JP2012149125A - Resin composition, thermoplastic resin composition, method for producing the resin composition, and molded body obtained by molding the resin composition - Google Patents

Abstract

PROBLEM TO BE SOLVED: To improve fluidity, eye mucus upon production, the delamination of a molded body or the like in a polyphenylene ether/hydrogenated block copolymer composition, and to improve fluidity, rigidity or the like in a polypropylene/polyphenylene ether resin composition.SOLUTION: The resin composition includes, in specified ranges: (a) specified polyphenylene ether; (b) polystyrene; and (c) a specified hydrogenated block copolymer. Further, the resin composition preferably includes (d) polypropylene, in a specified range.

Description

  The present invention relates to a resin composition, a thermoplastic resin composition, a method for producing the resin composition, and a molded body obtained by molding the resin composition.

Polyphenylene ether is known as an engineering plastic excellent in permeability, mechanical properties, heat resistance, dimensional stability, non-water absorption and electrical properties, but is poor in melt fluidity and impact resistance. For this reason, polyphenylene ether is often used in combination with other polymers for the purpose of taking advantage of its advantages and compensating for the drawbacks. Examples of the other polymer include many types of polymers such as hydrogenated block copolymer of styrene and conjugated diene (hereinafter also referred to as “hydrogenated block copolymer”) and polypropylene.
Although the hydrogenated block copolymer is excellent in thermal stability and weather resistance, it has drawbacks that the rubber elasticity at high temperature is insufficient, the heat and pressure deformation is large, and the compression set at high temperature is large. .
Polypropylene is a low specific gravity and inexpensive plastic and has excellent chemical resistance, solvent resistance, molding processability, etc., so it is used in various fields such as automobile parts, electrical / electronic equipment parts, and household electrical appliances. ing.
Various resin compositions in which these components are combined in an appropriate combination have been proposed in order to combine the advantages of these polyphenylene ethers, hydrogenated block copolymers, and polypropylene, and to make up for the drawbacks.
For example, Patent Documents 1 to 3 disclose a resin composition containing polyphenylene ether and a hydrogenated block copolymer, and Patent Documents 4 to 6 disclose a resin composition containing polyphenylene ether and polypropylene. .

Japanese Patent Publication No.51-27256 JP-A-50-71742 Japanese Examined Patent Publication No. 7-107126 International Publication No. 97/01600 Pamphlet Japanese Patent Laid-Open No. 09-12799 JP 09-12804 A

In applications where these resin compositions comprising polyphenylene ether and hydrogenated block copolymer or resin compositions comprising polypropylene and polyphenylene ether are used, in recent years, the size of molded products has increased, the design has become complicated, and the thickness has been reduced. Is required. Accordingly, the resin composition that is the raw material of the molded body is required to have high fluidity and other characteristics. In particular, when a molded product having a large area is thinned, higher fluidity is required in order to completely fill a resin composition in an injection mold.
In order to obtain a resin composition with improved fluidity, for example, it is conceivable to incorporate a low molecular weight polyphenylene ether, and the above-mentioned known literature discloses a wide range of molecular weight (viscosity) of polyphenylene ether. An example using a low molecular weight polyphenylene ether is also disclosed.
However, when the low molecular weight polyphenylene ether is used, the fluidity is improved, but other characteristics (such as mechanical strength, sag generated during the production of the composition, and delamination of the surface of the molded product) may be reduced. However, the above-mentioned known documents do not improve these characteristics. Therefore, the conventional resin composition still has an insufficient balance of the overall characteristics such as fluidity described above, and there is room for improvement.
Accordingly, the present invention is a resin composition comprising polyphenylene ether and a hydrogenated block copolymer, which is excellent in fluidity and rigidity, suppresses the occurrence of a resin during production, and can suppress delamination of a molded product, and An object is to provide a resin composition containing polypropylene and polyphenylene ether.

