JP2010138216A - Resin composition, method for producing the same and molded article obtained therefrom, cable covering material, and cable - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a resin composition having no foreign substance caused by thermal history and excellent in balance between rigidity and impact resistance and also in thermal aging resistance, and to provide a method for producing the same and a molded article obtained therefrom, a cable covering material, and a cable. <P>SOLUTION: The resin composition contains: total 100 pts.mass of (a) a polyolefin-based resin and (b) a polyphenylene ether-based resin; 1-100 pts.mass of (c) a hydrogenated block copolymer obtained by at least partially hydrogenating a block copolymer including a polymer block A, consisting primarily of a vinyl aromatic compound, and a polymer block B, consisting primarily of a conjugated diene compound of which a total amount of a 1,2-vinyl bond and a 3,4-vinyl bond is 30-90%; (d) ≥0.1 pt.mass and <1 pt.mass of a polyamine compound; (e) 0.05-3 pts.mass of a hindered phenol-based stabilizer, (f) 0.05-3 pts.mass of a sulfur-based stabilizer; and (g) 0-3 pts.mass of an acrylate-based compound. <P>COPYRIGHT: (C)2010,JPO&INPIT

Description

  The present invention relates to a resin composition, a method for producing the same, a molded product made of the resin composition, a cable covering material and a cable.

Polyphenylene ether resins are known as engineering plastics with excellent flame retardancy, heat resistance, dimensional stability, non-water absorption and electrical properties, but have poor melt flowability and inferior moldability, and There are disadvantages inferior in solvent resistance and impact resistance.
Polyolefin resins, on the other hand, are low specific gravity and inexpensive plastics, and are excellent in chemical resistance, solvent resistance, molding processability, etc., so they are used in various fields such as automobile parts, electrical / electronic equipment parts, and household electrical products. Has been.

  Patent Document 1 and Patent Document 2 describe that impact resistance is improved by blending polyphenylene ether with a hydrogenated block copolymer and polyolefin.

  Patent Document 3 describes that impact resistance is improved by blending polyphenylene ether with a polyolefin and a hydrogenated block copolymer.

U.S. Pat. No. 4,166,055 U.S. Pat. No. 4,239,673 U.S. Pat. No. 4,383,082

  However, when polyphenylene ether is subjected to a thermal history of about 300 to 350 ° C. during processing or the like, the oxidative degradation occurs remarkably, so that the thermally degraded product is mixed into the resin composition as a brown to black foreign material. Since this foreign material has poor affinity with the resin composition, when stress is applied to the resin composition, it causes cracks and has a drawback that the mechanical strength is remarkably impaired.

  The present invention has been made in view of the above circumstances, has no foreign matter due to thermal history, has a balance between rigidity and impact resistance, and further has excellent heat aging resistance, a method for producing the same, and a molding comprising the same. The object is to provide a product, a cable covering material and a cable.

  As a result of intensive investigations to give a high level of rigidity, impact resistance, and heat aging resistance to polyolefin resins, polyphenylene ether resins, and hydrogenated block copolymers, the present inventors have found that specific polyamine compounds, hindered It has been found that a resin composition having excellent rigidity, impact resistance and heat aging resistance can be obtained simultaneously by melt-kneading using a phenol-based stabilizer, a sulfur-based stabilizer or the like, and the present invention has been completed. .

（式中、Ｒ^１、Ｒ^２及びＲ^３は、同一又は異なって、アルキレン基を表す。ｘ、及びｙは、それぞれ１以上の整数を表す。）
［８］（ｄ）ポリアミン化合物の重量平均分子量が２００〜１０００００である、［１］〜［７］のいずれか一項に記載の樹脂組成物。
［９］（ｆ）成分が、ジラウリル−３，３’−チオジプロピオネート、ジミリスチル−３，３’−チオジプロピオネート、ジステアリル−３，３’−チオジプロピオネート、ビス〔２−メチル−４−｛３−ｎ−アルキルチオプロピオニルオキシ｝−５−ｔ−ブチルフェニル〕スルフィド、テトラキス〔メチレン−３−（ラウリルチオ）プロピオネート〕メタン、テトラキス〔メチレン−３−（ミリスチルチオ）プロピオネート〕メタン、テトラキス〔メチレン−３−（ステアリルチオ）プロピオネート〕メタン、２−メルカプトベンズイミダゾール、ジトリデシルチオジプロピオネート、ジラウリルチオジプロピオネート、ジステアリルチオジプロピオネート及びジミリスチルチオジプロピオネートからなる群より選ばれる少なくとも１種以上である、［１］〜［８］のいずれか一項に記載の樹脂組成物。
［１０］（ａ）成分がマトリックス相を、（ｂ）成分が分散相を、それぞれ形成する、［１］〜［９］のいずれか一項に記載の樹脂組成物。
［１１］（ａ）ポリオレフィン系樹脂と（ｂ）ポリフェニレンエーテル系樹脂の合計１００質量部と、（ｃ）ビニル芳香族化合物を主体とする重合体ブロックＡと、共役ジエン化合物の１，２−ビニル結合量と３，４−ビニル結合量の合計量が３０〜９０％である共役ジエン化合物を主体とする重合体ブロックＢと、を含むブロック共重合体の少なくとも一部が水素添加された水素添加ブロック共重合体１〜１００質量部と、（ｄ）ポリアミン化合物０．１〜１質量部未満と、（ｅ）ヒンダードフェノール系安定剤０．０５〜３質量部と、（ｆ）イオウ系安定剤０．０５〜３質量部と、（ｇ）アクリレート系化合物０〜３質量部と、を溶融混練するに際して、下記の（１）工程と、（２）工程と、を含む樹脂組成物の製造方法。
（１）（ｂ）成分と（ｄ）成分の全量と、（ｃ）成分と（ｅ）成分と（ｆ）成分と（ｇ）成分の一部あるいは全量と、（ａ）成分の一部と、を溶融混練する工程、
（２）（１）工程で得られた混練物に対して、（ａ）成分と（ｃ）成分と（ｅ）成分と（ｆ）成分と（ｇ）成分の残量を添加し、溶融混練する工程。
［１２］（ａ）ポリオレフィン系樹脂と（ｂ）ポリフェニレンエーテル系樹脂の合計１００質量部と、（ｃ）ビニル芳香族化合物を主体とする重合体ブロックＡと、共役ジエン化合物の１，２−ビニル結合量と３，４−ビニル結合量の合計量が３０〜９０％である共役ジエン化合物を主体とする重合体ブロックＢと、を含むブロック共重合体の少なくとも一部が水素添加された水添ブロック共重合体１〜１００質量部と、（ｄ）ポリアミン化合物０．１〜１質量部未満と、（ｅ）ヒンダードフェノール系安定剤０．０５〜３質量部と、（ｆ）イオウ系安定剤０．０５〜３質量部と、（ｇ）アクリレート系化合物０〜３質量部と、を溶融混練するに際して、下記（１）工程と、下記（２）工程と、を含む樹脂組成物の製造方法。
（１）（ｂ）成分と（ｄ）成分の全量と、（ｃ）成分と（ｅ）成分と（ｆ）成分と（ｇ）成分の一部あるいは全量とを、溶融混練する工程、
（２）（１）工程で得られた混練物に対して、（ａ）成分の全量と、（ｃ）成分と（ｅ）成分と（ｆ）成分と（ｇ）成分の残量を添加し、溶融混練する工程。
［１３］［１１］又は［１２］に記載された製造方法により得られる樹脂組成物。
［１４］［１］〜［１０］及び［１３］のいずれか一項に記載の樹脂組成物からなる成形品。
［１５］［１４］に記載の成形品からなるケーブル用被覆材。
［１６］［１５］に記載のケーブル用被覆材を用いたケーブル。 That is, the present invention provides the following.
[1] A total of 100 parts by mass of (a) polyolefin resin and (b) polyphenylene ether resin, (c) polymer block A mainly composed of vinyl aromatic compound, 1,2-vinyl bond amount and 3 Polymer block B mainly composed of a conjugated diene compound having a total amount of 1,4-vinyl bonds of 30 to 90%, and a hydrogenated block copolymer in which at least a part of the block copolymer is hydrogenated 1 to 100 parts by mass, (d) less than 0.1 to 1 part by mass of a polyamine compound, (e) 0.05 to 3 parts by mass of a hindered phenol stabilizer, and (f) a sulfur stabilizer 0.05 A resin composition containing ~ 3 parts by mass and (g) 0-3 parts by mass of an acrylate-based compound.
[2] The resin composition according to [1], further containing (h) a phosphorus compound in an amount of 0.05 to 3 parts by mass with respect to 100 parts by mass in total of the components (a) and (b).
[3] The resin composition according to [1] or [2], wherein the component (a) is a polypropylene resin.
[4] The melt flow rate (MFR) (230 ° C., load 2.16 kg) of the component (a) is 0.01 to 300 g / 10 minutes, according to any one of [1] to [3]. Resin composition.
[5] Any of [1] to [4], wherein the total amount of 1,2-vinyl bonds and 3,4-vinyl bonds in polymer block B of component (c) is 65 to 90%. The resin composition according to one item.
[6] The resin composition according to any one of [1] to [5], wherein the (d) polyamine compound is polyethyleneimine.
[7] The resin composition according to any one of [1] to [6], wherein the (d) polyamine compound is a compound represented by the following formula (1).

