JP2017082044A - Thermoplastic resin composition and connection structure for solar power generation module using the same - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a thermoplastic resin composition having fire resistance, mechanical property, and heat resistance, as well as tracking resistance allowing insulation distance reduction.SOLUTION: There are provided a thermoplastic resin composition containing 100 pts.mass of (A) a polyphenylene ether resin composition and 0.05 to 3 pts.mass of (B) one or more metal halide compound selected from a group consisting of a barium halide compound and a silver halide compound, and a connection structure for solar power generation module using the thermoplastic resin composition.SELECTED DRAWING: None

Description

  The present invention relates to a thermoplastic resin composition containing a polyphenylene ether resin.

  Polyphenylene ether-based resin composition based on polyphenylene ether has excellent characteristics such as electrical properties, dimensional stability, impact resistance, acid resistance, and alkali resistance, low water absorption, and low specific gravity. ing.

  Therefore, the polyphenylene ether-based resin composition is widely used for various electric / electronic parts, office equipment parts, automobile parts, building materials, other various exterior materials, industrial products, and the like.

  In recent years, insulating resin moldings used in electrical parts that require electrical insulation characteristics typified by tracking resistance performance are not only superior in insulation properties, but also have excellent flame resistance, mechanical properties, resistance to resistance. It is also required to have impact characteristics and long-term heat resistance.

  As what solves such a problem, what mix | blended specific amount polyphenylene ether, styrene resin, and hydrogenated block copolymer (patent document 1) etc. are illustrated.

International Publication No. 2010/047122

  In recent years, the usage forms of insulating resin moldings used in electrical parts in the electrical energy field have been widespread, such as solar cells, fuel cells and storage batteries, electric vehicles, LED lighting, and smart meters. There is an increasing demand for miniaturization and multifunctional parts.

  On the other hand, in the insulating resin molded body incorporated in the electrical component, in order to avoid malfunction due to tracking, it is sufficient between the live parts and between the live part and the outer surface part of the insulating resin molded body. It is necessary to ensure a sufficient insulation distance.

For this reason, it is desirable that the insulating resin molded body has sufficient insulating properties even when it is intended to achieve miniaturization and multi-functionalization of electrical components.
And the above-mentioned conventional insulation resin molding had room for improvement about various performances which enable sufficient insulation in a small and multifunctional electronic component.

  The present invention has been made in view of the above circumstances, and provides a thermoplastic resin composition having flame resistance, mechanical properties, and heat resistance, and also having tracking resistance capable of reducing an insulation distance. The purpose is to do.

  As a result of intensive studies to solve the above problems, the present inventors use a molded body of a thermoplastic resin composition in which a metal halide compound is added to a polyphenylene ether-based resin as an insulating resin molded body in contact with the live part. Thus, in addition to maintaining the conventional excellent resin performance, it has been found that the effect of dramatically improving tracking resistance can be obtained, and the present invention has been completed.

・・・・・・（１）
（式（１）中、Ｒ^a、Ｒ^b、Ｒ^c、及びＲ^dは、それぞれ独立して、アリール基であり、ここで、アリール基の１つ以上の水素が置換されていても置換されていなくてもよく；ｎは、自然数であり；Ｘは、フェノール類より誘導される２価の芳香族基であり；ｊ、ｋ、ｌ、及びｍは、それぞれ独立して、０又は１である。）

・・・・・・（２）
［式中、Ｒ¹¹及びＲ¹²は、各々独立して、直鎖状若しくは分岐状の炭素原子数１〜６のアルキル基及び／又は炭素原子数６〜１０のアリール基であり；Ｍ¹は、カルシウムイオン、マグネシウムイオン、アルミニウムイオン、亜鉛イオン、ビスマスイオン、マンガンイオン、ナトリウムイオン、カリウムイオン、及びプロトン化された窒素塩基からなる群より選ばれる少なくとも１種であり；ａは、１〜３の整数であり；ｍは、１〜３の整数であり；ａ＝ｍである］

・・・・・・（３）
［式中、Ｒ²¹及びＲ²²は、各々独立して、直鎖状若しくは分岐状の炭素原子数１〜６のアルキル基及び／又は炭素原子数６〜１０のアリール基であり；Ｒ²³は、直鎖状若しくは分岐状の炭素原子数１〜１０のアルキレン基、炭素原子数６〜１０のアリーレン基、炭素原子数６〜１０のアルキルアリーレン基又は炭素原子数６〜１０のアリールアルキレン基であり；Ｍ²は、カルシウムイオン、マグネシウムイオン、アルミニウムイオン、亜鉛イオン、ビスマスイオン、マンガンイオン、ナトリウムイオン、カリウムイオン、及びプロトン化された窒素塩基からなる群より選ばれる少なくとも１種であり；ｂは、１〜３の整数であり；ｎは、１〜３の整数であり；ｊは、１又は２の整数であり；ｂ・ｊ＝２ｎである］
［６］［１］〜［５］のいずれかに記載の熱可塑性樹脂組成物からなることを特徴とする、太陽光発電モジュール用接続構造体。
［７］［１］〜［５］のいずれかに記載の熱可塑性樹脂組成物からなることを特徴とする、太陽光発電モジュール用ジャンクションボックス。
［８］［１］〜［５］のいずれかに記載の熱可塑性樹脂組成物からなることを特徴とする、太陽光発電モジュール用コネクタ。 That is, the present invention is as follows.
[1] (A) One or more metal halide compounds selected from the group consisting of (B) a barium halide compound and a silver halide compound with respect to 100 parts by mass of the polyphenylene ether-based resin composition 0.05 to A thermoplastic resin composition comprising 3 parts by mass.
[2] When the total of (A) polyphenylene ether-based resin composition is 100 parts by mass of (a1) component, (a2) component, (a3) component, and (a4) component, (a1) polyphenylene ether 50 1 to 80 parts by mass, (a2) 0 to 25 parts by mass of a styrene resin, (a3) 1 to 25 parts by mass of a hydrogenated block copolymer, (a4) 2 to 30 parts by mass of an organophosphorus compound, [1 ] The thermoplastic resin composition as described in.
[3] The thermoplastic resin composition according to [1] or [2], further including (C) one or more colorants selected from the group consisting of organic pigments, inorganic pigments, and organic dyes.
[4] The thermoplastic resin according to [3], wherein the component (C) is carbon black, and the content of the carbon black in the thermoplastic resin composition is 0.01 to 2% by mass. Composition.
[5] The (a4) organophosphorus compound is represented by a phosphoric acid ester compound represented by the following general formula (1), a phosphinic acid salt represented by the following general formula (2), and the following general formula (3). The thermoplastic resin composition according to [2], which is at least one selected from the group consisting of diphosphinic acid salts.

(1)
(In formula (1), R ^a , R ^b , R ^c , and R ^d are each independently an aryl group, where one or more hydrogen atoms in the aryl group are substituted. N is a natural number; X is a divalent aromatic group derived from phenols; j, k, l, and m are each independently 0 or 1; is there.)

