pellets. The obtained resin composition was evaluated for deflection temperature under load and chemical resistance (crack generation, weight change rate). Moreover, regarding Example 4 and Comparative Example 2, the electrical characteristics were also evaluated. The physical property values are shown together with the composition in Table 2. In Examples 3 to 9, polyphenylene ether was the dispersed phase and polyether ether ketone was the continuous phase.

[Examples 10 and 11]
A twin screw extruder having an upstream supply port in the first barrel from the upstream side of the extruder and having L / D (extruder cylinder length / extruder cylinder diameter) = 44 (number of barrels: 11) [ ZSK-25: manufactured by Coperion (Germany)], from the upstream supply port to the die is set to 360 ° C., the screw rotation speed is 300 rpm, the discharge rate is 12 kg / h, and the ratio described in Table 3 is obtained. The raw material was supplied from the upstream supply port and melt kneaded to prepare resin composition pellets. The obtained resin composition was evaluated for deflection temperature under load, chemical resistance (weight change rate) and flame retardancy. The physical property values are shown together with the composition in Table 3.

  The thermoplastic resin composition of the present invention and a molded body made of the resin composition can be used in a wide range of fields such as electric / electronic parts, OA parts, vehicle parts, and machine parts. It can be suitably used for electrical / electronic parts.

Claims (15)

  A thermoplastic resin composition comprising (A) a polyphenylene ether resin and (B) a polyaryl ketone resin.   (A) The thermoplastic resin composition according to claim 1, wherein part or all of the polyphenylene ether resin is a polyphenylene ether resin modified with an epoxy group-containing compound.   Furthermore, the thermoplastic resin composition of Claim 1 or 2 which contains 0.1-10 mass parts of (C) epoxy compounds with respect to a total of 100 mass parts of (A) component and (B) component.   (A) The thermoplastic resin composition according to claim 2 or 3, wherein the polyphenylene ether resin modified with the epoxy group-containing compound has a modification rate of 0.1 to 50%.   (A) The thermoplastic resin composition according to any one of claims 2 to 4, wherein the polyphenylene ether resin modified with the epoxy group-containing compound is modified at a temperature lower than the glass transition temperature of the polyphenylene ether resin.   The thermoplastic resin composition according to any one of claims 1 to 5, wherein the component (A) is 1 to 49 parts by mass, and the component (B) is 51 to 99 parts by mass.   The thermoplastic resin composition according to any one of claims 1 to 6, wherein the component (A) forms a dispersed phase and the component (B) forms a continuous phase.   (B) Component is polyetheretherketone resin, The thermoplastic resin composition of any one of Claims 1-7.   The thermoplastic resin composition according to any one of claims 3 to 8, wherein (C) the epoxy compound is a copolymer of an unsaturated monomer having a glycidyl group and a monomer containing styrene as a main component.   (D) The thermoplastic resin composition according to any one of claims 1 to 9, comprising an elastomer.   The thermoplastic resin composition according to claim 10, wherein component (D) is a hydrogenated product of a block copolymer comprising a polymer block mainly comprising an aromatic vinyl compound and a polymer block mainly comprising a conjugated diene compound. .   (E) The thermoplastic resin composition according to any one of claims 1 to 11, comprising an inorganic filler.   (F) The thermoplastic resin composition according to any one of claims 1 to 12, comprising a flame retardant.   An injection-molded article comprising the thermoplastic resin composition according to any one of claims 1 to 13.   The sheet | seat which consists of a thermoplastic resin composition of any one of Claims 1-13.