As a result of intensive studies, the present inventors have found that a resin composition comprising (a) polyphenylene ether, (b) polystyrene, and (c) hydrogenated block copolymer, (a) polyphenylene ether having a molecular weight in a specific range. And (c) using a hydrogenated block copolymer having a specific range of molecular weight and a specific structure, and further controlling the content of each component to obtain a resin composition having excellent fluidity In addition, since the compatibility of each component is excellent, it has been found that the occurrence of sag and delamination during the production of the composition can be suppressed, and the present invention has been completed.
That is, the present invention is as follows.
[1]
(A) polyphenylene ether,
A block copolymer comprising (b) polystyrene, and (c) at least two polymer blocks A mainly composed of a vinyl aromatic compound and at least one polymer block B mainly composed of a conjugated diene compound. A resin composition comprising a hydrogenated block copolymer formed by adding,
The (a) polyphenylene ether contains 5 to 20% by mass of a component having a molecular weight of 50,000 or more and 12 to 30% by mass of a component having a molecular weight of 8,000 or less with respect to the whole polyphenylene ether. Including
The number average molecular weight (Mnc) of the (c) hydrogenated block copolymer is 100,000 or less,
The number average molecular weight (MncA) of the polymer block A in the (c) hydrogenated block copolymer is 8,000 or more,
The content of the component (a) is 50% by mass or more with respect to a total of 100% by mass of the components (a) and (b),
The total content of the components (a) and (b) is 1 to 99% by mass with respect to a total of 100% by mass of the components (a) to (c), and the content of the component (c) is The resin composition which is 99-1 mass%.
[2]
The resin composition according to [1], wherein the content of the bonded vinyl aromatic compound in the (c) hydrogenated block copolymer is 15 to 50% by mass with respect to the entire component (c).
[3]
(C) All conjugated diene compounds in which the total amount of conjugated diene compounds bonded by 1,2-vinyl bonds or 3,4-vinyl bonds in the hydrogenated block copolymer constitutes the polymer block B The resin composition according to [1] or [2], which is 70 to 90% by mass relative to the mass.
[4]
Use of a resin composition that improves the heat resistance of polypropylene by adding the resin composition according to any one of [1] to [3] to polypropylene.
[5]
Furthermore, (d) polypropylene is included, and the content of the component (d) is 1 to 95% by mass with respect to 100% by mass of the total amount of the components (a) to (d). ] The resin composition in any one of.
[6]
(D) The resin composition according to [5], wherein the polypropylene has a melting point of 155 ° C or higher.
[7]
The (d) polypropylene is a homopolypropylene and / or a block polypropylene, and the melt flow rate of the component (d) (MFR: measured at 230 ° C. under a load of 2.16 kg in accordance with ASTM D1238) is 0.1 to 0.1. The resin composition according to [5] or [6], which is 100 g / 10 minutes.
[8]
The pellet formed from the resin composition in any one of [1]-[3].
[9]
100 parts by mass of the pellet according to [8],
Vinyl aromatic compound polymer, vinyl aromatic compound copolymer, polypropylene, polyethylene, ethylene-α-olefin copolymer, polyamide 6, polyamide 66, polyamide 66/6, polycarbonate, polyacetal, polyethylene terephthalate, polybutylene terephthalate, One or more thermoplastic resins selected from the group consisting of polytrimethylene terephthalate, aromatic ring-containing polyamide, aliphatic ring-containing polyamide, polyphenylene sulfide, liquid crystal polymer, polyether ether ketone, polyarylate, polyether sulfone, and polysulfone The manufacturing method of a thermoplastic resin composition including the process of melt-mixing 10-1000 mass parts.
[10]
The method for producing a thermoplastic resin according to [9], wherein the thermoplastic resin is polypropylene.
[11]
The method for producing a thermoplastic resin composition according to [9] or [10], wherein the melt-mixing step is performed by an extruder or an injection molding machine.
[12]
A thermoplastic resin composition obtained by the production method according to [11].
[13]
A molded article obtained by molding the thermoplastic resin composition according to [12].
[14]
A molded product obtained by molding the resin composition according to any one of [1] to [3] or [5] to [7].
[15]
The molded body according to [13] or [14], wherein the molded body is at least one selected from the group consisting of the following (1) to (4).
(1) Sheet / film or stretched sheet / film (2) Automotive exterior / outboard parts, automotive interior parts, or automotive underhood parts (3) Electric wires / cables obtained by coating a resin composition on a metal conductor or optical fiber (4) Ink peripheral parts / members or chassis of ink jet printer

  According to the present invention, a resin composition containing polyphenylene ether and a hydrogenated block copolymer, and polypropylene, which is excellent in fluidity and rigidity, can suppress delamination of a molded product, and can prevent the occurrence of scouring during production, and polypropylene A composition containing polyphenylene ether and a hydrogenated block copolymer can be obtained. Furthermore, according to the present invention, a molded product having excellent characteristics can be obtained using these resin compositions.