(In the formula, R ¹ , R ² and R ³ are the same or different and each represents an alkylene group. X and y each represents an integer of 1 or more.)
[8] The resin composition according to any one of [1] to [7], wherein the weight average molecular weight of the (d) polyamine compound is 200 to 100,000.
[9] The component (f) is dilauryl-3,3′-thiodipropionate, dimyristyl-3,3′-thiodipropionate, distearyl-3,3′-thiodipropionate, bis [2- Methyl-4- {3-n-alkylthiopropionyloxy} -5-t-butylphenyl] sulfide, tetrakis [methylene-3- (laurylthio) propionate] methane, tetrakis [methylene-3- (myristylthio) propionate] methane, Tetrakis [methylene-3- (stearylthio) propionate] methane, 2-mercaptobenzimidazole, ditridecylthiodipropionate, dilaurylthiodipropionate, distearylthiodipropionate and dimyristylthiodipropionate At least one selected from That, [1] to the resin composition according to any one of [8].
[10] The resin composition according to any one of [1] to [9], wherein the component (a) forms a matrix phase, and the component (b) forms a dispersed phase.
[11] A total of 100 parts by mass of (a) a polyolefin-based resin and (b) a polyphenylene ether-based resin, (c) a polymer block A mainly composed of a vinyl aromatic compound, and 1,2-vinyl as a conjugated diene compound Hydrogenation in which at least a part of a block copolymer including a polymer block B mainly composed of a conjugated diene compound having a total amount of bonds and 3,4-vinyl bonds of 30 to 90% is hydrogenated 1 to 100 parts by weight of a block copolymer, (d) less than 0.1 to 1 part by weight of a polyamine compound, (e) 0.05 to 3 parts by weight of a hindered phenol stabilizer, and (f) a sulfur-based stabilizer. Production of a resin composition comprising the following (1) step and (2) step when melt kneading 0.05 to 3 parts by mass of the agent and (g) 0 to 3 parts by mass of the acrylate compound Method.
(1) the total amount of component (b) and component (d), the component (c), component (e), component (f), component (g) or part of component (g), component (a) A step of melt kneading,
(2) Add the remaining amount of component (a), component (c), component (e), component (f) and component (g) to the kneaded product obtained in step (1), and melt knead Process.
[12] A total of 100 parts by mass of (a) a polyolefin-based resin and (b) a polyphenylene ether-based resin, (c) a polymer block A mainly composed of a vinyl aromatic compound, and 1,2-vinyl as a conjugated diene compound A hydrogenated hydrogenated at least part of a block copolymer comprising a polymer block B mainly composed of a conjugated diene compound having a total amount of bonds and 3,4-vinyl bonds of 30 to 90% 1 to 100 parts by weight of a block copolymer, (d) less than 0.1 to 1 part by weight of a polyamine compound, (e) 0.05 to 3 parts by weight of a hindered phenol stabilizer, and (f) a sulfur-based stabilizer. Production of a resin composition comprising the following (1) step and the following (2) step when melt-kneading 0.05 to 3 parts by mass of the agent and (g) 0 to 3 parts by mass of the acrylate compound Method.
(1) a step of melt-kneading the total amount of the component (b) and the component (d) and the part or the total amount of the component (c), the component (e), the component (f), and the component (g);
(2) Add the total amount of component (a) and the remaining amount of component (c), component (e), component (f) and component (g) to the kneaded product obtained in step (1). , Melting and kneading.
[13] A resin composition obtained by the production method described in [11] or [12].
[14] A molded article comprising the resin composition according to any one of [1] to [10] and [13].
[15] A cable covering material comprising the molded article according to [14].
[16] A cable using the cable covering material according to [15].

  ADVANTAGE OF THE INVENTION According to this invention, a foreign material can be reduced and the resin composition excellent in rigidity, impact resistance, and heat aging resistance, its manufacturing method, the molded article consisting of this, the cable coating | covering material, and a cable can be provided.

  Hereinafter, the best mode for carrying out the present invention (hereinafter referred to as “the present embodiment”) will be described in detail. The following embodiment is an exemplification for explaining the present invention, and is not intended to limit the present invention only to this embodiment. And this invention can be deform | transformed suitably and implemented within the range of the summary.

The resin composition according to the present embodiment is a resin composition containing the following components (a) to (f).
(A) 100 parts by mass of polyolefin resin and (b) polyphenylene ether resin in total,
(C) Mainly a polymer block A mainly composed of a vinyl aromatic compound, and a conjugated diene compound whose conjugated diene compound has a 1,2-vinyl bond amount and a 3,4-vinyl bond amount of 30 to 90%. 1 to 100 parts by mass of a block copolymer in which at least a part of the block copolymer including the polymer block B is hydrogenated,
(D) 0.1 to less than 1 part by mass of a polyamine compound,
(E) 0.05 to 3 parts by mass of a hindered phenol stabilizer,
(F) 0.05 to 3 parts by mass of a sulfur stabilizer,
(G) 0-3 mass parts of acrylate compound.

<(A) component>
The polyolefin resin used as the component (a) in the present embodiment (hereinafter sometimes simply referred to as “PO”) is not particularly limited. For example, isotactic polypropylene (iPP), ultrahigh molecular weight isotactic Polypropylene (UHMW-iPP), poly (4-methyl-1-pentene), polybutene-1 (PB-1), high density polyethylene (HDPE), ultra high molecular weight high density polyethylene (UHMW-HDPE), medium density polyethylene ( MDPE), low density polyethylene (LDPE), linear low density polyethylene (L-LDPE), ultra low density polyethylene (UPDPE), ethylene, propylene, other α-olefins, unsaturated carboxylic acids or derivatives thereof And a copolymer of two or more compounds.

  Examples of the copolymer of two or more compounds include ethylene / butene-1 copolymer, ethylene- (meth) acrylic acid copolymer, ethylene- (meth) acrylic acid ester copolymer, propylene / ethylene ( Random, block) copolymers, propylene / 1-hexene copolymers, propylene / 4-methyl-1-pentene copolymers, and the like.

  These polyolefin resin may be used individually by 1 type, and may use 2 or more types together. Among these, a polypropylene-based polyolefin resin is preferable from the viewpoint of balance of physical properties such as rigidity and toughness.

  Polypropylene resin is, for example, crystalline propylene homopolymer; crystalline propylene homopolymer portion obtained in the first step of polymerization, and propylene, ethylene and / or at least one other α-olefin in the second and subsequent steps of polymerization. Examples thereof include crystalline propylene-ethylene block copolymers having a propylene-ethylene random copolymer portion obtained by copolymerizing (for example, butene-1, hexene-1, etc.). A mixture of a crystalline propylene homopolymer and a crystalline propylene-ethylene block copolymer may also be used.

  The method for producing such a polypropylene resin is not particularly limited. For example, in the presence of a titanium trichloride catalyst or a titanium halide catalyst supported on a carrier such as magnesium chloride and an alkylaluminum compound, a polymerization temperature range of 0 to 100 ° C. The polymerization pressure can be obtained by polymerization in the range of 3 to 100 atm.

  At this time, a chain transfer agent such as hydrogen may be added in order to adjust the molecular weight of the polymer. Moreover, the polymerization method is not limited, and either a batch method or a continuous method may be used.

  In addition, solution polymerization in a solvent such as butane, pentane, hexane, heptane, octane; slurry polymerization; bulk polymerization in a monomer without solvent; gas phase polymerization method in a gaseous monomer, and the like can be applied.