(2)
Wherein, R ¹¹ and R ¹² are each independently a straight-chain or branched alkyl and / or aryl group having 6 to 10 carbon atoms having from 1 to 6 carbon atoms; M ¹ is A calcium ion, a magnesium ion, an aluminum ion, a zinc ion, a bismuth ion, a manganese ion, a sodium ion, a potassium ion, and a protonated nitrogen base; M is an integer of 1 to 3; a = m]

(3)
Wherein, R ²¹ and R ²² are each independently a linear or branched alkyl and / or aryl group having 6 to 10 carbon atoms having from 1 to 6 carbon atoms; R ²³ is A linear or branched alkylene group having 1 to 10 carbon atoms, an arylene group having 6 to 10 carbon atoms, an alkylarylene group having 6 to 10 carbon atoms, or an arylalkylene group having 6 to 10 carbon atoms. Yes; M ² is at least one selected from the group consisting of calcium ions, magnesium ions, aluminum ions, zinc ions, bismuth ions, manganese ions, sodium ions, potassium ions, and protonated nitrogen bases; b Is an integer of 1 to 3; n is an integer of 1 to 3; j is an integer of 1 or 2; b · j = 2n]
[6] A connection structure for a photovoltaic power generation module, comprising the thermoplastic resin composition according to any one of [1] to [5].
[7] A junction box for photovoltaic modules, comprising the thermoplastic resin composition according to any one of [1] to [5].
[8] A photovoltaic module connector comprising the thermoplastic resin composition according to any one of [1] to [5].

  According to the present invention, a thermoplastic resin composition excellent in tracking resistance can be obtained while maintaining excellent flame retardancy, impact resistance and heat resistance.

  Hereinafter, a mode for carrying out the present invention (hereinafter referred to as “the present embodiment”) will be described in detail. The following embodiments are examples for explaining the present invention, and are not intended to limit the present invention to the following contents. The present invention can be appropriately modified within the scope of the gist.

(Thermoplastic resin composition)
The thermoplastic resin composition of the present embodiment comprises (B) one or more selected from the group consisting of a barium halide compound and a silver halide compound with respect to 100 parts by mass of the (A) polyphenylene ether-based resin composition. Contains 0.05 to 3 parts by weight of a metal halide compound.

-(A) Polyphenylene ether resin composition-
The (A) polyphenylene ether-based resin composition in the present embodiment has (a1) polyphenylene ether 50 when the total of the (a1) component, (a2) component, (a3) component, and (a4) component is 100 parts by mass. -80 parts by mass, (a2) 0-25 parts by mass of a styrene resin, (a3) 1-25 parts by mass of a hydrogenated block copolymer, and (a4) 2-30 parts by mass of an organophosphorus compound. It is preferable.

-(A1) Polyphenylene ether-
Examples of (a1) polyphenylene ether include, but are not limited to, poly (2,6-dimethyl-1,4-phenylene ether) and 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. Further, a copolymer of 2,6-dimethylphenol and other phenols (for example, 2,6-dimethylphenol and 2,3,6-trimethylphenol described in JP-B-52-018880) And a polyphenylene ether copolymer such as a copolymer of 2,6-dimethylphenol and 2-methyl-6-butylphenol).
Among these, from the viewpoint of mechanical strength, poly (2,6-dimethyl-1,4-phenylene ether), a copolymer of 2,6-dimethylphenol and 2,3,6-trimethylphenol, Mixtures are preferred.
These may be used alone or in combination of two or more.

(A1) The manufacturing method of polyphenylene ether is not specifically limited, A well-known method is also employable.
Specific examples include, for example, U.S. Pat. No. 3,306,874, U.S. Pat. No. 3,306,875, U.S. Pat. No. 3,257,357, U.S. Pat. No. 3,257,358, JP-A-50-051197, and JP-B-52- And the production methods described in Japanese Patent No. 017880 and Japanese Patent Laid-Open No. 63-152628.

(A1) The lower limit of the reduced viscosity of polyphenylene ether (measured using 0.5 g / dL chloroform solution, 30 ° C., Ubbelohde viscometer) is preferably 0.30 dL / g or more, 0.35 dL / G or more is more preferable, and 0.38 dL / g or more is still more preferable. The upper limit of the reduced viscosity of the polyphenylene ether is preferably 0.80 dL / g or less, more preferably 0.75 dL / g or less, and further preferably 0.55 dL / g or less.
The combination of the lower limit and the upper limit of the reduced viscosity of the polyphenylene ether is preferably 0.30 to 0.80 dL / g, more preferably 0.35 to 0.75 dL / g, and More preferably, it is 38-0.55 dL / g. (A1) When the reduced viscosity of the polyphenylene ether is within the above range, impact resistance and heat resistance are further improved.
(A1) The polyphenylene ether may be a mixture of two or more polyphenylene ethers having different reduced viscosities. (A1) The reduced viscosity of polyphenylene ether can be controlled by production conditions such as the amount of catalyst during polymerization and the polymerization time.

・・・・・・（４）
（式（４）中、２つのＲ₁、２つのＲ₂は、それぞれ独立して、水素原子又は炭素数１〜３のアルキル基である、但し、２つのＲ₁が共に水素原子であることはない。） In the (a1) polyphenylene ether of the present embodiment, the concentration of the terminal hydroxyl group-containing portion represented by the following general formula (4) (hereinafter, also simply referred to as “hydroxyl concentration”) is a monomer constituting the polyphenylene ether. 0.5 or more is preferable per 100 units, and 0.7 or more is more preferable.

(4)
(In formula (4), two R ₁ and two R ₂ are each independently a hydrogen atom or an alkyl group having 1 to 3 carbon atoms, provided that both R ₁ are both hydrogen atoms. No.)

  The hydroxyl group concentration is a value measured with a U3310 type spectrophotometer manufactured by Hitachi High-Technology Co., Ltd. based on the method described in Journal of Applied Polymer Science: Applied Polymer Symposium 34, 103-117 (1978). The unit is the number of hydroxyl groups per 100 monomer units constituting the polyphenylene ether.

The hydroxyl group concentration of polyphenylene ether varies depending on the conditions for polymerizing the phenolic compound and the conditions for the quinone reaction after termination of the polymerization.
As an example of polymerization, poly (2,6-dimethyl-1,4-phenylene) ether is described in JP-A Nos. 2000-28176 and 2000-281778. The amount of quinone compound produced varies depending on the amount of phenol added and the time. Generally, the greater the amount to be added and the shorter the addition time, the greater the amount of quinone compound produced. In the quinone reaction after the termination of the polymerization, the terminal hydroxyl group concentration varies depending on the temperature and time. The higher the temperature and the longer the time, the higher the hydroxyl group concentration. In the present invention, the conditions for polymerizing the phenolic compound and the conditions for the quinone reaction after the termination of the polymerization are not limited. By generally adding a quinone compound to PPE obtained by polymerization, a quinone reaction is carried out. The hydroxyl group concentration can also be increased.

  The polyphenylene ether-based resin composition is often colored black when used as an electrical component that requires electrical insulation characteristics. However, when coloring with carbon black and other organic pigments and inorganic pigments, poor color tone may occur when processed into a molded product (parts of different color tone may occur near the weld of the molded product). is there. When the hydroxyl group concentration of polyphenylene ether is 0.5 or more per 100 monomer units, the effect of suppressing the occurrence of this poor color tone can be obtained.

  In the present embodiment, in the (A) polyphenylene ether-based resin composition, the copper content attributable to the residual catalyst is preferably 2.0 ppm or less based on the weight of the (a1) polyphenylene ether. When the copper content of polyphenylene ether exceeds 2.0 ppm, the thermal stability of the resin composition is lowered, and when it is exposed to a high temperature for a long time, the impact strength may be lowered. (A1) The copper content of the polyphenylene ether is preferably 1.0 ppm or less, more preferably 0.5 ppm or less.