  Hereinafter, a 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 of the present embodiment includes (a) polyphenylene ether, (b) polystyrene, and a specific (c) hydrogenated block copolymer, and (a) the polyphenylene ether is based on the whole polyphenylene ether. And a component having a molecular weight of 50,000 or more in an amount of 5 to 20% by mass and a component having a molecular weight of 8,000 or less in an amount of 12 to 30% by mass, the (c) hydrogenated block copolymer The number average molecular weight (Mnc) is 100,000 or less, the number average molecular weight (MncA) of the polymer block A in the (c) hydrogenated block copolymer is 8,000 or more, and (a) and ( b) The content of the component (a) is 50% by mass or more with respect to a total of 100% by mass of the components, and the component (a) with respect to the total 100% by mass of the components (a) to (c). and b) the total content of component is 1 to 99 wt%, and the content of the component (c) is 99 to 1% by weight.

The present invention uses (a) a polyphenylene ether having a specific molecular weight in order to impart good fluidity and mechanical properties, and a vinyl aroma having an appropriate molecular weight to be compatible with the polyphenylene ether having the specific molecular weight. (C) using a hydrogenated block copolymer having a block mainly composed of a group compound, and (b) using polystyrene to further control the compatibility of both in an appropriate range. . By satisfying each requirement, it is possible to obtain a resin composition which is excellent in fluidity and free from delamination, cracking and generation of chips.
Hereinafter, each component which comprises a resin composition is demonstrated in detail.

[(A) component]
The (a) polyphenylene ether (hereinafter sometimes simply referred to as “PPE”) used in the present embodiment is a homopolymer and / or copolymer having a repeating unit structure represented by the following formula (1). is there.

In formula (1), R ₁ , R ₂ , R ₃ , and R ₄ each independently represent a hydrogen atom, a halogen atom, an alkyl group having 1 to 7 carbon atoms, a phenyl group, a haloalkyl group, an aminoalkyl group, It is selected from the group consisting of a hydrocarbonoxy group or a halohydrocarbonoxy group in which at least two carbon atoms separate a halogen atom and an oxygen atom.
In the formula (1), examples of the halogen atom represented by R ₁ , R ₂ , R ₃ and R ₄ include a fluorine atom, a chlorine atom and a bromine atom, and a chlorine atom and a bromine atom are preferable.
In the formula (1), the “alkyl group” represented by R ₁ , R ₂ , R ₃ , and R ₄ is linear or branched having 1 to 6 carbon atoms, more preferably 1 to 3 carbon atoms. It represents a chain alkyl group, and examples thereof include methyl, ethyl, propyl, isopropyl, butyl, isobutyl, sec-butyl, tert-butyl, pentyl, hexyl and the like. Methyl and ethyl are preferable, and methyl is more preferable.
In the formula (1), the alkyl group represented by R ₁ , R ₂ , R ₃ and R ₄ may be substituted with one or more substituents at substitutable positions.
Examples of such a substituent include a halogen atom (for example, fluorine atom, chlorine atom, bromine atom), an alkyl group having 1 to 6 carbon atoms (for example, methyl, ethyl, propyl, isopropyl, butyl, isobutyl, sec-butyl, tert-butyl, pentyl, hexyl), aryl groups (eg, phenyl, naphthyl), alkenyl groups (eg, ethenyl, 1-propenyl, 2-propenyl), alkynyl groups (eg, ethynyl, 1-propynyl, 2-propynyl) , Aralkyl groups (for example, benzyl, phenethyl), alkoxy groups (for example, methoxy, ethoxy) and the like.

The polyphenylene ether is not particularly limited, and a known one 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 these, preferably, poly (2,6-dimethyl-1,4-phenylene ether), a copolymer of 2,6-dimethylphenol and 2,3,6-trimethylphenol, more preferably Poly (2,6-dimethyl-1,4-phenylene ether).
These polyphenylene ethers may be used alone or in combination of two or more.

