JP5312928B2 - RESIN COMPOSITION, PROCESS FOR PRODUCING THE SAME, MOLDED ARTICLE COMPRISING THE SAME, CABLE COVERING MATERIAL AND CABLE - Google Patents

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 matter has a poor affinity with the resin composition, when the resin composition is stressed, it has the disadvantage of causing cracks and significantly reducing the mechanical strength.

  The present invention has been made in view of the above circumstances, there is no foreign matter resulting from thermal history, the resin composition excellent in the balance between rigidity and tensile elongation, and further excellent in heat-resistant creep resistance, its production method, and molding comprising the same The object is to provide a product, a cable covering material and a cable.

  The present inventors have obtained a resin composition excellent in rigidity, tensile elongation and heat-resistant creep resistance by melt-kneading a polyolefin resin, polyphenylene ether resin and hydrogenated block copolymer using a specific polyamine compound. The present inventors have found that a product can be obtained, and have completed the present invention.

（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］（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］〜［８］のいずれか一項に記載の樹脂組成物。
［１０］（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、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）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、（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、（ａ）成分の一部と、（ｃ）成分と（ｅ）成分の一部又は全量と、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）成分と（ｃ）成分と（ｅ）成分の残量を添加し、溶融混練する工程。
［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、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）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、（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）成分の一部又は全量と、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）成分の残量を添加し、溶融混練する工程。
［１２］［１０］又は［１１］に記載の製造方法により得られる樹脂組成物。
［１３］［１］〜［９］及び［１２］のいずれか一項に記載の樹脂組成物からなる成形品。
［１４］［１３］に記載の成形品からなるケーブル用被覆材。
［１５］［１４］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 , A polymer block B mainly composed of a conjugated diene compound having a total amount of 4-vinyl bonds of 30 to 90%, and a block copolymer 1 to which at least a part of the block copolymer is hydrogenated A resin composition comprising 100 parts by mass, (d) less than 0.1 to 1 part by mass of a polyamine compound, and (e) 0 to 3 parts by mass of an acrylate compound.
[2] The resin composition according to [1], wherein the component (a) is a polypropylene resin.
[3] The resin composition according to [1] or [2], wherein the melt flow rate (MFR) (230 ° C., load 2.16 kg) of the component (a) is 0.01 to 300 g / 10 minutes.
[4] The resin composition according to any one of [1] to [3], wherein the number average molecular weight of the polymer block A in the component (c) is 15000 or more.
[5] Any of [1] to [4], wherein the total amount of 1,2-vinyl bonds and 3,4-vinyl bonds in polymer block B in 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 represent 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 resin composition according to any one of [1] to [8], wherein the component (a) forms a matrix phase, and the component (b) forms a dispersed phase.
[10] 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 In melt kneading 1 to 100 parts by mass, (d) less than 0.1 to 1 part by mass of a polyamine compound, and (e) 0 to 3 parts by mass of an acrylate compound, the following (1) step and (2 ) Step, a method for producing a resin composition.
(1) a step of melt-kneading a total amount of the component (b) and the component (d), a part of the component (a), a part or the total amount of the component (c) and the component (e),
(2) A step of adding the remaining amount of the component (a), the component (c), and the component (e) to the kneaded product obtained in the step (1) and melt-kneading.
[11] 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 In melt kneading 1 to 100 parts by mass, (d) less than 0.1 to 1 part by mass of a polyamine compound, and (e) 0 to 3 parts by mass of an acrylate compound, the following (1) step and (2 ) Step, a method for producing a resin composition.
(1) a step of melt-kneading the whole amount of the component (b) and the component (d), a part or the whole amount of the component (c) and the component (e),
(2) A step of adding the total amount of the component (a) and the remaining amount of the components (c) and (e) to the kneaded product obtained in the step (1), and melt-kneading.
[12] A resin composition obtained by the production method according to [10] or [11].
[13] A molded article comprising the resin composition according to any one of [1] to [9] and [12].
[14] A cable covering material comprising the molded article according to [13].
[15] A cable using the cable covering material according to [14].

  ADVANTAGE OF THE INVENTION According to this invention, a foreign material can be reduced and the resin composition excellent in rigidity, tensile elongation, and heat-resistant creep property, its manufacturing method, a molded article consisting of this, a 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 (e).
(A) 100 parts by mass of polyolefin resin and (b) polyphenylene ether resin in total,
(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 block copolymer in which at least a part of the block copolymer including the combined block B is hydrogenated,
(D) 0.1 to less than 1 part by mass of a polyamine compound,
(E) 0 to 3 parts by mass of an 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), high molecular weight high density polyethylene (HMW-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, Two or more compounds selected from unsaturated carboxylic acids and derivatives thereof Copolymers.