  In this embodiment, in order to stabilize (a1) polyphenylene ether, various known stabilizers may be added to the thermoplastic resin composition. Examples of the stabilizer include metal stabilizers such as zinc oxide and zinc sulfide; organic stabilizers such as hindered phenol stabilizers, phosphorus stabilizers, and hindered amine stabilizers. The content of the stabilizer is preferably less than 5 parts by mass with respect to 100 parts by mass of (a1) polyphenylene ether.

  Furthermore, in the present embodiment, in addition to the stabilizer described above, other additives that can be added to (a1) polyphenylene ether can also be added to the thermoplastic resin composition. In that case, the total content of other additives is preferably less than 10 parts by mass with respect to 100 parts by mass of (a1) polyphenylene ether.

--Modified polyphenylene ether--
In the present embodiment, a modified polyphenylene ether obtained by modifying a part or all of the polyphenylene ether with an unsaturated carboxylic acid or a derivative thereof can be used as the (a1) polyphenylene ether.
This modified polyphenylene ether is disclosed in JP-A-2-276823 (US Pat. No. 5,159,027, US Reissue Patent No. 35695), JP-A 63-108059 (US Pat. No. 5,214,109). No. 5216089), JP-A-59-59724, and the like.

  The modified polyphenylene ether can be produced, for example, by melting and kneading an unsaturated carboxylic acid or a derivative thereof with polyphenylene ether in the presence or absence of a radical initiator. Or it can manufacture by dissolving polyphenylene ether, unsaturated carboxylic acid, and its derivative (s) in the organic solvent in the presence or absence of a radical initiator, and making it react under a solution.

  Examples of the unsaturated carboxylic acid or derivative thereof include, but are not limited to, maleic acid, fumaric acid, itaconic acid, halogenated maleic acid, cis-4-cyclohexene-1,2-dicarboxylic acid. , Endo-cis-bicyclo (2,2,1) -5-heptene-2,3-dicarboxylic acid, etc .; acid anhydrides, esters, amides, imides, etc. of these dicarboxylic acids; and further acrylic acid, methacrylic acid And esters of these monocarboxylic acids, amides, and the like.

  Further, in the production of the modified polyphenylene ether, even if it is a saturated carboxylic acid, it itself thermally decomposes at the reaction temperature at the time of producing the modified polyphenylene ether, and (a1) polyphenylene ether used as a derivative thereof is used in this embodiment. A compound that can be used as a modified polyphenylene ether can also be used. Specific examples of such compounds include malic acid and citric acid. These may be used alone or in combination of two or more.

The aforementioned polyphenylene ether is generally available as a powder.
The average particle size of the aforementioned polyphenylene ether powder is preferably 1 to 1000 μm, more preferably 10 to 700 μm, and even more preferably 100 to 500 μm. The average particle diameter of the polyphenylene ether is preferably 1 μm or more from the viewpoint of handleability during processing, and preferably 1000 μm or less from the viewpoint of suppressing the generation of unmelted material in the melt kneading described later.
The average particle size of the polyphenylene ether powder can be measured by, for example, a laser particle size meter.

  In the thermoplastic resin composition used in the present embodiment, the content of (a1) polyphenylene ether is 100 parts by mass of the total of the components (a1), (a2), (a3), and (a4). 50 parts by mass to 80 parts by mass, more preferably 55 parts by mass to 80 parts by mass, and more preferably 60 parts by mass to 80 parts by mass.

-(A2) Styrenic resin-
The styrene resin refers to a polymer obtained by polymerizing a styrene compound or a styrene compound and a compound copolymerizable with the styrene compound in the presence or absence of a rubbery polymer.

  Examples of the styrenic compound include, but are not limited to, styrene, α-methylstyrene, 2,4-dimethylstyrene, monochlorostyrene, p-methylstyrene, p-tert-butylstyrene, and ethylstyrene. Etc., and styrene is preferable.

The compounds copolymerizable with the styrene compound are not limited to the following, but include, for example, methacrylic acid esters such as methyl methacrylate and ethyl methacrylate; unsaturated nitrile compounds such as acrylonitrile and methacrylonitrile. An acid anhydride such as maleic anhydride is used, and is used together with a styrenic compound.
The amount of the compound copolymerizable with the styrene compound is preferably 20% by mass or less, more preferably 100% by mass with respect to the total of 100% by mass of the styrene compound and the compound copolymerizable with the styrene compound. It is 15 mass% or less.

Examples of the rubbery polymer include conjugated diene rubbers, copolymers of conjugated dienes and aromatic vinyl compounds, and ethylene-propylene copolymer rubbers. Specifically, polybutadiene and styrene-butadiene copolymer are preferable.
The rubbery polymer is more preferably a partially hydrogenated polybutadiene having an unsaturation of 80 to 20% or a polybutadiene containing 90% or more of 1,4-cis bonds.

  Examples of the styrene resin include, but are not limited to, polystyrene, rubber reinforced polystyrene, styrene-acrylonitrile copolymer (AS resin), rubber reinforced styrene-acrylonitrile copolymer (ABS resin), and others. And styrene-based copolymers. In particular, a combination of polystyrene and rubber-reinforced polystyrene using partially hydrogenated polybutadiene having an unsaturation degree of 80 to 20% is preferable.

  As the styrene-based resin in the component (A) constituting the thermoplastic resin composition used in the present embodiment, homopolystyrene is preferable, and both atactic polystyrene and syndiotactic polystyrene can be used.

  In the thermoplastic resin composition used in the present embodiment, the content of the (a2) styrenic resin is 100 parts by mass with the total of the (a1) component, the (a2) component, the (a3) component, and the (a4) component. Sometimes, it is preferably 25 parts by mass or less. The fluidity of the resin composition is improved according to the content of the component (a2), and by setting it to 25 parts by mass or less, a thermoplastic resin composition excellent in heat resistance and flame retardancy can be obtained, and no additive is added. In that case, a thermoplastic resin composition having particularly excellent heat resistance and heat aging resistance can be obtained.

-(A3) Hydrogenated block copolymer--
The (a3) hydrogenated block copolymer used in this embodiment is a block copolymer obtained by hydrogenating a block copolymer composed of a polystyrene block and a conjugated diene compound polymer block.

The structure of the block copolymer before hydrogenation is not particularly limited. For example, when the polystyrene block chain is represented by S and the conjugated diene compound polymer block chain is represented by B, S-B-S, S-B-S- B, (S—B—) ₄ —S, S—B—S—B—S, etc.

  The hydrogenation rate (hydrogenation rate) of the unsaturated bond derived from the conjugated diene compound is preferably 60% or more, more preferably 80% or more, and still more preferably 95% or more. The hydrogenation rate here can be determined by a nuclear magnetic resonance apparatus (NMR).

  The microstructure of the conjugated diene compound polymer block is not particularly limited and can be arbitrarily selected. Usually, the amount of vinyl bond (1,2-vinyl bond and 3,4-vinyl, which are incorporated in 1,2-bond, 3,4-bond and 1,4-bond bond modes of conjugated dienes) The proportion of those incorporated as bonds) is preferably 2 to 60%, more preferably 8 to 40%. Here, the vinyl bond amount can be determined by a nuclear magnetic resonance apparatus (NMR).

The weight average molecular weight of the component (a3) is 100,000 to 500,000, preferably 150,000 to 400,000, and more preferably 200,000 to 400,000.
When the weight average molecular weight of the component (a3) is less than 100,000, sufficient impact resistance cannot be obtained, and the deterioration degree of the component (a3) cannot be sufficiently controlled. When the weight average molecular weight of the component (a3) exceeds 500,000, the load at the time of melt extrusion becomes high, so that it becomes difficult to control the melt kneading and deterioration of the component (a3).
The weight average molecular weight here can be determined as a styrene equivalent molecular weight by gel permeation chromatography (GPC).