  Furthermore, in order to increase the isotacticity and polymerization activity of the obtained polypropylene, an electron donating compound can be used as an internal donor component or an external donor component as a third component in addition to the above polymerization catalyst. The kind of the electron donating compound is not limited, and a known one can be used. For example, ester compounds such as ε-caprolactone, methyl methacrylate, ethyl benzoate and methyl toluate, phosphorous acid esters such as triphenyl phosphite and tributyl phosphite, and phosphoric acid derivatives such as hexamethylphosphoramide; Examples include alkoxy ester compounds, aromatic monocarboxylic acid esters, aromatic alkyl alkoxy silanes, aliphatic hydrocarbon alkoxy silanes, various ether compounds, various alcohols, and / or various phenols.

  The (a) polypropylene resin used in the present embodiment can be obtained by the method described above. Further, it may be a polypropylene resin having any crystallinity or melting point, and may be used alone or in combination of two or more.

The melt flow rate (MFR) (230 ° C., load 2.16 kg) of the polypropylene resin is preferably 0.01 to 300 g / 10 minutes, more preferably 0.1 to 100 g / 10 minutes, and still more preferably 0. .1 to 30 g / 10 min.
By setting the MFR within such a range, it is possible to balance rigidity and impact resistance.
Moreover, as long as it is a polypropylene resin which is MFR of these ranges, you may use independently and may use it together.

  Further, in addition to the above polypropylene resin, the polypropylene resin and the α, β-unsaturated carboxylic acid or derivative thereof are used in a molten state or in a solution state in the presence or absence of a radical generator. You may use the modified polypropylene resin which can be obtained by making it react at the temperature of (degreeC).

  Examples of the modified polypropylene resin include polypropylene resins obtained by grafting or adding 0.01 to 10% by mass of α, β-unsaturated carboxylic acid or a derivative thereof. The mixing ratio of the polypropylene resin and the modified polypropylene resin is not limited and can be mixed in any ratio.

<(B) component>
The (b) polyphenylene ether resin (hereinafter sometimes simply referred to as “PPE”) used in the present embodiment is a homopolymer and / or a copolymer having a repeating unit structure represented by the following formula (2). It is a coalescence.
The reduced viscosity (0.5 g / dL chloroform solution, measured at 30 ° C.) is not particularly limited, but is preferably in the range of 0.15 to 2.50, more preferably 0.30 to 2.00, More preferably, it is the range of 0.35-2.00.

In formula (2), R ⁴ , R ⁵ , R ⁶ , and R ⁷ are each independently a hydrogen atom, a halogen atom, a primary or secondary alkyl group having 1 to 7 carbon atoms, or a phenyl group. , A haloalkyl group, an aminoalkyl group, a hydrocarbonoxy group, or a group consisting of a halohydrocarbonoxy group in which at least two carbon atoms separate a halogen atom and an oxygen atom.

  The polyphenylene ether resin that can be used in the present embodiment is not particularly limited, and a known resin may be used. 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) Phenylene ether), poly (2,6-dichloro-1,4-phenylene ether) and the like, and 2,6-dimethylphenol and other phenols (for example, 2,3,6-trimethylphenol and 2- Polyphenylene ether copolymers such as methyl-6-butylphenol can also be used.

  Among them, preferred are poly (2,6-dimethyl-1,4-phenylene ether), a copolymer of 2,6-dimethylphenol and 2,3,6-trimethylphenol, and more preferred is poly (2,6-dimethyl-1,4-phenylene ether).

  The production method of the polyphenylene ether resin is not particularly limited, and a conventionally known one can be used. For example, it can be easily produced by, for example, oxidative polymerization of 2,6-xylenol using a complex of cuprous salt and amine described in US Pat. No. 3,306,874 as a catalyst. Alternatively, U.S. Pat. No. 3,306,875, U.S. Pat. No. 3,257,357, U.S. Pat. No. 3,257,358, JP-B-52-17880, JP-A-50-51197, JP-A-63-152628. It can be manufactured by a method described in a gazette or the like.

  Furthermore, in addition to the above polyphenylene ether resin, the polyphenylene ether resin and the styrene monomer or derivative thereof in the presence of or in the absence of a radical generator, in a molten state, a solution state or a slurry state, You may use together the modification | denaturation polyphenylene ether resin obtained by making it react at 350 degreeC.

  Examples of such modified polyphenylene ether resins include polyphenylene ether resins obtained by grafting or adding 0.01 to 10% by mass of a styrene monomer or a derivative thereof.

The mixing ratio of the polyphenylene ether resin and the modified polyphenylene ether resin is not limited, and can be mixed at an arbitrary ratio.
As the polyphenylene ether resin, in addition to the above-described resin, a mixture of polystyrene, syndiotactic polystyrene, or high impact polystyrene in a polyphenylene ether resin can be suitably used.
More preferably, it is mixed in a range not exceeding 400 parts by mass with respect to 100 parts by mass of the polyphenylene ether resin.

  In the present embodiment, it is preferable that the component (a) forms a matrix phase and the component (b) forms a dispersed phase. Thereby, heat-resistant creep property can be expressed. The dispersed phase may be the component (b) alone or the combination of the component (b) and the component (c). Such a resin composition comprises a matrix phase (component (a)) and dispersed particles constituting a dispersed phase (component (b), or component (b) and component (c)).

The length of the short axis diameter of the dispersed particles is preferably 2 μm or less, more preferably 1 μm or less. The ratio of the major axis diameter / minor axis diameter of the dispersed particles is preferably 1 to 10, more preferably 1 to 3. By setting the ratio of the short axis diameter and the long axis diameter / short axis diameter in such a range as the morphology of the dispersed particles, it is possible to impart further excellent heat-resistant creep resistance to the resin composition.
The dispersed particle size can usually be measured with a transmission electron microscope. The dispersed particles have [major axis diameter / minor axis diameter] ≧ 1.
Specifically, when [major axis diameter / minor axis diameter] = 1, that is, when the major axis diameter = minor axis diameter, circular dispersed particles are taken. When [major axis diameter / minor axis diameter]> 1, dispersed particles having a fibril structure or a lamellar structure are taken. The dispersed phase may be composed of one type or two or more types of dispersed particles having these structures.

  Although most of the component (c) is included in the dispersed particles composed of the component (b), the heat resistance and the creep resistance, which are the effects of the present embodiment, are not impaired in the matrix phase. Alternatively, it may be present separately from the dispersed particles.

<(C) component>
The hydrogenated block copolymer that can be used as the component (c) in the present embodiment includes a polymer block A mainly composed of a vinyl aromatic compound, a 1,2-vinyl bond amount of the conjugated diene compound, and 3, At least a part of a block copolymer containing a polymer block B mainly composed of a conjugated diene compound having a total amount of 4-vinyl bonds of 30 to 90% is hydrogenated.

  The component (c) acts as at least one of an admixture or an impact resistance imparting agent for the polyolefin resin as the component (a) and the polyphenylene ether resin as the component (b).

(Polymer block A mainly composed of vinyl aromatic compounds)
The polymer block A mainly composed of a vinyl aromatic compound is a homopolymer block of a vinyl aromatic compound or a copolymer block of a vinyl aromatic compound and a conjugated diene compound.

  In the polymer block A, “mainly composed of a vinyl aromatic compound” means that the polymer block A contains a vinyl aromatic compound in an amount exceeding 50 mass%. It is preferable to contain 70% by mass or more of a vinyl aromatic compound.

  Examples of the vinyl aromatic compound constituting the block polymer A include styrene, α-methylstyrene, vinyltoluene, p-tert-butylstyrene, diphenylethylene, and the like. These may be used alone or in combination of two or more. Of these, styrene is preferred.

The number average molecular weight of the block polymer A is not particularly limited, but is preferably 15000 or more. Thereby, the impact resistance of the resin composition of this Embodiment can be made more excellent.
The number average molecular weight of the block polymer A can be measured by GPC (moving layer: tetrahydrofuran, standard material: polystyrene).

(Polymer block B mainly composed of a conjugated diene compound having a total amount of 1,2-vinyl bonds and 3,4-vinyl bonds of 30 to 90%)
The polymer block B mainly composed of a conjugated diene compound is a homopolymer block of a conjugated diene compound or a random copolymer block of a conjugated diene compound and a vinyl aromatic compound.
In the polymer block B, “consisting mainly of a conjugated diene compound” means that the polymer block B contains a conjugated diene compound in an amount exceeding 50 mass%. And it is preferable to contain 70 mass% or more of conjugated diene compounds.