The polyphenylene ether used in the present embodiment has a low molecular weight (a component amount having a molecular weight of 50,000 or more is 5 to 20% by mass) and contains a specific amount of a molecular weight component in a specific range (a molecular weight of 8,000 or less). Component amount is 12 to 30% by mass) polyphenylene ether. By specifying the amount of the component having a molecular weight of 8,000 or less and the amount of the component having a molecular weight of 50,000 or more, the resulting resin composition has sufficiently high fluidity at the time of melt processing and can maintain high mechanical properties. .
From the viewpoint of fluidity, the polyphenylene ether used in the present embodiment has a component amount with a molecular weight of 50,000 or more of 5 to 20% by mass and preferably 5 to 18% by mass with respect to the whole polyphenylene ether. From the viewpoint of mechanical properties, the amount of the component having a molecular weight of 8,000 or less is 12 to 30% by mass, and more preferably 15 to 30% by mass with respect to the whole polyphenylene ether.

  In addition, the information regarding the molecular weight of polyphenylene ether used for this Embodiment is obtained by the measurement using a gel permeation chromatography measuring apparatus. As specific measurement conditions of gel permeation chromatography, Showa Denko Co., Ltd. Gel Permeation Chromatography System 21 (Column: Showa Denko K-805L in series, column temperature: 40 ° C., solvent : Chloroform, solvent flow rate: 1.0 ml / min, sample concentration: 1 g / L chloroform solution of polyphenylene ether), standard polystyrene (the molecular weight of standard polystyrene is 3,650,000, 2,170,000, 1 , 090,000, 681,000, 204,000, 52,000, 30,200, 13,800, 3,360, 1,300, 550). The UV wavelength of the detector can be selected from 254 nm for standard polystyrene and 283 nm for polyphenylene ether.

  The polyphenylene ether having a specific molecular weight used in the present embodiment controls the catalyst type, catalyst concentration, polymerization time, oxygen concentration used for polymerization, and the like, which will be described later, and also controls the type and amount of solvent (polymerization solution concentration). Can be obtained. It can also be obtained by mixing two or more polyphenylene ethers having different average molecular weights.

  The number average molecular weight (Mna) of the polyphenylene ether is preferably 7,000 or more and 15,000 or less. A more preferable lower limit is 8,000 or more, and a further preferable lower limit is 9,000 or more. Moreover, a more preferable upper limit is 14,000 or less, and a more preferable upper limit is 13,000 or less. From the viewpoint of suppressing deformation during heating of the resin composition, the lower limit of the number average molecular weight of the polyphenylene ether is preferably 7,000 or more. From the viewpoint of obtaining good fluidity during molding, the number of polyphenylene ethers The upper limit of the average molecular weight is preferably 15,000 or less.

The polyphenylene ether represented by the above formula (1) can be produced by polymerizing the following phenol compounds.
Examples of the phenol compound include o-cresol, 2,6-dimethylphenol, 2-ethylphenol, 2-methyl-6-ethylphenol, 2,6-diethylphenol, 2-n-propylphenol, and 2-ethyl-6. -N-propylphenol, 2-methyl-6-chlorophenol, 2-methyl-6-bromophenol, 2-methyl-6-isopropylphenol, 2-methyl-6-n-propylphenol, 2-ethyl-6 Bromophenol, 2-methyl-6-n-butylphenol, 2,6-di-n-propylphenol, 2-ethyl-6-chlorophenol, 2-methyl-6-phenylphenol, 2-phenylphenol, 2,6 -Diphenylphenol, 2,6-bis- (4-fluorophenyl) phenol, 2-methyl -6-tolylphenol, 2,6-ditolylphenol, 2,5-dimethylphenol, 2,3,6-trimethylphenol, 2,5-diethylphenol, 2-methyl-5-ethylphenol, 2-ethyl- 5-methylphenol, 2-allyl-5-methylphenol, 2,5-diallylphenol, 2,3-diethyl-6-n-propylphenol, 2-methyl-5-chlorophenol, 2-methyl-5-bromo Phenol, 2-methyl-5-isopropylphenol, 2-methyl-5-n-propylphenol, 2-ethyl-5-bromophenol, 2-methyl-5-n-butylphenol, 2,5-di-n-propyl Phenol, 2-ethyl-5-chlorophenol, 2-methyl-5-phenylphenol, 2,5-diphenylphenol Diol, 2,5-bis- (4-fluorophenyl) phenol, 2-methyl-5-tolylphenol, 2,5-ditolylphenol, 2,6-dimethyl-3-allylphenol, 2,3,6- Triallylphenol, 2,3,6-tributylphenol, 2,6-di-n-butyl-3-methylphenol, 2,6-di-t-butyl-3-methylphenol, 2,6-dimethyl-3- Examples include n-butylphenol and 2,6-dimethyl-3-t-butylphenol.
In particular, 2,6-dimethylphenol, 2,6-diethylphenol, 2,6-diphenylphenol, 2,3,6-trimethylphenol, and 2,5-dimethylphenol are preferable because they are inexpensive and easily available. 2,6-dimethylphenol and 2,3,6-trimethylphenol are more preferable.
The said phenol compound may be used independently or may be used in combination of 2 or more type.
For example, a method using a combination of 2,6-dimethylphenol and 2,6-diethylphenol, a method using a combination of 2,6-dimethylphenol and 2,6-diphenylphenol, 2,3,6-trimethyl Examples thereof include a method using a combination of phenol and 2,5-dimethylphenol, a method using a combination of 2,6-dimethylphenol and 2,3,6-trimethylphenol, and the like. The mixing ratio can be arbitrarily selected. In addition, the phenolic compounds used contain a small amount of m-cresol, p-cresol, 2,4-dimethylphenol, 2,4,6-trimethylphenol, etc., which are contained as by-products during production. May be.