The component (a3) preferably has a weight average molecular weight of at least 1 polystyrene block chain of 15,000 or more, more preferably 20,000 to 70,000. More preferably, the weight average molecular weight of all the polystyrene block chains is 15,000 or more.
By setting the weight average molecular weight of the polystyrene block chain of the component (a3) within the above range, sufficient impact resistance can be obtained, and the deterioration degree of the component (a3) can be controlled sufficiently and easily. .
The weight average molecular weight of a polystyrene block chain here can be measured as a styrene conversion molecular weight by gel permeation chromatography (GPC).

(A3) The content of the polystyrene block in the hydrogenated block copolymer is not particularly limited, but is preferably 20 to 50% by mass from the viewpoint of more easily expressing impact resistance, and 20 to 40% by mass. It is more preferable that
The content of the polystyrene block in the component (a3) can be measured, for example, by the following method. A method of oxidatively decomposing a copolymer before hydrogenation with tert-butyl hydroperoxide using osmium tetroxide as a catalyst (described in IM Koltoff et al., J. Polym. Sci. 1, 429 (1946)) From the mass of the polystyrene block obtained by the method (hereinafter also referred to as “osmium tetroxide decomposition method”) (where the styrene polymer having an average degree of polymerization of about 30 or less is excluded), based on the following formula: Can be sought.
Polystyrene block content (mass%) = (mass of polystyrene block in copolymer before hydrogenation / mass of copolymer before hydrogenation) × 100

  As the component (a3), two or more hydrogenated block copolymers having different compositions and structures can be used in combination. For example, hydrogenated blocks having different block contents such as a combined use of a hydrogenated block copolymer having a polystyrene block content of 50% or more and a hydrogenated block copolymer having a polystyrene block content of 30% or less. Combination of block copolymers; or hydrogenated random block copolymers obtained by hydrogenating block copolymers containing random copolymer blocks of styrene and conjugated diene are possible.

  Examples of the method for producing the component (a3) include Japanese Patent Publication No. 36-19286, Japanese Patent Publication No. 43-17879, Japanese Patent Publication No. 48-2423, Japanese Patent Publication No. 49-36957, Japanese Patent Publication No. 57-49567. The method described in gazette, Japanese Examined Patent Publication No.58-11446, etc. is mentioned.

In the thermoplastic resin composition used in the present embodiment, the content of the (a3) hydrogenated block copolymer is the sum of the (a1) component, the (a2) component, the (a3) component, and the (a4) component. When it is made into a mass part, Preferably it is the range of 1-25 mass parts, More preferably, it is 5-20 mass parts, More preferably, it is 10-15 mass parts.
(A3) By setting the content of the hydrogenated block copolymer to 1 part by mass or more, a thermoplastic resin composition excellent in impact resistance can be obtained, and by setting it to 25 parts by mass or less, the flexural modulus and A thermoplastic resin composition having excellent rigidity such as bending strength can be obtained. In addition, when the content of the (a3) hydrogenated block copolymer is 25 parts by mass or less, the compatibility between the component (a1) and the component (a2) described above is improved, and generation of layered peeling is caused in the molded body. Can be prevented.

  In the thermoplastic resin composition used in this embodiment, the (a3) hydrogenated block copolymer is dispersed in the form of particles.

-(A4) Organophosphorus compound-
Examples of the (a4) organic phosphorus compound used in the present embodiment include, but are not limited to, phosphate ester compounds, phosphazene compounds, and phosphinates.
(A4) The organophosphorus compound is added to improve the flame retardancy of the resin composition, and any organophosphorus compound generally used as a flame retardant can be used. .

・・・・・・（１）
（式（１）中、Ｒ^a、Ｒ^b、Ｒ^c、及びＲ^dは、それぞれ独立して、アリール基であり、ここで、アリール基の１つ以上の水素が置換されていても置換されていなくてもよく；ｎは、自然数であり、１〜３としてよく；Ｘは、フェノール類より誘導される２価の芳香族基であり；ｊ、ｋ、ｌ、及びｍは、それぞれ独立して、０又は１である。） More specifically, a phosphoric ester compound represented by the following general formula (1) can be mentioned.

(1)
(In formula (1), R ^a , R ^b , R ^c , and R ^d are each independently an aryl group, where one or more hydrogen atoms in the aryl group are substituted. N may be a natural number and may be 1 to 3; X is a divalent aromatic group derived from phenols; j, k, l, and m are each independently 0 or 1)

Examples of the phosphate ester-based compound include, but are not limited to, triphenyl phosphate, trisnonylphenyl phosphate, resorcinol bis (diphenyl phosphate), resorcinol bis [di (2,6-dimethylphenyl) phosphate]. 2,2-bis {4- [bis (phenoxy) phosphoryloxy] phenyl} propane, 2,2-bis {4- [bis (methylphenoxy) phosphoryloxy] phenyl} propane, and the like.
Further, the phosphate ester compounds other than the above are not limited to the following, but examples include trimethyl phosphate, triethyl phosphate, tributyl phosphate, trioctyl phosphate, tributoxyethyl phosphate, tricresyl phosphate, cresyl phenyl. Phosphate ester flame retardants such as phosphate, octyl diphenyl phosphate, diisopropylphenyl phosphate; diphenyl-4-hydroxy-2,3,5,6-tetrabromobenzyl phosphonate, dimethyl-4-hydroxy-3,5-dibromo Benzyl phosphonate, diphenyl-4-hydroxy-3,5-dibromobenzyl phosphonate, tris (chloroethyl) phosphate, tris (dichloropropyl) phosphate, tris ( Rolopropyl) phosphate, bis (2,3-dibromopropyl) -2,3-dichloropropyl phosphate, tris (2,3-dibromopropyl) phosphate, bis (chloropropyl) monooctyl phosphate, hydroquinonyl diphenyl phosphate, phenylnonyl Examples thereof include monophosphate compounds such as phenylhydroquinonyl phosphate and phenyldinonylphenyl phosphate; aromatic condensed phosphate compounds.
Of these, aromatic condensed phosphate compounds are preferred because they generate less gas during processing and are excellent in thermal stability and the like.

・・・・・・（５）

・・・・・・（６）
（式（５）及び式（６）中、ｎは、３〜２５の整数であり；ｍは、３〜１００００の整数であり；置換基Ｘは、炭素数が１〜６のアルキル基、炭素数が６〜１１のアリール基、フッ素原子、下記一般式（７）で示されるアリールオキシ基、ナフチルオキシ基、炭素数が１〜６のアルコキシ基及びアルコキシ置換アルコキシ基で表される置換基からなる群から選ばれる置換基であり、それぞれ異なっていても、同じでもよく、ここで、置換基上の水素は、その一部又は全部が、フッ素、水酸基、シアノ基に置換されていてもよく；置換基Ｙは、−Ｎ＝Ｐ（Ｏ）（Ｘ）又は−Ｎ＝Ｐ（Ｘ）₃であり；置換基Ｚは、−Ｐ（Ｘ）₄又は−Ｐ（Ｏ）（Ｘ）₂である。）

・・・・・・（７）
（式（７）中、のＹ₁、Ｙ₂、Ｙ₃、Ｙ₄、及びＹ₅は、それぞれ独立して、水素原子、フッ素原子、炭素数が１〜５のアルキル基、炭素数が１〜５のアルコキシ基、フェニル基、ヘテロ元素含有基からなる群より選ばれる置換基を表す。） Examples of the phosphazene compound include a cyclic phosphazene compound represented by the following general formula (5) and a chain phosphazene compound represented by the following general formula (6).