  The conjugated diene compound constituting the polymer block B is not particularly limited, and examples thereof include butadiene, isoprene, 1,3-pentadiene, 2,3-dimethyl-1,3-butadiene and the like. These may be used alone or in combination of two or more. Of these, butadiene, isoprene and combinations thereof are preferred.

  The microstructure of the polymer block B (bonded form of the conjugated diene compound) is the total amount of 1,2-vinyl bonds and 3,4-vinyl bonds in the polymer block B (hereinafter referred to as “all vinyl bonds”). May be referred to as “amount”.) Is 30 to 90%, preferably 45 to 85%. By setting the total vinyl bond amount within such a range, excellent miscibility can be obtained.

In particular, when the polymer block B is a polymer mainly composed of butadiene, the total vinyl bond content of the polymer block B is preferably 65 to 90%.
By setting the total vinyl bond amount to 30% or more, the dispersibility of the polyphenylene ether resin dispersed in the resulting resin composition can be improved. By setting the total vinyl bond amount to 90% or less, the polyphenylene ether resin can have excellent dispersibility.

  In the present embodiment, the total vinyl bond amount is measured with an infrared spectrophotometer. The calculation method is described in Analytical Chemistry, Volume 21, No. 8, according to the method described in August 1949.

The component (c) is a hydrogenated block copolymer of a block copolymer including the block polymer A and the block polymer B. Assuming that the block polymer A is “A” and the block polymer B is “B”, as the component (c), for example, AB, ABA, BABA, (A— B-) 4 _Si, vinyl aromatic compounds having a structure such as _a-B-a-B- a - hydrogenated product of a conjugated diene compound block copolymer.
(A-B-) ₄ Si is a reaction residue of a polyfunctional coupling agent such as silicon tetrachloride or tin tetrachloride, or a residue of an initiator such as a polyfunctional organolithium compound.

  The molecular structure of the block copolymer including the block polymer A and the block polymer B is not particularly limited, and may be, for example, linear, branched, radial, or any combination thereof.

In addition, the polymer block A mainly composed of vinyl aromatic compounds and the polymer block B mainly composed of conjugated diene compounds have a distribution of vinyl aromatic compounds or conjugated diene compounds in the molecular chains in the respective polymer blocks. It may consist of random, tapered (in which the monomer component increases or decreases along the molecular chain), a partial block, or any combination thereof.
When two or more polymer blocks A or polymer blocks B are present in the repeating unit, each polymer block may have the same structure or a different structure.

The hydrogenated block copolymer of component (c) preferably contains 20 to 95% by mass, and 30 to 80% by mass of the vinyl aromatic compound bonded to the block copolymer before hydrogenation. Further preferred.
In the present embodiment, the content of the vinyl aromatic compound can be measured with an ultraviolet spectrophotometer.

Moreover, the number average molecular weight of the block copolymer before hydrogenation is not particularly limited, but is preferably 5,000 to 1,000,000, more preferably 10,000 to 800,000, and still more preferably 30,000 to 500,000.
The number average molecular weight can be measured by gel permeation chromatography (GPC, solvent: tetrahydrofuran, standard material: polystyrene).

The molecular weight distribution of the block copolymer before hydrogenation is not particularly limited, but is preferably 10 or less. The molecular weight distribution can be calculated by the ratio of the weight average molecular weight (M _w ) and the number average molecular weight (M _n ) measured by gel permeation chromatography (GPC, solvent: tetrahydrofuran, standard substance: polystyrene).

The component (c) is a hydrogenated double bond derived from the conjugated diene compound in the block copolymer, and the hydrogenation rate for the conjugated diene compound in the component (c) is not limited. It is preferably 50% or more of the double bond amount derived from the diene compound, more preferably 80% or more, and still more preferably 90% or more.
In the present embodiment, the hydrogenation rate can be measured by NMR.

  (C) The manufacturing method of the hydrogenated block copolymer of a component is not specifically limited, For example, it can obtain with a well-known manufacturing method. For example, Japanese Patent Application Laid-Open Nos. 47-11486, 49-66743, 50-75651, 54-126255, and 56-10542 are disclosed. No. 5, JP-A 56-62847, JP-A 56-100900, JP-A 2-300218, British Patent 1130770, US Pat. No. 3,281,383, US Pat. No. 3639517 The methods described in the specification, British Patent No. 1020720, US Pat. No. 3,333,024 and US Pat. No. 4,501,857 can be used.

  In addition to the above-mentioned hydrogenated block copolymer, the hydrogenated block copolymer of component (c) includes a hydrogenated block copolymer and an α, β-unsaturated carboxylic acid or derivative thereof (ester compound or acid). It may be a modified hydrogenated block copolymer obtained by reacting an anhydride compound) in a molten state, a solution state or a slurry state at 80 to 350 ° C. in the presence or absence of a radical generator.

  In this case, it is preferable that the α, β-unsaturated carboxylic acid or derivative thereof is grafted or added to the hydrogenated block copolymer at a ratio of 0.01 to 10% by mass. Furthermore, it may be a mixture of the above hydrogenated block copolymer and modified hydrogenated block copolymer in an arbitrary ratio.

<(D) component>
The polyamine compound as the component (d) may be a compound having a primary amino group and / or a secondary amino group, and the type thereof is not particularly limited. Here, the secondary amino group refers to an imino group (—NH—).
Specific examples thereof include polyalkyleneimines such as polyethyleneimine and polypropyleneimine; methylenediamine, ethylenediamine, propylenediamine, 1,2-diaminopropane, 1,3-diaminopentane, hexamethylenediamine, diaminoheptane, diaminododecane, diethylenetriamine , Diethylaminopropylamine, N-aminoethylpiperazine, triethylenetetramine, and other aliphatic polyamines; diaminocyclohexane, bis- (4-aminocyclohexyl) methane, and other alicyclic amines; diaminotoluene, diaminoxylene, tetramethylxylylenediamine And aromatic polyamines such as metaphenylenediamine, diaminodiphenylmethane, and diaminodiphenylsulfone.
Among these, polyethyleneimine is preferable from the viewpoint of reducing foreign substances in the resin composition.

  Moreover, it is preferable that (d) component has branched carbon and / or branched nitrogen, and it is more preferable that it has a tertiary amino group. Here, the branched carbon means a carbon atom that is a starting point from which the main chain skeleton of the polyamine compound is branched. Branched nitrogen refers to a nitrogen atom that is the starting point from which the main chain skeleton of a polyamine compound is branched. The tertiary amino group refers to a group consisting of a nitrogen atom in which no hydrogen atom is bonded to any bond.

  As described above, preferable polyamine compounds used in the present embodiment include those having a primary amino group and a secondary amino group, primary amino groups, secondary amino groups, and tertiary amino groups. And the like. Of these, more preferred are those having a primary amino group, a secondary amino group, and a tertiary amino group.

  As a polyamine compound which has a primary amino group, a secondary amino group, and a tertiary amino group, the compound represented by following formula (1) is mentioned, for example.

In the formula, R ¹ , R ² and R ³ represent an alkylene group, and may be the same or different. x and y each represents an integer of 1 or more. R ^{1 to} R ³ may be an alkylene group, for example, —CH ₂ CH ₂ —, —CH ₂ CH ₂ CH ₂ —, —CH ₂ CH ₂ CH ₂ CH ₂ —, —CH ₂ CH (CH ₃ )-, etc.

  The weight average molecular weight of a polyamine compound is not specifically limited, Preferably it is 200-100000, A more preferable lower limit is 300 or more, A more preferable upper limit is 10,000 or less. The weight average molecular weight is measured by gel permeation chromatography (GPC, mobile phase: tetrahydrofuran, standard substance: polystyrene). By setting the weight average molecular weight in such a range, the fluidity of the resin composition can be prevented from deteriorating while having dispersibility, stability and water resistance.