  Polyphenylene ether can be produced by two kinds of production methods, precipitation polymerization method and solution polymerization method. The precipitation polymerization method is a polymerization method in which polyphenylene ether having a predetermined molecular weight is precipitated. In the precipitation polymerization method, as the polymerization of polyphenylene ether proceeds, polyphenylene ether having a molecular weight determined according to the solvent composition or the like is precipitated, and polyphenylene ether having a molecular weight lower than that is dissolved. As the solvent, a mixed solvent of a good solvent of polyphenylene ether such as toluene, xylene and ethylbenzene and a poor solvent of polyphenylene ether such as methanol and butanol is used. In the precipitation polymerization method, the precipitated polyphenylene ether has a slow polymerization reaction rate, so that the molecular weight distribution of the obtained polyphenylene ether is theoretically narrowed. Furthermore, since polyphenylene ether precipitates during the polymerization, the viscosity in the system gradually decreases, so that the monomer concentration (phenol compound concentration) during the polymerization can be increased. The precipitated polyphenylene ether can be easily taken out by filtration. Therefore, according to the precipitation polymerization method, polyphenylene ether can be obtained by an extremely simple process.

On the other hand, the solution polymerization method is a polymerization method in which polymerization is performed in a good solvent of polyphenylene ether and no precipitate is deposited during the polymerization. In the solution polymerization method, all polyphenylene ether molecules are in a dissolved state, and the molecular weight distribution of the obtained polyphenylene ether tends to be wide. In the solution polymerization method, a powdered polyphenylene ether is obtained by developing a polymerization solution in which polyphenylene ether is dissolved in a poor solvent for polyphenylene ether such as methanol.
From the viewpoint of efficiently producing polyphenylene ether used in the present embodiment and from the viewpoint of producing polyphenylene ether having a specific molecular weight distribution, the concentration of the phenol compound is 10 to 30% by mass based on the total amount of the polymerization solution. It is preferably 15 to 28% by mass, more preferably 15 to 25% by mass. When the concentration is 10% by mass or more, the production efficiency of polyphenylene ether increases.
On the other hand, when the concentration is 30% by mass or more, it tends to be impossible to adjust to a specific molecular weight. The present inventors presume this cause as follows. When the concentration is as high as 30% by mass or more, the liquid viscosity at the end of polymerization becomes high, and uniform stirring becomes difficult. Therefore, a heterogeneous reaction occurs, and an unexpected molecular weight polyphenylene ether may be obtained. As a result, it may be difficult to efficiently produce polyphenylene ether having a specific molecular weight used in the present embodiment.