  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; 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 above-described method or the like. Moreover, even if it is a polypropylene resin which has what kind of crystallinity and melting | fusing point, you may use independently and may use 2 or more types together.

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 in such a range, it is possible to balance rigidity and heat-resistant creep resistance.
Moreover, if MFR is a polypropylene resin of these ranges, it may be used independently and may use 2 or more types together.

  Further, in addition to the above polypropylene resin, a polypropylene resin and an α, β-unsaturated carboxylic acid or a derivative thereof in a molten state or a solution state in the presence or absence of a radical generator, You may use the modified polypropylene resin obtained by making it react at 350 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 arbitrarily determined.

<(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 the formula, 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, a phenyl group, or a haloalkyl group. , An aminoalkyl group, a hydrocarbonoxy group or 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.

  Of these, poly (2,6-dimethyl-1,4-phenylene ether) and a copolymer of 2,6-dimethylphenol and 2,3,6-trimethylphenol are preferable. 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. Can be produced by the method described in the above.

  Further, in addition to the above polyphenylene ether resin, the polyphenylene ether resin and the styrene monomer or derivative thereof may be 80 to 350 in a molten state, a solution state or a slurry state in the presence or absence of a radical generator. You may use together the modification | denaturation polyphenylene ether-type resin which can be obtained by making it react at ° C.

  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 also be suitably used.
More preferably, 100 parts by mass of the polyphenylene ether resin is a mixture of polystyrene, syndiotactic polystyrene, high impact polystyrene and a mixture thereof in a range not exceeding 400 parts by mass in total.

  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, and a 3,4-vinyl bond. 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 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%. And it is preferable to contain a vinyl aromatic compound 70 mass% or more.

  Examples of the vinyl aromatic compound constituting the polymer block 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 polymer block A is not particularly limited, but is preferably 15000 or more. Thereby, the heat-resistant creep property of the resin composition of this Embodiment can be made more excellent.
The number average molecular weight of the polymer block 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.

  Examples of the conjugated diene compound constituting the polymer block B 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.

  And about the microstructure of the polymer block B (bonded form of the conjugated diene compound), the total amount of 1,2-vinyl bond amount and 3,4-vinyl bond amount (hereinafter referred to as “total vinyl bond 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 making the total vinyl bond amount 30% or more, the dispersibility of the polyphenylene ether resin dispersed in the obtained resin composition can be made excellent. By setting the total vinyl bond amount to 90% or less, a resin composition having excellent dispersibility of the polyphenylene ether resin and excellent in economic efficiency can be obtained.
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 containing at least the polymer block A and at least the polymer block B.

When 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 the polymer block A and the polymer block B, the distribution of vinyl aromatic compound or conjugated diene compound in the molecular chain in each polymer block is random and tapered (in which the monomer component increases or decreases along the molecular chain). , May be partially block-shaped or any combination thereof.
And when there are two or more polymer blocks A or polymer blocks B 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, more preferably 30 to 80% by mass of the vinyl aromatic compound to which the block copolymer before hydrogenation is bonded. .
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 becomes like this. Preferably it is 5000-1 million, More preferably, it is 10000-800000, More preferably, it is 30000-500000.
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 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).

Further, the hydrogenation rate with respect to the conjugated diene compound in the component (c) is not limited, but is preferably 50% or more, more preferably 80% or more, more preferably 90% of the double bond derived from the conjugated diene compound. % 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.

<(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.

  The component (d) preferably has branched carbon and / or branched nitrogen, and more preferably 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>
The acrylate compound of the component (e) in the present embodiment is not particularly limited, and a known one can be used, and is preferably a compound represented by the following formula (3). The component (e) can be used as a heat deterioration preventing agent in the resin composition according to the present embodiment.

In the above formula (3), ^{R 8} is an alkyl group having 1 to 5 carbon atoms, such as methyl group, ethyl group, propyl group, t- butyl group, 2,2-dimethylpropyl group and the like. 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.

Examples of the acrylate compound of the present embodiment include 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) -4-methylphenyl acrylate Etc.
Preferably, 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 (e) 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 GS (registered trademark) 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.

  The resin composition according to the present embodiment is composed of components (a) to (e) as basic components.