<(E) component>
As the hindered phenol stabilizer of the component (e) in the present embodiment, a compound having a hindered phenol structure can be used.
(E) By containing a component, it can be set as the heat stabilizer which exhibits an effect over a long period of time not only at the time of a process.
The kind of the compound that can be used as the hindered phenol stabilizer is not particularly limited, and specifically, triethylene glycol-bis [3- (3-t-butyl-5-methyl-4-hydroxyphenyl). Propionate], 1,6-hexanediol-bis [3- (3,5-di-t-butyl-4-hydroxyphenyl) propionate], 2,4-bis- (n-octylthio) -6- (4- Hydroxy-3,5-di-t-butylanilino) -1,3,5-triazine, pentaerythritol tetrakis [3- (3,5-di-t-butyl-4-hydroxyphenyl) propionate], octadecyl-3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionate, N, N′-hexane-1,6-diylbis [3- (3,5-di- t-butyl-4-hydroxyphenyl) propionamide], 3,5-di-t-butyl-4-hydroxy-benzylphosphonate-diethyl ester, 1,3,5-trimethyl-2,4,6-tris (3,5-di-t-butyl-4-hydroxybenzyl) benzene, tris- (3,5-di-t-butyl-4-hydroxybenzyl) -isocyanurate, N, N′-bis [3- ( 3,5-di-tert-butyl-4-hydroxyphenyl) propionyl] hydrazine dibutylhydroxytoluene, 4,4′-butylidenebis- (6-tert-butyl-3-methylphenol), 2,2′-methylenebis- ( 4-methyl-6-tert-butylphenol), 1,3,5-tris (3 ′, 5′-di-tert-butyl-4′-hydroxybenzyl) -1,3,5-triazine 2,4,6 (1H, 3H, 5H) -trione, 1,1,3-tris (2-methyl-4-hydroxy-5-tert-butylphenyl) butane, 4,4′-butylidenebis (3-methyl) -6-t-butylphenol), n-octadecyl-3- (3 ′, 5′-di-t-butyl-4′-hydroxyphenyl) propionate, tetrakis [methylene-3- (3 ′, 5′-di-) t-butyl-4-hydroxyphenyl) propionate] methane, 3,9-bis [2- [3- (3-t-butyl-4-hydroxy-5-methylphenyl) propionyloxy] -1,1-dimethylethyl ] -2,4,8,10-tetraoxaspiro [5,5] undecane and the like.

The component (e) can be appropriately selected from commercially available products. Specifically, Irganox (registered trademark) 1010, Irganox 1076, Irganox 1098, Irganox 1330, Irganox 245, Irganox 259, Irganox 3114, Irganox 3790, and Adeka 30 registered trademark of Adeka (Adeka Tab 30 registered by ADEKA), manufactured by Ciba Japan. Adeka Stub AO-80 and the like are preferable.
Among them, compounds having 2,6-dt-butylphenol having a large steric hindrance in the structure are preferable, and specific examples include Irganox 1010, Irganox 1076, Irganox 1098, Irganox 1330, Adeka Stab AO-80 and the like.

<Component (f)>
The sulfur stabilizer of the component (f) in the present embodiment is not particularly limited, and examples thereof include dilauryl-3,3′-thiodipropionate, dimyristyl-3,3′-thiodipropionate, and distearyl. -3,3'-thiodipropionate, bis [2-methyl-4- {3-n-alkylthiopropionyloxy} -5-t-butylphenyl] sulfide, tetrakis [methylene-3- (dodecylthio) propionate] methane Tetrakis [methylene-3- (myristylthio) propionate] methane, tetrakis [methylene-3- (stearylthio) propionate] methane, 2-mercaptobenzimidazole, ditridecylthiodipropionate, dilaurylthiodipropionate, di Stearyl thiodipropionate and dimyristilchi Dipropionate, and the like.

The component (f) can be appropriately selected from commercially available products. Specifically, compounds derived from sulfur-based stabilizers such as Irganox PS800FD and Irganox PS802FD manufactured by Ciba Japan, Adeka Stub AO-23, Adeka Stub AO-412S, and Adeka Stab AO-503 manufactured by ADEKA are preferable.
Among them, a compound derived from a compound having an ADK STAB AO-412S structure is most preferable from the viewpoint of heat aging resistance. Use of such a compound is preferable because it functions as an antioxidant capable of exhibiting an effect over a long period of time.

  In order to more effectively exhibit the synergistic effect of heat aging resistance, it is more preferable to use the component (e) and the component (f) in combination. And heat resistance aging property can further be improved by using together (d) component, (e) component, and (f) component.

In the resin composition according to the present embodiment, it is preferable to use a compound having a sulfur element and a phenolic hydroxyl group in the same molecule in addition to the components (e) and (f). This is preferable because it works as an antioxidant that can exhibit an effect over a long period of time as well as during processing.
Such a compound is not particularly limited, and examples thereof include 4,6-bis (octylthiomethyl) -o-cresol, 4,6-bis (dodecylthiomethyl) -o-cresol, and 2,2′-thiobis. (6-tert-butyl-4-methylphenol), 2,2′-thiobis (4-octylphenol), 4,4′-thiobis (6-tert-butyl-3-methylphenol), 4,4′-thiobis (3,6-di-sec-amylphenol), 4,4′-thiobis (6-tert-butyl-2-methylphenol), 4,4′-bis (2,6-dimethyl-4-hydroxyphenyl) And disulfide, 2,6-di-tert-butyl-4- {4,6-bis (octylthio) -1,3,5-triazin-2-ylamino} phenol, and the like.

<(G) component>
In the resin composition according to the present embodiment, an acrylate compound as the component (g) can be used. The acrylate compound acts as a heat deterioration inhibitor in the resin composition according to the present embodiment. Although it does not specifically limit as an acrylate type compound, The compound represented by following formula (3) is preferable. By using such a compound, thermal deterioration can be more effectively prevented.

In said formula (3), R < ⁸ > is a C1-C5 alkyl group, for example, a methyl group, an ethyl group, a propyl group, t-butyl group, 2, 2- dimethylpropyl group etc. are mentioned. It is done. A methyl group or an ethyl group is preferable, and an ethyl group is more preferable.
R ⁹ is an alkyl group having 1 to 8 carbon atoms, and examples thereof include a methyl group, an ethyl group, a propyl group, a t-butyl group, a t-pentyl group, and a t-octyl group. A methyl group, a t-butyl group or a t-pentyl group is preferred, and a t-pentyl group is more preferred.
R ¹⁰ is a hydrogen atom or an alkyl group having 1 to 8 carbon atoms, and examples thereof include a hydrogen atom, a methyl group, an ethyl group, a propyl group, a butyl group, a pentyl group, and an octyl group. Preferably they are a hydrogen atom or a methyl group, More preferably, it is a methyl group.
R ¹¹ is a hydrogen atom or alkyl having 1 to 5 carbon atoms, and examples thereof include a hydrogen atom, a methyl group, an ethyl group, a propyl group, a butyl group, and a pentyl group. Preferably, it is a hydrogen atom.

The acrylate compound of the present embodiment is not particularly limited, and for example, 2,4-di-t-amyl-6- [1- (3,5-di-t-amyl-2-hydroxyphenyl) ethyl ] Phenyl acrylate, 2,4-di-t-amyl-6- [1- (3,5-di-t-amyl-2-hydroxyphenyl) butyl] phenyl acrylate, 2,4-di-t-amyl- 6- [1- (3,5-di-t-amyl-2-hydroxyphenyl) propyl] phenyl acrylate, 2-t-butyl-6- (3-t-butyl-2-hydroxy-5-methylbenzyl) Examples include -4-methylphenyl acrylate.
Among them, 2,4-di-t-amyl-6- [1- (3,5-di-t-amyl-2-hydroxyphenyl) ethyl] phenyl acrylate and 2-t-butyl-6- (3-t-butyl-2-hydroxy-5-methylbenzyl) -4-methylphenyl acrylate.

  The component (g) can be appropriately selected from commercially available products. For example, Sumitizer (registered trademark) GM manufactured by Sumitomo Chemical Co., Ltd., which is 2-t-butyl-6- (3-t-butyl-2-hydroxy-5-methylbenzyl) -4-methylphenyl acrylate, 2, Sumitizer (registered trademark) GS manufactured by Sumitomo Chemical Co., Ltd., which is 4-di-t-amyl-6- [1- (3,5-di-t-amyl-2-hydroxyphenyl) ethyl] phenyl acrylate, etc. Can be used.

<(H) component>
In the resin composition according to the present embodiment, it is preferable to use the phosphorus compound of component (h). The phosphorus compound that can be used as the component (h) decomposes hydroperoxycide generated during molding in the resin composition according to the present embodiment into an ionically harmless alcohol. As a result, it works well as a heat stabilizer during processing and for a long time.