(5)

(6)
(In Formula (5) and Formula (6), n is an integer of 3 to 25; m is an integer of 3 to 10000; substituent X is an alkyl group having 1 to 6 carbon atoms, carbon From a substituent represented by an aryl group having 6 to 11 atoms, a fluorine atom, an aryloxy group represented by the following general formula (7), a naphthyloxy group, an alkoxy group having 1 to 6 carbon atoms and an alkoxy-substituted alkoxy group Each of which may be different or the same, and the hydrogen on the substituent may be partially or entirely substituted with fluorine, a hydroxyl group, or a cyano group. The substituent Y is —N═P (O) (X) or —N═P (X) ₃ ; the substituent Z is —P (X) ₄ or —P (O) (X) ₂ ; is there.)

(7)
(In Formula (7), Y ₁ , Y ₂ , Y ₃ , Y ₄ , and Y ₅ are each independently a hydrogen atom, a fluorine atom, an alkyl group having 1 to 5 carbon atoms, or 1 carbon atom. Represents a substituent selected from the group consisting of ˜5 alkoxy groups, phenyl groups, and hetero-element-containing groups.)

  And as a phosphazene compound, what contains 95 mass% or more of phosphazene compounds which have a structure of Formula (5) and / or Formula (6) is preferable.

  Among these, as the phosphazene compound, a phosphazene compound having a cyclic structure is preferable because it is particularly excellent in flame retardancy, and a compound containing 95% by mass or more of the cyclic phosphazene compound represented by the formula (5) is preferable.

・・・・・・（２）
［式中、Ｒ¹¹及びＲ¹²は、各々独立して、直鎖状若しくは分岐状の炭素原子数１〜６のアルキル基及び／又は炭素原子数６〜１０のアリール基であり；Ｍ¹は、カルシウムイオン、マグネシウムイオン、アルミニウムイオン、亜鉛イオン、ビスマスイオン、マンガンイオン、ナトリウムイオン、カリウムイオン、及びプロトン化された窒素塩基からなる群より選ばれる少なくとも１種であり；ａは、１〜３の整数であり；ｍは、１〜３の整数であり；ａ＝ｍである］

・・・・・・（３）
［式中、Ｒ²¹及びＲ²²は、各々独立して、直鎖状若しくは分岐状の炭素原子数１〜６のアルキル基及び／又は炭素原子数６〜１０のアリール基であり；Ｒ²³は、直鎖状若しくは分岐状の炭素原子数１〜１０のアルキレン基、炭素原子数６〜１０のアリーレン基、炭素原子数６〜１０のアルキルアリーレン基又は炭素原子数６〜１０のアリールアルキレン基であり；Ｍ²は、カルシウムイオン、マグネシウムイオン、アルミニウムイオン、亜鉛イオン、ビスマスイオン、マンガンイオン、ナトリウムイオン、カリウムイオン、及びプロトン化された窒素塩基からなる群より選ばれる少なくとも１種であり；ｂは、１〜３の整数であり；ｎは、１〜３の整数であり；ｊは、１又は２の整数であり；ｂ・ｊ＝２ｎである］ More specifically, phosphinic acid salts include phosphinic acid represented by the following general formula (2) and diphosphinic acid represented by the following formula (3).

(2)
Wherein, R ¹¹ and R ¹² are each independently a straight-chain or branched alkyl and / or aryl group having 6 to 10 carbon atoms having from 1 to 6 carbon atoms; M ¹ is A calcium ion, a magnesium ion, an aluminum ion, a zinc ion, a bismuth ion, a manganese ion, a sodium ion, a potassium ion, and a protonated nitrogen base; M is an integer of 1 to 3; a = m]

(3)
Wherein, R ²¹ and R ²² are each independently a linear or branched alkyl and / or aryl group having 6 to 10 carbon atoms having from 1 to 6 carbon atoms; R ²³ is A linear or branched alkylene group having 1 to 10 carbon atoms, an arylene group having 6 to 10 carbon atoms, an alkylarylene group having 6 to 10 carbon atoms, or an arylalkylene group having 6 to 10 carbon atoms. Yes; M ² is at least one selected from the group consisting of calcium ions, magnesium ions, aluminum ions, zinc ions, bismuth ions, manganese ions, sodium ions, potassium ions, and protonated nitrogen bases; b Is an integer of 1 to 3; n is an integer of 1 to 3; j is an integer of 1 or 2; b · j = 2n]

  The phosphinic acid salts include, for example, phosphinic acid, metal carbonate, and the like as described in JP-A-2005-179362, European Patent Application Publication No. 699708, JP-A-08-073720, and the like. It can also be produced in an aqueous solution using a metal hydroxide or a metal oxide.

The phosphinates are usually monomeric compounds, but may contain, for example, polymeric phosphinates that are condensates having a degree of condensation of 1 to 3 depending on reaction conditions and environment.
Examples of the phosphinic acid in the general formula (2) and the diphosphinic acid in the general formula (3) include, for example, dimethylphosphinic acid, ethylmethylphosphinic acid, diethylphosphinic acid, methyl-n-propylphosphinic acid, methandi (Methylphosphinic acid), benzene-1,4- (dimethylphosphinic acid), methylphenylphosphinic acid, diphenylphosphinic acid and the like. These may be used alone or in combination of two or more.

M ¹ and M ² in general formula (2) and general formula (3) are at least one selected from the group consisting of calcium ions, magnesium ions, aluminum ions and zinc ions from the viewpoint of the surface appearance of the molded product. Preferably there is.

Specific examples of phosphinic acid salts include, for example, calcium dimethylphosphinate, magnesium dimethylphosphinate, aluminum dimethylphosphinate, zinc dimethylphosphinate, calcium ethylmethylphosphinate, magnesium ethylmethylphosphinate, aluminum ethylmethylphosphinate, ethyl Zinc methylphosphinate, calcium diethylphosphinate, magnesium diethylphosphinate, aluminum diethylphosphinate, zinc diethylphosphinate, calcium methyl-n-propylphosphinate, magnesium methyl-n-propylphosphinate, methyl-n-propylphosphinic acid Aluminum, zinc methyl-n-propylphosphinate, methandi (methylphosphinic acid) calcium, methandi (methyl) Phosphinic 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, diphenylphosphinic acid Examples include calcium, magnesium diphenylphosphinate, aluminum diphenylphosphinate, and zinc diphenylphosphinate.
Among the above, from the viewpoint of flame retardancy and surface appearance of molded products, calcium dimethylphosphinate, aluminum dimethylphosphinate, zinc dimethylphosphinate, calcium ethylmethylphosphinate, aluminum ethylmethylphosphinate, zinc ethylmethylphosphinate, Calcium diethylphosphinate, aluminum diethylphosphinate, and zinc diethylphosphinate are preferred, and aluminum diethylphosphinate is more preferred.

The content of the (a4) organophosphorus compound in the thermoplastic resin composition of the present embodiment is 100 parts by mass with the sum of the (a1) component, the (a2) component, the (a3) component, and the (a4) component. When it is, it is preferable that it is 2-30 mass parts, It is more preferable that it is 5-25 mass parts, It is still more preferable that it is 5-20 mass parts.
(A4) By making content of an organophosphorus compound more than the said lower limit, a flame retardance can be improved further. Moreover, the balance of mechanical strength, moldability, and surface appearance of a molded article can be maintained at a higher level by setting the content of the (a4) organophosphorus compound to the upper limit or less.
In the (a4) organophosphorus compound, an unreacted product or a by-product during production may remain as long as the effect of the present embodiment is obtained.