Although the compounding quantity of (a) component is not specifically limited, In 100 mass parts in total of (a) component and (b) component, the compounding quantity of (a) component becomes like this. Preferably it is 1-99 mass parts, More preferably, 5 ~ 95 parts by mass.
When the blending amount of component (a) is 1 part by mass or more, the balance of heat resistance, molding processability and solvent resistance of the obtained resin composition can be further improved. Moreover, if it is 99 mass parts or less, it can be made further excellent in the balance of moldability, solvent resistance, and heat resistance.

Although the compounding quantity of (b) component is not specifically limited, In the total of 100 mass parts of (a) component and (b) component, the compounding quantity of (b) component becomes like this. Preferably it is 99-1 mass part, More preferably, it is 95. -5 parts by mass.
When the blending amount of the component (b) is 99 parts by mass or less, the balance of heat resistance, molding processability, and solvent resistance of the obtained resin composition can be further improved. Moreover, by making it 1 weight or more, the moldability and solvent resistance can be further improved.

(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 1 part by mass or more, the effect as an admixture of the resin composition according to the present embodiment (the effect of finely emulsifying and dispersing the polyphenylene ether resin in the polyolefin resin, the polyphenylene ether resin) The effect of finely emulsifying and dispersing the polyolefin-based resin therein can be obtained.
On the other hand, if the blending amount exceeds 100 parts by mass, the effects of the heat resistance and solvent resistance of the component (a) and component (b) are markedly lowered, which is not preferable.

Component (d) is blended in an amount of 0.1 parts by mass or more and 1 part by mass with respect to a total of 100 parts by mass of component (a) and component (b) from the viewpoints of rigidity, tensile elongation, heat resistance creep resistance and foreign matter reduction. Less than part. In cases other than the range of the blending amount, for example, when the component (d) is 1 part by mass or more, the heat resistance is lowered, which is not preferable.
(E) The compounding quantity of a component is 0-3 mass parts with respect to 100 mass parts of (a) component and (b) component from a viewpoint of foreign material reduction.

In the present embodiment, in addition to the above components, other additional components may be added as necessary within the scope of the effects of the present embodiment.
The additional component is not particularly limited. For example, a vinyl aromatic compound-conjugated diene compound block copolymer, an olefin elastomer, an antioxidant, a metal deactivator, a heat stabilizer, a flame retardant (organophosphorus) Acid ester 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 and reinforcing materials (GF, GF long fiber, CF, CF long fiber, polyacrylonitrile fiber, carbon black, oxidized titanium , 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) 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) 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) a step of melt-kneading a total amount of the component (b) and the component (d), a part of the component (a), a part or the total amount of the component (c) and the component (e),
(2) A step of adding the remaining amount of the component (a), the component (c), and the component (e) to the kneaded product obtained in the step (1) and melt-kneading.

Alternatively, when the components (a), (b), (c), (d) and (e) are melt-kneaded, a resin composition comprising the following steps (1) and (2): The manufacturing method of a thing is also preferable.
(1) a step of melt-kneading the whole amount of the component (b) and the component (d), a part or the whole amount of the component (c) and the component (e),
(2) A step of adding the total amount of the component (a) and the remaining amount of the components (c) and (e) to the kneaded product obtained in the step (1), and melt-kneading.

  In the resin composition obtained by these production methods, the thermal deterioration of the component (b) is effectively suppressed by the component (d), and the mixture of the component (a), the component (b), and the component (c) is excellently dispersed. A form can be obtained. Thereby, the resin composition which is excellent in rigidity, tensile elongation, and heat-resistant creep property can be obtained efficiently.

These methods can be performed using a melt kneader, and the type of the melt kneader is not particularly limited. 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 these, the melt kneading method using a twin screw extruder is more preferable. Specific examples include the ZSK series manufactured by Coperion, the TEM series manufactured by Toshiba Machine Co., Ltd., and the TEX series manufactured by Nippon Steel Works.

  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 these, 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.

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

  The melt kneading temperature and the screw rotation speed are not particularly limited, but can usually 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 parts, a sheet | seat, a film, etc., for example. The molding method is not particularly limited, and a known method 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, exterior parts such as bumpers, fenders, door panels, various moldings, emblems, engine hoods, wheel caps, roofs, spoilers, various aero parts, etc .; It is suitable for interior parts such as an instrument panel, console box, trim, etc .; secondary battery battery case parts mounted on automobiles, electric cars, hybrid electric cars, etc., separators for lithium ion batteries, and the like.

  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.