  The phosphorus compound as the component (h) is not particularly limited, and di (nonylphenyl) pentaerythritol diphosphite, phenyl-bisphenol A pentaerythritol diphosphite, distearyl pentaerythritol diphosphite, dioctyl pentaerythritol diphosphite, Dilauryl pentaerythritol diphosphite, diphenylpentaerythritol diphosphite, dicyclohexylpentaerythritol diphosphite, bis (2,4-di-t-butylphenyl) pentaerythritol diphosphite, bis (2,6-di-t -Butyl-4-methylphenyl) pentaerythritol diphosphite, bis (2,4,6-tri-t-butylphenyl) pentaerythritol diphosphite, tetrakis (2,4-di-t-butylphenyl) -4,4′-biphenylene phosphonite, 2,2′-ethylidenebis (4,6-di-t-butylphenyl) fluorophosphite, 2,2 ′ -Methylenebis (4,6-di-t-butylphenyl) octyl phosphite, 9,10-dihydro-9-oxa-10-phosphenanthrene-10-oxide, tris (isodecyl) phosphite, tris (tridecyl) phos Phyto, phenyl diisooctyl phosphite, phenyl diisodecyl phosphite, phenyl di (tridecyl) phosphite, diphenyl isooctyl phosphite, diphenyl isodecyl phosphite, diphenyl tridecyl phosphite, triphenyl phosphite, tris (2,4- G-t Butylphenyl) phosphite, tris (mononolylphenyl) phosphite, tris (mono, dinolylphenyl) phosphite, 4,4′-isopropylidenediphenol tetraalkyldiphosphite having an alkyl group having 12 to 15 carbon atoms 4,4′-butylidene-bis- (3-methyl-6-tert-butylphenyl-di-tridecyl) phosphite, 1,1,3-tris (2-methyl-4-di-tridecyl phosphite) 5-t-butylphenyl) butane and the like.

The resin composition of the present embodiment is composed of components (a) to (g) as basic components. In the present embodiment, the amount of component (a) is preferably 1 to 99 parts by mass, more preferably 5 to 95 parts by mass, with respect to 100 parts by mass in total of component (a) and component (b). .
By setting it as this compounding quantity, it can be set as the resin composition excellent in the heat resistance of the resin composition obtained, a moldability, and solvent resistance.

  The amount of component (b) is preferably 99-1 parts by weight, more preferably 95-5, with respect to 100 parts by weight of component (a) and component (b). Part by mass. By setting it as this compounding quantity, it can be set as the resin composition excellent not only in the heat resistance of the resin composition obtained but also in moldability and solvent resistance.

(C) The compounding quantity of a component is 1-100 mass parts with respect to a total of 100 mass parts of (a) component and (b) component.
When the blending amount is less than 1 part by mass, the effect as an admixture is not seen in the resin composition of the present embodiment, which is not preferable. The effect as this admixture means the effect of finely emulsifying and dispersing the polyphenylene ether resin in the polyolefin resin and / or the effect of finely emulsifying and dispersing the polyolefin resin in the polyphenylene ether resin.
Moreover, when this compounding quantity exceeds 100 mass parts, the fall of the heat resistance and solvent resistance which (a) component and (b) component show are remarkable, and it is unpreferable.

The blending amount of the component (d) is 0.1 parts by mass or more and 1 part by mass with respect to 100 parts by mass of the total of the components (a) and (b) from the viewpoint of rigidity, tensile elongation, heat-resistant creep resistance, and reduction of foreign matter. Less than part.
When the amount is less than 0.1 parts by mass, the effects of rigidity, impact resistance, heat and heat aging resistance, and foreign matter reduction are not sufficient.
Moreover, since the heat resistance falls when this compounding quantity is 1 mass part or more, it is unpreferable.

  (E) As a compounding quantity of a component, it is 0.05-3 mass parts with respect to a total of 100 mass parts of (a) component and (b) component, and when it is less than this lower limit, improvement in heat aging resistance An effect is not seen and it is not preferable.

  (F) As a compounding quantity of a component, it is 0.05-3 mass parts with respect to a total of 100 mass parts of (a) component and (b) component, and when it does not satisfy this lower limit, improvement in heat aging resistance An effect is not seen and it is not preferable.

  Further, the heat aging resistance is further improved by the synergistic effect of the component (d), the component (e) and the component (f). (G) The compounding quantity of a component is 0-3 mass parts with respect to a total of 100 mass parts of (a) component and (b) component.

In the present embodiment, in addition to the above components, other additional components may be added as necessary within the range not impairing the features and effects of the present embodiment.
Other additional components are not particularly limited. For example, vinyl aromatic compound-conjugated diene compound block copolymer, olefin elastomer, antioxidant, metal deactivator, heat stabilizer, flame retardant ( Organophosphate compounds, ammonium polyphosphate compounds, melamine polyphosphate compounds, phosphinates, magnesium hydroxide, aromatic halogen flame retardants, silicone flame retardants, etc.), fluorine polymers, plasticizers (low molecular weight) Polyethylene, epoxidized soybean oil, polyethylene glycol, fatty acid esters, etc.), flame retardant aids such as antimony trioxide, weather resistance (light) improvers, polyolefin nucleating agents, slip agents, inorganic or organic fillers, Reinforcing material (GF, GF long fiber, CF, CF long fiber, polyacrylonitrile fiber, carbon black, titanium oxide , Calcium carbonate, conductive metal fibers, conductive carbon black, etc.), various colorants, mold release agents and the like.

<Method for producing resin composition>
The manufacturing method of the resin composition of this Embodiment is demonstrated. The resin composition of the present embodiment can be produced using various melt mixers and kneading extruders, but a production method having the following steps is preferred.

A total of 100 parts by mass of (a) polyolefin resin and (b) polyphenylene ether resin;
(C) a polymer block A mainly composed of a vinyl aromatic compound, and a conjugated diene compound having a total amount of 1,2-vinyl bonds and 3,4-vinyl bonds of the conjugated diene compound of 30 to 90%. 1 to 100 parts by mass of a block copolymer in which at least a part of the block copolymer including the polymer block B as a main component is hydrogenated,
(D) 0.1 to less than 1 part by mass of a polyamine compound,
(E) 0.05 to 3 parts by mass of a hindered phenol stabilizer,
(F) 0.05 to 3 parts by mass of a sulfur stabilizer;
(G) A method for producing a resin composition comprising the following steps (1) and (2) when melt-kneading 0 to 3 parts by mass of an acrylate compound.
(1) (b) component and (d) total amount of component, (c) component, (e) component, (f) component, (g) part or all of component, (a) part of component A step of melt kneading,
(2) Add the remaining amount of component (a), component (c), component (e), component (f) and component (g) to the kneaded product obtained in step (1), and melt knead Process.

Alternatively, when melt kneading the component (a), component (b), component (c), component (d), component (e), component (f) and component (g), the following step (1) and ( 2) A method for producing a resin composition including a step is also preferable.
(1) a step of melt-kneading the total amount of the component (b) and the component (d), the component (c), the component (e), the component (f), and a part or the total amount of the component (g);
(2) Add the total amount of component (a) and the remaining amount of component (c), component (e), component (f) and component (g) to the kneaded product obtained in step (1). , Melting and kneading.

  The resin composition obtained by these production methods effectively suppresses the thermal deterioration of the component (b) by the component (d), and the mixture of the component (a), the component (b), and the component (c) is excellent. In addition, a resin composition having excellent rigidity, impact resistance and heat aging resistance can be obtained.

  A melt kneader for performing these methods is not particularly limited, and a known kneader can be used. For example, a single screw extruder, a multi-screw extruder including a twin screw extruder, a roll, a kneader, a Brabender A heat melting and kneading machine such as a plastograph or a Banbury mixer can be used. Among them, the melt kneading method using a twin screw extruder is preferable. Specifically, the ZSK series manufactured by Coperion, the TEM series manufactured by Toshiba Machine Co., Ltd., the TEX series manufactured by Nippon Steel Works, Ltd., and the like can be used.

  Moreover, if it is a case where an extruder is used, the kind, specification, etc. will not be specifically limited, A well-known extruder can be used suitably. The L / D (barrel effective length / barrel inner diameter) of the extruder is preferably in the range of 20 to 75, and more preferably in the range of 30 to 60.