  The content of the (A) polyphenylene ether resin composition in the thermoplastic resin composition of the present embodiment is preferably 60 to 99.94% by mass with respect to 100% by mass of the thermoplastic resin composition, 65 More preferably, it is -99.94 mass%, and it is still more preferable that it is 65-99.85 mass%.

[(B) Metal halide compound]
The thermoplastic resin composition of the present embodiment contains one or more metal halide compounds selected from a barium halide compound and a silver halide compound.

Examples of the barium halide include barium bromide, chlorinated barium, and barium iodide. Of these, barium chloride is preferred. These may be anhydrous or may contain crystal water.
Examples of the silver halide include silver bromide, silver chloride, silver iodide and the like. Among these, silver chloride is preferable.

The content of the (B) metal halide compound in the thermoplastic resin composition of the present embodiment is 0.05 to 3 parts by mass with respect to 100 parts by mass of the (A) polyphenylene ether-based resin composition. It is preferably 05 to 2.5 parts by mass, more preferably 0.1 to 2.5 parts by mass, and still more preferably 0.1 to 2 parts by mass.
(B) By making content of metal halide salt more than the said lower limit, the composition excellent in tracking resistance can be obtained. Moreover, the balance of mechanical strength, moldability, and the surface appearance of a molded article can be maintained at a higher level by setting the content of the (B) metal halide salt to the upper limit or less.

[(C) Colorant]
If necessary, the thermoplastic resin composition of the present embodiment is at least one colorant selected from the group consisting of (C) an organic pigment, an inorganic pigment, and an organic dye (hereinafter referred to as “(C) colorant”). Etc.) in some cases.
(C) As a coloring agent, a well-known organic pigment, an inorganic pigment, and organic dye can be used, for example.

  Examples of organic pigments and organic dyes include, but are not limited to, azo pigments such as azo lake pigments, benzimidazolone pigments, diarylide pigments, and condensed azo pigments; phthalocyanine pigments such as phthalocyanine blue and phthalocyanine green; isoindolinone Examples include pigments, quinophthalone pigments, quinacridone pigments, perylene pigments, anthraquinone pigments, perinone pigments, condensed polycyclic pigments such as dioxazine violet; azine dyes, and carbon black. These may be used individually by 1 type and may use 2 or more types together.

In particular, the carbon black preferably has a dibutyl phthalate (DBP) absorption of less than 250 mL / 100 g, and more preferably less than 150 mL / 100 g. And the nitrogen adsorption specific surface area of carbon black is preferably less than 900 m ² / g, and more preferably less than 400 m ² / g. Furthermore, it is particularly preferable that the DBP absorption amount of carbon black is within the above range, and the nitrogen adsorption specific surface area is within the above range. When the DBP absorption amount and the nitrogen adsorption specific surface area are in the above ranges, respectively, the colorability, mechanical strength, and flame retardancy are further improved. The DBP absorption can be measured by a method based on ASTM D2414. The nitrogen adsorption specific surface area can be measured by a method based on JIS K6217.
Examples of azine dyes include Solvent Black 5 (CI. 50415, CAS No. 11099-03-9) and Solvent Black 7 (CI. 50415: 1, CAS No. 8005-20-) in the color index. 5 / 101357-15-7), Acid Black 2 (C.I. 50420, CAS No. 8005-03-6 / 68510-98-5) and the like. These may be used individually by 1 type and may use 2 or more types together.

  Examples of inorganic pigments include metal oxides such as titanium oxide, zinc oxide, chromium oxide, and iron oxide, and composite metal oxides such as titanium yellow, cobalt blue, and ultramarine blue. These may be used individually by 1 type and may use 2 or more types together.

  The content of the (C) colorant in the thermoplastic resin composition of the present embodiment is preferably 0.01 to 5% by mass with respect to 100% by mass of the thermoplastic resin composition, and 0.01 to 3%. More preferably, it is 0.01 mass%, It is still more preferable that it is 0.01-2 mass%, It is especially preferable that it is 0.05-2 mass%.

[Other materials]
The thermoplastic resin composition of the present embodiment may further contain other components (for example, inorganic fillers and various additives other than those described above) as necessary.

Examples of the inorganic filler include glass fiber, potassium titanate fiber, gypsum fiber, brass fiber, ceramic fiber, boron whisker fiber, mica, talc, silica, calcium carbonate, kaolin, calcined kaolin, wollastonite, zonotrite, apatite. Examples thereof include fiber-like, granular, plate-like, or needle-like inorganic reinforcing materials such as glass beads, flaky glass, and titanium oxide. These may be used individually by 1 type and may use 2 or more types together.
Among these, glass fibers, carbon fibers, and glass beads are preferable as the inorganic filler.
The inorganic filler may be surface-treated with a surface treatment agent such as a silane coupling agent.

  Examples of additives include other thermoplastic resins such as polyester and polyolefin, plasticizers (low molecular weight olefins, polyethylene glycols, fatty acid esters, etc.), antistatic agents, nucleating agents, fluidity improvers, reinforcing agents, and various types. Examples thereof include peroxides, spreading agents, copper-based heat stabilizers, organic heat stabilizers represented by hindered phenol-based oxidative degradation inhibitors, antioxidants, ultraviolet absorbers, and light stabilizers.

  The content of the other components described above in the thermoplastic resin composition of the present embodiment is preferably 30% by mass or less in the case of an inorganic filler with respect to 100% by mass of the thermoplastic resin composition. In the case of an additive, it is preferably 10% by mass or less, more preferably less than 5% by mass, and still more preferably 3% by mass or less.