  In addition, the molded product according to the present embodiment is a coating material for an optical fiber obtained by using a known wire extrusion coating device or the like, a low voltage type electric wire / cable, an instrument cable, an electronic wire, an automobile wire harness, and It is also suitable for control cables such as cables for nuclear power plants.

  And the molded article which concerns on this Embodiment can be used as the coating | covering material for cables. Since the resin composition according to the present embodiment has an excellent balance between rigidity and tensile elongation, and also has excellent heat-resistant creep resistance, a molded article 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. .

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

  A cable using the cable covering material according to the present embodiment is excellent in the balance between rigidity and tensile elongation, and is excellent in heat-resistant creep resistance, and therefore can be suitably used as a flexible cable. In addition, the cable according to the present embodiment may be referred to as “electric wire”.

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

Each physical property of each material was measured 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 total vinyl bond content]
The total 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)]
MFR was measured under the conditions of 230 ° C. and a load of 2.16 kg.

[Reduced viscosity]
The reduced viscosity was measured under conditions of 0.5 g / dL chloroform solution and 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 the 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 the 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
Polybutadiene part hydrogenation rate: 99.9%

(C-3) A block copolymer having an ABA type structure of polystyrene (1) -hydrogenated polybutadiene-polystyrene (2) was synthesized.
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 (acrylate compound)
2,4-di-t-amyl-6- [1- (3,5-di-t-amyl-2-hydroxyphenyl) ethyl] phenyl acrylate (Sumilyzer GS (registered trademark, manufactured by Sumitomo Chemical Co., Ltd.)) )

<Example 1>
Using a twin screw extruder (manufactured by Coperion, ZSK-25), a first raw material supply port is provided on the upstream side with respect to the flow direction of the raw material, a second raw material supply port is provided downstream thereof, and a vacuum vent is further provided downstream thereof. Provided. 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 (e) were blended in the composition shown in Table 1, and the conditions were an extrusion temperature of 270 to 320 ° C., a screw rotation speed of 300 rpm, and a discharge rate of 12 kg / hour. And kneaded to obtain pellets.

<Examples 2 to 8>
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 1-7>
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 2.

<Bending elastic modulus and tensile elongation>
The pellets obtained in the examples and comparative examples were supplied to a screw in-line type injection molding machine set at 240 to 280 ° C., and the test piece for measuring the flexural modulus and tensile elongation was measured at a mold temperature of 60 ° C. It was injection-molded, and left in an environment of 80 ° C. for 24 hours using a gear oven to perform a heat history treatment. Using these molded articles, the flexural modulus was measured according to ISO178, and the tensile elongation was measured according to ISO527.

<Heat resistant creep resistance>
The pellets obtained in the examples and comparative examples are supplied to a screw in-line type injection molding machine set at 240 to 280 ° C., and a test piece for creep measurement is injection molded at a mold temperature of 60 ° C. Was left to stand in an environment of 80 ° C. for 24 hours to perform a heat history treatment. The test piece for creep measurement was a dumbbell molded product (thickness 1 mm) having the shape shown in FIG. 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. Creep measurement was performed using a creep tester (Yasuda Seiki Seisakusho Co., Ltd., 145-B-PC type) for 40 hours between chucks and at a temperature equivalent to a stress of 12.25 MPa at a temperature of 80 ° C. for 120 hours. The test was conducted to confirm the presence or absence of breakage.

<Foreign matter test>
The pellets obtained in Examples and Comparative Examples were supplied to a screw in-line injection molding machine set at 240 to 280 ° C., and a dumbbell molded product (thickness 1 mm) having the shape shown in FIG. ). 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.

In each of Examples 1 to 8, the flexural modulus was 1689 MPa or more, the tensile elongation was 160% or more, the heat creep resistance was “no break”, and the foreign matter test was “◯”.
On the other hand, in Comparative Example 1, the flexural modulus was 1710 MPa, the tensile elongation was 137%, the heat creep resistance was “break”, and the foreign matter test was “x”. In Comparative Example 2, the tensile elongation was 210%, the heat creep resistance was “no break”, and the foreign matter test was “◯”, but the flexural modulus was 1420 MPa. In Comparative Example 3, the flexural modulus was 1710 MPa, the tensile elongation was 145%, the heat creep resistance was “breaking”, and the foreign matter test was “x”. In Comparative Example 4, the tensile elongation was 160% and the foreign matter test was “◯”, but the flexural modulus was 1710 MPa and the heat creep resistance was “breaking”. In Comparative Example 5, the flexural modulus was 1690 MPa, the tensile elongation was 90%, the heat creep resistance was “breaking” and the foreign matter test was “x”. In Comparative Example 6, the tensile elongation was 250% and the foreign matter test was “◯”, but the flexural modulus was 950 MPa and the heat creep resistance was “breaking”. In Comparative Example 7, the flexural modulus was 1690 MPa, the tensile elongation was 160%, and the foreign matter test was “◯”, but the heat resistant creep property was “breaking”.
From the above, it was shown that the resin composition according to the present embodiment is excellent in rigidity, tensile elongation, heat-resistant creep resistance and foreign matter reduction.