  The extruder has a first raw material supply port on the upstream side with respect to the flow direction of the raw material, a first vacuum vent on the downstream side, a second raw material supply port on the downstream side, and a second vacuum vent on the downstream side. In addition, it is preferable to provide a first raw material supply port on the upstream side, a first vacuum vent on the downstream side, a second and third raw material supply port on the downstream side, and a second vacuum vent on the downstream side.

  Among them, a kneading section is provided upstream of the first vacuum vent, a kneading section is provided between the first vacuum vent and the second raw material supply port, and further between the second raw material supply port and the second vacuum vent. A kneading section is provided, a kneading section is provided upstream of the first vacuum vent, a kneading section is provided between the first vacuum vent and the second raw material supply port, and a second raw material supply port and a third More preferably, a kneading section is provided at the raw material supply port, and a kneading section is provided between the second raw material supply port and the second vacuum vent.

  Moreover, the raw material supply method to a 2nd, 3rd raw material supply port is not specifically limited, Rather than the mere addition supply from the open port of the 2nd, 3rd raw material supply port of an extruder, it is from an extruder side open port. It is more stable and preferable to supply using a forced side feeder.

  The melt-kneading temperature and the screw rotation speed are not particularly limited, but can be appropriately selected from a melt-kneading temperature of 200 to 370 ° C. and a screw rotation speed of 100 to 1200 rpm.

The resin composition of the present embodiment can be used as a molded product.
As a molded article, it can be set as various components, a sheet | seat, a film, etc., for example. The molding method is not particularly limited, and various conventionally known methods can be employed. For example, injection molding, extrusion molding, extrusion profile forming, hollow molding and the like can be mentioned.

  Examples of the various parts include automobile parts. Specifically, bumpers, fenders, door panels, various moldings, emblems, engine hoods, wheel caps, roofs, spoilers, various aero parts, and other exterior parts, It is suitable for interior parts such as instrument panels, console boxes and trims, as well as secondary battery battery case parts and lithium ion battery separators mounted on automobiles, electric cars and hybrid electric cars.

  Furthermore, it can be suitably used as an interior / exterior part of electrical equipment, specifically, various computers and peripheral equipment, other office automation equipment, televisions, videos, various disk player cabinets, chassis, refrigerators, air conditioners, and liquid crystal projectors. Is mentioned. It is also suitable for a lithium ion battery separator for electrical equipment. Industrial use is suitable for parts such as various pump casings and boiler casings.

  The molded product according to the present embodiment is an optical fiber coating material obtained by using a known wire extrusion coating apparatus, a low-voltage type wire / cable, an instrument cable, an electronic wire, an automotive wire harness, and a nuclear power plant. Suitable for control cables such as cables.

  The molded article according to the present embodiment can be used as a cable covering material. Since the resin composition according to the present embodiment is excellent in the balance between rigidity and tensile strength and excellent in heat-resistant creep resistance, a molded product made of this resin composition can be suitably used as a coating material for cables. .

  Furthermore, it can be set as a cable by using the coating | covering material for cables and conducting wire which concern on this Embodiment. The use, size, structure, and the like of the cable are not limited. For example, a cable or the like in which the outer periphery of a conducting wire (center conductor) is coated with an insulating coating layer and the outer periphery is further coated with a cable coating material. .

  Note that the shape and type of the conductive wire that can be used for the cable according to the present embodiment is not particularly limited, and may be a single wire or a double wire. The material of the conducting wire is not particularly limited, and is appropriately selected from known materials, and examples thereof include copper and its alloy wire, aluminum and its alloy wire, or those obtained by plating these wires. Moreover, the conducting wire may be covered with tin or silver.

  The present embodiment will be described in more detail with reference to examples, but the present invention is not limited to these examples.

Each physical property of each material was performed as follows.
[Number average molecular weight]
The number average molecular weight of each component was measured by GPC (mobile phase: tetrahydrofuran, standard substance: polystyrene).

[Measurement of bound styrene content]
The amount of bound styrene was measured with an ultraviolet spectrophotometer.

[Measurement of vinyl bond content]
The vinyl bond amount was measured with an infrared spectrophotometer.

[Measurement of hydrogenation rate]
The hydrogenation rate was measured by NMR.

[Melting point]
The melting point of each component was measured with a differential scanning calorimeter.

[MFR (melt flow rate)
The MFR was measured with a load of 2.16 kg at 230 ° C.

[Reduced viscosity]
The reduced viscosity was measured by 0.5 g / dL chloroform solution at 30 ° C.

[Production of resin composition]
1. Component (a) (polyolefin resin)
Propylene homopolymer Melting point: 167 ° C., MFR: 0.4 g / 10 min

2. Component (b) (polyphenylene ether resin)
2,6-xylenol was oxidatively polymerized to obtain a polyphenylene ether homopolymer.
Reduced viscosity: 0.54

3. Component (c) (hydrogenated block copolymer)
(C-1) A hydrogenated polybutadiene-polystyrene (1) -hydrogenated polybutadiene-polystyrene (2) block copolymer having a B-A-B-A type structure was synthesized by a conventional method. This block copolymer was hydrogenated by a conventional method to obtain a hydrogenated block copolymer.
Bonded styrene content: 43%
Total amount of 1,2-vinyl bonds and 3,4-vinyl bonds in polybutadiene before hydrogenation (total vinyl bonds): 75%
Number average molecular weight of hydrogenated block copolymer: 98000
Number average molecular weight of polystyrene (1): 20000
Number average molecular weight of polystyrene (2): 22000
Polybutadiene part hydrogenation rate: 99.9%
(C-2) A block copolymer having an ABA type structure of polystyrene (1) -hydrogenated polybutadiene-polystyrene (2) was synthesized by a conventional method. This block copolymer was hydrogenated by a conventional method to obtain a hydrogenated block copolymer.
Bonded styrene content: 43%
Total amount of 1,2-vinyl bonds and 3,4-vinyl bonds in polybutadiene before hydrogenation (total vinyl bonds): 75%
Number average molecular weight of hydrogenated block copolymer: 97000
Number average molecular weight of polystyrene (1): 22000
Number average molecular weight of polystyrene (2): 20000
Hydrogenation rate of polybutadiene part: 99.9% hydrogenated product of styrene-butadiene block copolymer (c-3) ABA structure of polystyrene (1) -hydrogenated polybutadiene-polystyrene (2) The block copolymer having was synthesized by a conventional method.
Bonded styrene content: 45%
Total amount of 1,2-vinyl bonds and 3,4-vinyl bonds in polybutadiene before hydrogenation (total vinyl bonds): 20%,
Number average molecular weight of hydrogenated block copolymer: 92000
Number average molecular weight of polystyrene (1): 21000
Number average molecular weight of polystyrene (2): 20400
Polybutadiene part hydrogenation rate: 99.9%

4). (D) Component (polyamine compound)
(D-1) Weight average molecular weight of polyethyleneimine: 10,000
Epomin SP-200 (registered trademark, manufactured by Nippon Shokubai Co., Ltd.)
(D-2) Weight average molecular weight of polyethyleneimine: 1800
Epomin SP-018 (registered trademark, manufactured by Nippon Shokubai Co., Ltd.)
(D-3) Weight average molecular weight of polyethyleneimine: 300
Epomin SP-003 (registered trademark, manufactured by Nippon Shokubai Co., Ltd.)

5). (E) component (hindered phenol stabilizer)
Pentaerythritol tetrakis [3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionate]
Irganox 1010 (Ciba Japan)
6). (F) Sulfur-based stabilizer Tetrakis [methylene-3- (dodecylthio) propionate] methane AO-412S (manufactured by ADEKA)
7). (G) Acrylate compound 2,4-di-t-amyl-6- [1- (3,5-di-t-amyl-2-hydroxyphenyl) ethyl] phenyl acrylate Sumitizer GS (Sumitomo Chemical Co., Ltd.) Made)
8). (H) Phosphorus compound Tris (2,4-di-t-butylphenyl) phosphite Irgafos 168 (manufactured by Ciba Japan)

<Example 1>
Using a twin screw extruder ZSK-25 (manufactured by Coperion), a first raw material supply port is provided upstream of the raw material flow direction, a second raw material supply port is provided downstream of this, and a vacuum vent is further provided downstream thereof. It was. Moreover, the raw material supply method to a 2nd supply port is supplied using a forced side feeder from an extruder side open port. Using the extruder set as described above, the components (a) to (h) were blended with the composition shown in Table 1, and the conditions were such that the extrusion temperature was 270 to 320 ° C., the screw rotation speed was 300 rpm, and the discharge rate was 12 kg / hour. And kneaded to obtain pellets.