[Method for producing thermoplastic resin composition]
The thermoplastic resin composition of the present embodiment is a conventionally known melt-kneading method using the above-described component (A), component (B), component (C) (colorant), and other materials as necessary. Can be manufactured.
Examples of the production method include a method of melt kneading using, for example, a single screw extruder, a twin screw extruder, a roll, a kneader, a Brabender plastograph, a Banbury mixer, etc. Among them, a method using a twin screw extruder Is preferred.
Examples of the twin screw extruder include, but are not limited to, a twin screw extruder with a screw diameter of 58 mm, a barrel number of 13, and a vacuum vent port.
A method for producing a thermoplastic resin composition using the twin screw extruder will be specifically described. For example, when melt-kneading, the (a1) component, the (a2) component, the (a3) component, and the (B) component are supplied to the first barrel 1 in the upstream barrel 1 with respect to the flow direction of the twin-screw extruder. Supply from mouth. Thereafter, the component (a4) is extruded through an injection nozzle to the side of the extruder from the second (liquid) supply port located downstream of the first supply port using a gear pump.
The screw configuration of the twin-screw extruder is preferably 45 to 75%, more preferably 60 to 70% from the upstream side of the barrel when the total length of the unmelted mixing zone is 100%. preferable.
In the melt-kneading zone in the twin-screw extruder, a kneading element having a phase of 45 degrees (usually indicated as R), a kneading element having a phase of 90 degrees (usually indicated as N), and a kneading element having a negative phase of 45 degrees (Usually indicated as L) is preferably used, and a kneading element (usually indicated as R) having a phase of 45 degrees is used in the unmelted mixing zone after feeding the flame retardant from the second supply port. It is preferable to do.
The screw in the melt-kneading zone is not limited to the following. For example, a kneading disc R (L (screw length) / combination of 3 to 7 discs with a twist angle of 15 to 75 degrees) D (positive screw element having a screw diameter) of 0.5 to 2.0) and kneading disc N (3 to 7 discs are combined at a twist angle of 90 degrees, L / D is 0.5 to 2 .. neutral screw element), kneading disk L (a reverse screw element having L / D of 0.5 to 1.0, in which 3 to 7 disks are combined at a twist angle of 15 to 75 degrees), etc. It is preferable to have a screw configuration in which the two are appropriately combined, and a reverse screw screw (two-thread reverse screw screw element having an L / D of 0.5 to 1.0) SME screw (screw element with an L / D of 0.5 to 1.5 with a notch on the positive screw to improve kneadability), ZME screw (notch on the reverse screw screw to improve kneadability A screw element such as an improved screw element having an L / D of 0.5 to 1.5) may be appropriately incorporated into the screw structure and kneaded.
In the melt-kneading in the production process of the thermoplastic resin composition used in the present embodiment, it is preferable to perform degassing under reduced pressure.
Moreover, it is preferable to make the resin temperature at the time of melt-kneading into the range of 290-350 degreeC. Specifically, it is preferable to set the set temperature of the first stage of the twin-screw extruder (the barrel on the upstream side of the extrusion flow among all the barrels) in the range of 150 to 250 ° C. The set temperature of the barrel) is preferably in the range of 250 to 330 ° C, and the die outlet resin temperature is not particularly limited, but is preferably in the range of 290 to 350 ° C.
The screw rotation speed of the twin screw extruder is preferably in the range of 150 to 600 rpm.
By producing a thermoplastic resin composition according to the production method described above, a thermoplastic resin composition having excellent tracking resistance, impact resistance, and flame retardancy can be obtained.

(Molding)
The molded article of the present embodiment is obtained by using conventionally known molding methods such as injection molding, extrusion molding, press molding, blow molding, calender molding, and casting using the thermoplastic resin composition of the present embodiment described above. It can manufacture by using and shape | molding.
For example, a thermoplastic resin composition is melted in a cylinder of an injection molding machine whose cylinder temperature is adjusted to a range of 350 ° C. or lower, and injected into a mold having a predetermined shape, whereby a molded product having a predetermined shape is obtained. Can be manufactured.
Moreover, a fibrous molded article can be manufactured by melting the thermoplastic resin composition in an extruder whose cylinder temperature is adjusted within the above range and spinning from the nozzle nozzle.
Furthermore, a film-like or sheet-like molded product can be produced by melting the thermoplastic resin composition in an extruder whose cylinder temperature is adjusted within the above range and extruding it from a T-die.
Furthermore, the molded article manufactured by such a method may have a form in which a coating layer made of a paint, metal, another type of polymer, or the like is formed on the surface.

The thermoplastic resin composition of the present invention is an electrical component, an industrial machine, such as an office machine, a measuring instrument, a chassis, an internal part component of an electrical device, a power adapter such as a household appliance, a recording medium, its drive, a sensor device, Terminal blocks, secondary batteries in the energy / environment field, fuel cells and solar cells, solar thermal power generation, geothermal power generation, wind power generation, smart meters, etc., electrical and electronic components used in power transmission equipment, cable terminals, automobiles It can be used as a part.
In particular, the thermoplastic resin composition of the present invention can be suitably used for, for example, a solar cell including a solar power generation module. Specifically, a solar cell connection structure, a solar cell junction box, and a solar cell. It can be used as a connector for an automobile, a hybrid vehicle / electric vehicle part.

Hereinafter, the present invention will be described with reference to specific examples and comparative examples, but the present invention is not limited thereto.
Measurement methods and raw materials used in Examples and Comparative Examples are shown below.

[Measurement method of characteristics]
(1) Flame retardancy (UL-94 standard)
Using the method of UL94 (standard established by Under Writer's Laboratories Inc., USA), five samples were measured per sample.
In addition, as a test piece for a combustion test, two types of those having a length of 127 mm, a width of 12.7 mm, and a thickness of 1.5 mm, and a length of 127 mm, a width of 12.7 mm, and a thickness of 2.0 mm were used.
Using the injection molding machine (manufactured by Toshiba Machine Co., Ltd .: IS-80EPN), the cylinder temperature was set to 320 ° C. and the mold temperature was set to 80 ° C. A test piece for combustion test was molded.
In particular, it was determined as a desirable resin composition in the case of determination of flame retardancy level V-0 or higher.

(2) Charpy impact strength with notch After the resin composition pellets produced in Examples and Comparative Examples described later were dried at 100 ° C. for 2 hours, the injection molding machine (manufactured by Toshiba Machine Co., Ltd .: IS-80EPN) was used. The cylinder temperature was set to 280 ° C. and the mold temperature was set to 80 ° C., and a multipurpose test piece of JIS K7139 A type was molded. A test piece was further cut out from the multipurpose test piece, and Charpy impact strength (kJ / m ² ) was evaluated under a temperature condition of 23 ° C. according to ISO179. It was determined that the higher the measured value, the better the impact resistance.

(3) DTUL (deflection temperature under load)
The resin composition pellets produced in Examples and Comparative Examples described later were dried at 100 ° C. for 2 hours, and then the cylinder temperature was set to 280 ° C. and the mold using an injection molding machine (Toshiba Machine Co., Ltd .: IS-80EPN). The temperature was set to 80 ° C., and a JIS K7139 A type multipurpose test piece was molded. A test piece was further cut out from the multipurpose test piece, and the deflection temperature under load (° C.) was evaluated by the flatwise method under the condition of 1.8 MPa according to ISO75. The higher the measured value, the better the heat resistance.

(4) Tracking resistance After the resin composition pellets produced in Examples and Comparative Examples described later were dried at 100 ° C. for 2 hours, the cylinder temperature was measured by an injection molding machine (manufactured by Toshiba Machine Co., Ltd .: IS-80EPN). Was set to 280 ° C. and the mold temperature was set to 80 ° C., a 65 mm × 90 mm × 3.0 mm test piece was molded, and a comparative tracking index (CTI) (V) was measured according to the IEC60112 standard. The applied voltage was changed in units of 25V. It was determined that the higher the measured value, the better the tracking resistance.

・・・・・・（８） [Raw materials used in Examples and Comparative Examples]
(A) Polyphenylene ether-based resin composition (a1) Polyphenylene ether Poly-2,6-dimethyl-1,4-phenylene ether (reduced viscosity = 0.52 g / dL, hydroxyl group concentration = 0.80 / PPE monomer 100 units, copper content = 0.4ppm)
(A2) Styrenic resin High impact polystyrene: manufactured by PS Japan Co., Ltd., trade name “PSJ-polystyrene H9302”
(A3) Hydrogenated block copolymer)
Hydrogenated block copolymer obtained by hydrogenating a styrene-butadiene block copolymer (polystyrene-polybutadiene-polystyrene bond structure): Kraton Polymers LLC, trade name “Clayton G1651” (number average molecular weight: about 250 , Styrene polymer block content: about 33% by mass, hydrogenation rate of butadiene unit: 98% or more)
(A4) Organophosphorus compound Bisphenol A condensed phosphate ester: Daihachi Chemical Co., Ltd., trade name “CR-741” (the following general formula (8), where n = 1 is the main component (liquid chromatography 85% by area ratio by analysis, acid value = 0.2))

(8)

(B) Metal halide compound (B-1) Barium chloride dihydrate)
Wako Pure Chemical Industries, first grade (purity: 98.5 wt%)
(B-2) Silver chloride Wako Pure Chemical Industries, special grade (purity: 99.5 wt%)
(B-3) Barium bromide Wako Pure Chemical Industries, first grade (purity: 98.5 wt%)
(B-4) Silver bromide Wako Pure Chemical Industries, Ltd. (purity: 99.5 wt%)

(C) Colorant 50 parts by mass of Mitsubishi Carbon Black # 960 (manufactured by Mitsubishi Chemical Corporation) is melt-kneaded together with 47 parts by mass of GPPS (PSJ polystyrene 680, manufactured by PS Japan) and 3 parts by mass of magnesium stearate. Dispersed master batch pellets.