  Since the resin composition according to the present invention, the production method thereof, the molded article made of the resin composition, the cable covering material and the cable are excellent in rigidity, tensile elongation and heat-resistant creep resistance, various properties are required for these properties. It can use suitably for the use of.

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

Explanation of symbols

1 Test piece

Claims (11)

A total of 100 parts by mass of (a) a polyolefin-based resin forming a matrix phase and (b) a polyphenylene ether-based resin forming a dispersed phase;
(C) Polymer block A containing more than 50% by mass of vinyl aromatic compound, and a conjugated diene compound in which the total amount of 1,2-vinyl bonds and 3,4-vinyl bonds is 30 to 90% And a polymer block B containing more than 50% by mass, and a hydrogenated block copolymer (excluding a modified hydrogenated block copolymer) 1 to 100 in which at least a part of the block copolymer containing 1 to 100 is hydrogenated Part by mass;
(D) 0.1 to less than 1 part by mass of polyethyleneimine having a weight average molecular weight of 200 to 100,000,
(E) 2,4-di-t-amyl-6- [1- (3,5-di-t-amyl-2-hydroxyphenyl) ethyl] phenyl acrylate and / or 2-t-butyl-6- ( 3-t-butyl-2-hydroxy-5-methylbenzyl) -4-methylphenyl acrylate 0 to 3 parts by mass of resin, including the following (1) step and (2) step A method for producing the composition.
(1) Melt-knead the total amount of the component (b) and the component (d), a part of the component (a), the component (c) and a part or the total amount of the component (e). Process,
(2) A step of adding the remaining amount of the component (a), the component (c) and the component (e) to the kneaded product obtained in the step (1), and melt-kneading. A total of 100 parts by mass of (a) a polyolefin-based resin forming a matrix phase and (b) a polyphenylene ether-based resin forming a dispersed phase;
(C) Polymer block A containing more than 50% by mass of vinyl aromatic compound, and a conjugated diene compound in which the total amount of 1,2-vinyl bonds and 3,4-vinyl bonds is 30 to 90% And a polymer block B containing more than 50% by mass, and a hydrogenated block copolymer (excluding a modified hydrogenated block copolymer) 1 to 100 in which at least a part of the block copolymer containing 1 to 100 is hydrogenated Part by mass;
(D) 0.1 to less than 1 part by mass of polyethyleneimine having a weight average molecular weight of 200 to 100,000,
(E) 2,4-di-t-amyl-6- [1- (3,5-di-t-amyl-2-hydroxyphenyl) ethyl] phenyl acrylate and / or 2-t-butyl-6- ( 3-t-butyl-2-hydroxy-5-methylbenzyl) -4-methylphenyl acrylate 0 to 3 parts by mass of resin, including the following (1) step and (2) step A method for producing the composition.
(1) a step of melt-kneading the total amount of the component (b) and the component (d), a part or the total amount of the component (c) and the component (e),
(2) A step of adding the total amount of the component (a) and the remaining amount of the component (c) and the component (e) to the kneaded product obtained in the step (1), and melt-kneading. The resin composition obtained by the production method according to claim 1 or 2. The resin composition according to claim 3 , wherein the component (a) is a polypropylene resin. The resin composition according to claim 3 or 4 , wherein the melt flow rate (MFR) (230 ° C, load 2.16 kg) of the component (a) is 0.01 to 300 g / 10 minutes. The resin composition as described in any one of Claims 3-5 whose number average molecular weights of the said polymer block A in the said (c) component are 15000 or more. The total amount of 1,2-vinyl bonds and 3,4-vinyl bonds in the polymer block B in the component (c) is 65 to 90% according to any one of claims 3 to 6. The resin composition as described. The resin composition according to any one of claims 3 to 7 , wherein the component (d) 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 molded article which consists of a resin composition as described in any one of Claims 3-8 . A cable covering material comprising the molded product according to claim 9 . A cable using the cable covering material according to claim 10 .

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