<Examples 2 to 7>
Pellets were obtained in the same manner as in Example 1 except that the components (a) to (e) were performed under the conditions shown in Table 1.

<Comparative Examples 1-9>
Pellets were obtained in the same manner as in Example 1 except that the components (a) to (e) were performed under the conditions shown in Table 2.

<Bending elastic modulus, Charpy impact strength>
Test pieces for measuring flexural modulus and Charpy impact strength are supplied to a screw in-line injection molding machine set at 240 to 280 ° C. using the resin pellets obtained in the examples and comparative examples, under the conditions of a mold temperature of 60 ° C. Was subjected to heat history treatment by being left in an environment of 80 ° C. for 24 hours using a gear oven. Using these molded articles, the flexural modulus was measured according to ISO178, and the Charpy impact strength was measured according to ISO179.

<Heat resistant aging property>
The resin pellets obtained in the examples and comparative examples are supplied to a screw in-line injection molding machine set at 240 to 280 ° C., and the dumbbell molded product (thickness) shown in FIG. 1 mm) was injection molded. Reference numeral 1 in FIG. 1 indicates a test piece. The width L1 is 65 mm, the width L2 is 40 mm, and the width L3 is 22 mm. The height H is 10 mm.
The test piece was allowed to stand for 24 hours in an environment of 80 ° C. using a gear oven, and a heat history treatment was performed. After the heat history treatment, aging was performed for 240 hours in a 150 ° C. environment using a gear oven. In the measurement of heat aging resistance, a tensile test was performed, and the retention of tensile elongation obtained below was evaluated as heat aging resistance.

Tensile elongation retention (%) = (tensile elongation after aging) / (tensile elongation after heat history treatment) × 100

<Foreign matter test>
The resin composition pellets obtained in the examples and comparative examples are supplied to a screw in-line injection molding machine set at 240 to 280 ° C., and a dumbbell molded product having the shape shown in FIG. 1 mm thick) was molded. The obtained three test pieces were visually observed, and the number of brown or black foreign matters was counted. The case where the total value of the number of foreign matters was less than 10 was indicated as “◯”, and the case where the total number was 10 or more was indicated as “X”.

  The above results are shown in Tables 1 and 2.

From Tables 1 and 2, the resin compositions of Examples 1 to 7 are excellent in rigidity, impact resistance, heat aging resistance and foreign matter reduction at the same time, but the resin compositions of Comparative Examples 1 to 9 are rigid and impact resistant. The heat resistance, heat aging resistance and foreign matter were not excellent at the same time.
From the above, it was shown that by using the resin composition according to the present embodiment, a resin composition excellent in rigidity, impact resistance, heat aging resistance, and foreign matter reduction can be obtained.

  The resin composition obtained in the present invention and a molded product, a cable covering material and a cable made of the resin composition can reduce foreign matters, and the molded product has excellent rigidity, impact resistance, and heat aging resistance. It can be suitably used for various applications that require the above characteristics.

It is a simplified side view of the test piece used in the Example.

Explanation of symbols

1 Test piece

Claims (16)

A total of 100 parts by mass of (a) polyolefin resin and (b) polyphenylene ether resin;
(C) Polymer block A mainly composed of a vinyl aromatic compound, and a heavy composed mainly of a conjugated diene compound whose total amount of 1,2-vinyl bonds and 3,4-vinyl bonds is 30 to 90%. 1 to 100 parts by mass of a hydrogenated block copolymer obtained by hydrogenating at least a part of a block copolymer including the combined block B;
(D) 0.1 to less than 1 part by mass of a polyamine compound,
(E) 0.05 to 3 parts by mass of a hindered phenol stabilizer,
(F) 0.05 to 3 parts by mass of a sulfur stabilizer;
(G) 0 to 3 parts by mass of an acrylate compound,
Containing a resin composition.   Furthermore, the resin composition of Claim 1 which contains 0.05-3 mass parts of (h) phosphorus compounds with respect to a total of 100 mass parts of the said (a) component and the said (b) component.   The resin composition according to claim 1 or 2, wherein the component (a) is a polypropylene resin.   The resin composition as described in any one of Claims 1-3 whose melt flow rate (MFR) (230 degreeC, load 2.16kg) of the said (a) component is 0.01-300 g / 10min.   The total amount of 1,2-vinyl bonds and 3,4-vinyl bonds in the polymer block B of the component (c) is 65 to 90% according to any one of claims 1 to 4. The resin composition as described.   The resin composition according to claim 1, wherein the (d) polyamine compound is polyethyleneimine. The resin composition according to any one of claims 1 to 6, wherein the (d) polyamine compound is a compound represented by the following formula (1).

(In the formula, R ¹ , R ² and R ³ are the same or different and each represents an alkylene group. X and y each represents an integer of 1 or more.)   The resin composition as described in any one of Claims 1-7 whose weight average molecular weights of the said (d) polyamine compound are 200-100000.   The component (f) is dilauryl-3,3′-thiodipropionate, dimyristyl-3,3′-thiodipropionate, distearyl-3,3′-thiodipropionate, bis [2-methyl- 4- {3-n-alkylthiopropionyloxy} -5-t-butylphenyl] sulfide, tetrakis [methylene-3- (laurylthio) propionate] methane, tetrakis [methylene-3- (myristylthio) propionate] methane, tetrakis [ Methylene-3- (stearylthio) propionate] selected from the group consisting of methane, 2-mercaptobenzimidazole, ditridecylthiodipropionate, dilaurylthiodipropionate, distearylthiodipropionate and dimyristylthiodipropionate At least one kind There, the resin composition according to any one of claims 1-8.   The resin composition according to any one of claims 1 to 9, wherein the component (a) forms a matrix phase, and the component (b) forms a dispersed phase. A total of 100 parts by mass of (a) polyolefin resin and (b) polyphenylene ether resin;
(C) a polymer block A mainly composed of a vinyl aromatic compound, and a conjugated diene compound having a total amount of 1,2-vinyl bonds and 3,4-vinyl bonds of the conjugated diene compound of 30 to 90%. 1 to 100 parts by mass of a hydrogenated block copolymer obtained by hydrogenating at least a part of a block copolymer including a main polymer block B;
(D) 0.1 to less than 1 part by mass of a polyamine compound,
(E) 0.05 to 3 parts by mass of a hindered phenol stabilizer,
(F) 0.05 to 3 parts by mass of a sulfur stabilizer;
(G) A method for producing a resin composition comprising the following steps (1) and (2) when melt-kneading 0 to 3 parts by mass of an acrylate compound.
(1) the total amount of the component (b) and the component (d), the component (c), the component (e), the component (f), a part or the total amount of the component (g), a) a step of melt-kneading a part of the components;
(2) The remaining amount of the component (a), the component (c), the component (e), the component (f), and the component (g) with respect to the kneaded product obtained in the step (1). Adding and melt-kneading. A total of 100 parts by mass of (a) polyolefin resin and (b) polyphenylene ether resin;
(C) a polymer block A mainly composed of a vinyl aromatic compound, and a conjugated diene compound having a total amount of 1,2-vinyl bonds and 3,4-vinyl bonds of the conjugated diene compound of 30 to 90%. 1 to 100 parts by mass of a hydrogenated block copolymer obtained by hydrogenating at least a part of a block copolymer including a main polymer block B;
(D) 0.1 to less than 1 part by mass of a polyamine compound,
(E) 0.05 to 3 parts by mass of a hindered phenol stabilizer,
(F) 0.05 to 3 parts by mass of a sulfur stabilizer;
(G) A method for producing a resin composition comprising the following (1) step and the following (2) step when melt-kneading 0 to 3 parts by mass of an acrylate compound.
(1) Melting the total amount of the component (b) and the component (d), the component (c), the component (e), the component (f), and part or all of the component (g) The kneading step,
(2) The total amount of the component (a), the component (c), the component (e), the component (f) and the component (g) with respect to the kneaded product obtained in the step (1). The process of adding the remaining amount and melt-kneading.   A resin composition obtained by the production method according to claim 11.   A molded article comprising the resin composition according to any one of claims 1 to 10 and 13.   A cable covering material comprising the molded product according to claim 14.   A cable using the cable covering material according to claim 15.

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