In the polymerization process of polyphenylene ether used in the present embodiment, both precipitation precipitation polymerization and solution polymerization are performed while supplying an oxygen-containing gas.
As the oxygen-containing gas, pure oxygen, oxygen and an inert gas such as nitrogen mixed at an arbitrary ratio, air, and further an inert gas such as air and nitrogen or a rare gas at an arbitrary ratio. A mixture or the like can be used.
The system pressure during the polymerization reaction may be ordinary pressure, but can be used under reduced pressure or increased pressure as necessary.
The supply rate of the oxygen-containing gas can be arbitrarily selected in consideration of heat removal, polymerization rate, etc., but is preferably 5 NmL / min or more, and more preferably 10 NmL / min or more, as pure oxygen per mole of phenol compound used for polymerization. .
To the polyphenylene ether polymerization reaction system, alkali metal hydroxides, alkaline earth metal hydroxides, alkali metal alkoxides, neutral salts such as magnesium sulfate and calcium chloride, zeolite, and the like may be added.
Further, a surfactant that has been conventionally known to have an effect of improving the polymerization activity may be added to the polymerization solvent. As such a surfactant, for example, trioctylmethylammonium chloride known as Aliquat 336 and CapRiquat (trade name, manufactured by Dojindo Laboratories Co., Ltd.) can be mentioned. The amount used is preferably within a range not exceeding 0.1 mass% with respect to the total amount of the polymerization reaction raw material.

As a catalyst in the production of polyphenylene ether used in the present embodiment, a known catalyst system generally used in the production of polyphenylene ether can be used.
For example, there is a transition metal ion having oxidation-reduction ability and an amine compound capable of complexing with the metal ion. Specifically, a catalyst system comprising a copper compound and an amine, and a manganese compound and an amine. And a catalyst system composed of a cobalt compound and an amine.