[Examples 1 to 6 and Comparative Examples 1 to 3]
Using a screw diameter of 58 mm, a barrel number of 13 and a twin screw extruder with a reduced pressure vent (TEM58SS: manufactured by Toshiba Machine Co., Ltd.), each raw material was supplied and melt-kneaded according to the composition described in Table 1 below.
The strand coming out from the tip of the extruder die was cooled through a SUS strand bath filled with cooling water, and then cut with a strand cutter to obtain a resin composition pellet.

The screw configuration of the above twin screw extruder was as follows.
The configuration of the twin-screw extruder was such that an unmelted kneading zone (first stage) that does not melt the thermoplastic resin and a melt kneading zone (second stage) were provided in order from the upstream side. Here, the unmelted kneading zone had a length of 70% when the barrel length of the extruder was 100%.

In addition, the supply method of each component at the time of the melt kneading was as follows.
First, in the unmelted kneading zone, the (a1) component, the (a2) component, the (a3) component, the (B) component, and the (C) component are placed in the upstream barrel 1 with respect to the flow direction of the extruder. After supplying from one supply port, in the unmelted kneading zone, the component (a4) is injected into the side of the extruder using a gear pump from the second (liquid) supply port in the barrel 5 downstream from the first supply port. Fed through.

  The screw configuration of the unmelted kneading zone was composed of two progressive screw elements and two progressive feed (phase 45 degrees) kneading disk elements (indicated as R) in order from the upstream side. In the unmelted kneading zone, the component (a4) was fed from the second supply port, and after feeding the component (a4), a progressive feed (phase 45 degrees) kneading disk element (indicated as R) was arranged.

  The screw configuration of the melt-kneading zone is composed of two progressive (phase 45 degrees) kneading disk elements (labeled R) and one orthogonal (phase 90 degrees) kneading disk elements (labeled N) in order from the upstream side. One reverse feed (negative phase 45 degrees) kneading disk element (denoted L).

  A vacuum degassing zone was provided in the barrel 11 and degassed under reduced pressure at -900 hPa. Further, the barrel 5 was provided with a second supply port for supplying the component (a4). The barrel set temperature was barrel 1: water cooling, barrel 2: 100 ° C, barrel 3-6: 200 ° C, barrel 7: 250 ° C, barrel 8: 270 ° C, barrel 9-13: 280 ° C, and die: 290 ° C. . The screw rotation speed was 350 rpm, and the discharge amount (extrusion rate) was 400 kg / hr. Extrusion was performed under the above conditions.

  Using the resin composition pellets obtained in the examples and comparative examples, the above (1) to (4) were evaluated. The results are shown in Table 1 below.

In Examples 1-6, it turned out that it is excellent in tracking resistance, maintaining impact strength, heat resistance, and a flame retardance.
On the other hand, Comparative Examples 1 and 2 were inferior in tracking resistance, and Comparative Example 3 was inferior in impact strength.

The thermoplastic resin composition of the present invention is an electrical component, an industrial machine, such as an office machine, a measuring instrument, a chassis, an internal part component of an electrical device, a power adapter such as a household appliance, a recording medium, its drive, a sensor device, Terminal blocks, secondary batteries in the energy / environment field, fuel cells and solar cells, solar thermal power generation, geothermal power generation, wind power generation, smart meters, etc., electrical and electronic components used in power transmission equipment, cable terminals, automobiles As a part, it has industrial applicability.
In particular, the thermoplastic resin composition of the present invention can be suitably used for, for example, a solar cell including a solar power generation module. Specifically, a solar cell connection structure, a solar cell junction box, and a solar cell. It has industrial applicability as a connector for automobiles and parts for hybrid vehicles and electric vehicles.

Claims (8)

  (A) 0.05 to 3 parts by mass of one or more metal halide compounds selected from the group consisting of (B) a barium halide compound and a silver halide compound with respect to 100 parts by mass of the polyphenylene ether-based resin composition A thermoplastic resin composition, comprising:   When the total of (A) polyphenylene ether-based resin composition is 100 parts by mass of (a1) component, (a2) component, (a3) component, and (a4) component, (a1) 50-80 mass of polyphenylene ether 1 to 25 parts by mass of (a2) styrene-based resin, (a3) 1 to 25 parts by mass of a hydrogenated block copolymer, and (a4) 2 to 30 parts by mass of an organophosphorus compound. Thermoplastic resin composition.   (C) The thermoplastic resin composition according to claim 1 or 2, further comprising one or more colorants selected from the group consisting of organic pigments, inorganic pigments, and organic dyes. The component (C) is carbon black,
The content of the carbon black in the thermoplastic resin composition is 0.01 to 2% by mass.
The thermoplastic resin composition according to claim 3. The (a4) organophosphorus compound is a phosphate compound represented by the following general formula (1), a phosphinic acid salt represented by the following general formula (2), a diphosphinic acid salt represented by the following general formula (3) The thermoplastic resin composition according to claim 2, which is one or more selected from the group consisting of:

(1)
(In formula (1), R ^a , R ^b , R ^c , and R ^d are each independently an aryl group, where one or more hydrogen atoms in the aryl group are substituted. N is a natural number; X is a divalent aromatic group derived from phenols; j, k, l, and m are each independently 0 or 1; is there.)

(2)
Wherein, R ¹¹ and R ¹² are each independently a straight-chain or branched alkyl and / or aryl group having 6 to 10 carbon atoms having from 1 to 6 carbon atoms; M ¹ is A calcium ion, a magnesium ion, an aluminum ion, a zinc ion, a bismuth ion, a manganese ion, a sodium ion, a potassium ion, and a protonated nitrogen base; M is an integer of 1 to 3; a = m]

(3)
Wherein, R ²¹ and R ²² are each independently a linear or branched alkyl and / or aryl group having 6 to 10 carbon atoms having from 1 to 6 carbon atoms; R ²³ is A linear or branched alkylene group having 1 to 10 carbon atoms, an arylene group having 6 to 10 carbon atoms, an alkylarylene group having 6 to 10 carbon atoms, or an arylalkylene group having 6 to 10 carbon atoms. Yes; M ² is at least one selected from the group consisting of calcium ions, magnesium ions, aluminum ions, zinc ions, bismuth ions, manganese ions, sodium ions, potassium ions, and protonated nitrogen bases; b Is an integer of 1 to 3; n is an integer of 1 to 3; j is an integer of 1 or 2; b · j = 2n]   A connection structure for a photovoltaic power generation module, comprising the thermoplastic resin composition according to any one of claims 1 to 5.   A junction box for a photovoltaic power generation module, comprising the thermoplastic resin composition according to any one of claims 1 to 5.   A connector for a photovoltaic power generation module, comprising the thermoplastic resin composition according to any one of claims 1 to 5.