上記式（２）中、Ｒ₅、Ｒ₆、Ｒ₇およびＲ₈は、それぞれ独立して、水素原子、炭素数１〜６の直鎖状または分岐鎖状のアルキル基からなる群から選ばれるいずれかを示す。なお全てが同時に水素ではないものとする。Ｒ₉は炭素数２〜５の直鎖状または分岐鎖状のアルキレン基を示す。
触媒成分を構成する銅化合物としては、第一銅化合物、第二銅化合物またはこれらの混合物を使用できる。第一銅化合物としては、例えば塩化第一銅、臭化第一銅、硫酸第一銅、硝酸第一銅等が挙げられる。第二銅化合物としては、例えば、塩化第二銅、臭化第二銅、硫酸第二銅、硝酸第二銅等が挙げられる。これらの中で特に好ましい銅化合物は、塩化第一銅、塩化第二銅、臭化第一銅、臭化第二銅である。
また、これらの銅化合物は、酸化物（例えば酸化第一銅）、炭酸塩、水酸化物等と対応するハロゲンまたは酸から合成してもよい。
例えば、酸化第一銅とハロゲン化合物（例えばハロゲン化水素の溶液）とを混合することにより合成できる。
これらの銅化合物は、単独でも用いられるし、２種類以上組み合わせて用いてもよい。
触媒成分を構成するハロゲン化合物としては、例えば、塩化水素、臭化水素、ヨウ化水素、塩化ナトリウム、臭化ナトリウム、ヨウ化ナトリウム、塩化カリウム、臭化カリウム、ヨウ化カリウム、塩化テトラメチルアンモニウム、臭化テトラメチルアンモニウム、ヨウ化テトラメチルアンモニウム、塩化テトラエチルアンモニウム、臭化テトラエチルアンモニウム、ヨウ化テトラエチルアンモニウム等である。またこれらは水溶液や適当な溶媒を用いた溶液として使用できる。
これらのハロゲン化合物は、単独でも用いられるし、２種類以上組み合わせて用いてもよい。
好ましいハロゲン化合物は、塩化水素の水溶液、臭化水素の水溶液である。
これらの化合物の使用量は特に限定されないが、銅原子のモル量に対してハロゲン原子として２倍以上２０倍以下が好ましく、使用されるフェノール化合物の１００モルに対して好ましい銅原子の使用量としては０．０２モルから０．６モルの範囲である。
上記式（２）により示されるジアミン化合物としては、例えば、Ｎ，Ｎ，Ｎ’，Ｎ’−テトラメチルエチレンジアミン、Ｎ，Ｎ，Ｎ’−トリメチルエチレンジアミン、Ｎ，Ｎ’−ジメチルエチレンジアミン、Ｎ，Ｎ−ジメチルエチレンジアミン、Ｎ−メチルエチレンジアミン、Ｎ，Ｎ，Ｎ’，Ｎ’−テトラエチルエチレンジアミン、Ｎ，Ｎ，Ｎ’−トリエチルエチレンジアミン、Ｎ，Ｎ’−ジエチルエチレンジアミン、Ｎ，Ｎ−ジエチルエチレンジアミン、Ｎ−エチルエチレンジアミン、Ｎ，Ｎ−ジメチル−Ｎ’−エチルエチレンジアミン、Ｎ，Ｎ’−ジメチル−Ｎ−エチルエチレンジアミン、Ｎ−ｎ−プロピルエチレンジアミン、Ｎ，Ｎ’−ジーｎ−プロピルエチレンジアミン、Ｎ−ｉ−プロピルエチレンジアミン、Ｎ，Ｎ’−ジーｉ−プロピルエチレンジアミン、Ｎ−ｎ−ブチルエチレンジアミン、Ｎ，Ｎ’−ジーｎ−ブチルエチレンジアミン、Ｎ−ｉ−ブチルエチレンジアミン、Ｎ，Ｎ’−ジーｉ−ブチルエチレンジアミン、Ｎ−ｔ−ブチルエチレンジアミン、Ｎ，Ｎ’−ジーｔ−ブチルエチレンジアミン、Ｎ，Ｎ，Ｎ’，Ｎ’−テトラメチル−１，３−ジアミノプロパン、Ｎ，Ｎ，Ｎ’−トリメチル−１，３−ジアミノプロパン、Ｎ，Ｎ’−ジメチル−１，３−ジアミノプロパン、Ｎ−メチル−１，３−ジアミノプロパン、Ｎ，Ｎ，Ｎ’，Ｎ’−テトラメチル−１，３−ジアミノ−１−メチルプロパン、Ｎ，Ｎ，Ｎ’，Ｎ’−テトラメチル−１，３−ジアミノ−２−メチルプロパン、Ｎ，Ｎ，Ｎ’，Ｎ’−テトラメチル−１，４−ジアミノブタン、Ｎ，Ｎ，Ｎ’，Ｎ’−テトラメチル−１，５−ジアミノペンタン等が挙げられる。
好ましいジアミン化合物は、２つの窒素原子をつなぐアルキレン基（Ｒ₉）の炭素数が２または３のものである。
これらのジアミン化合物の使用量は特に限定されないが、通常使用されるフェノール化合物１００モルに対して０．０１モル〜１０モルの範囲で用いられる。
重合触媒を構成するその他の成分について説明する。
重合工程で用いる重合触媒には、上述した触媒成分の他、さらに、例えば３級モノアミン化合物または２級モノアミン化合物を、それぞれ単独でまたは組み合わせて含有させてもよい。
３級モノアミン化合物とは、脂環式３級アミンを含む脂肪族３級アミンである。
例えば、トリメチルアミン、トリエチルアミン、トリプロピルアミン、トリブチルアミン、トリイソブチルアミン、ジメチルエチルアミン、ジメチルプロピルアミン、アリルジエチルアミン、ジメチル−ｎ−ブチルアミン、ジエチルイソプロピルアミン、Ｎ−メチルシクロヘキシルアミン等が挙げられる。
これらの第３級モノアミンは、単独で用いてもよいし、２種以上を組み合わせて用いてもよい。使用量は特に限定されないが、重合するフェノール化合物１００モルに対して１５モル以下が好ましい。
２級モノアミン化合物としては、第２級脂肪族アミンが適用できる。
例えば、ジメチルアミン、ジエチルアミン、ジ−ｎ−プロピルアミン、ジ−ｉ−プロピルアミン、ジ−ｎ−ブチルアミン、ジ−ｉ−ブチルアミン、ジ−ｔ−ブチルアミン、ジペンチルアミン類、ジヘキシルアミン類、ジオクチルアミン類、ジデシルアミン類、ジベンジルアミン類、メチルエチルアミン、メチルプロピルアミン、メチルブチルアミン、シクロヘキシルアミンが挙げられる。
また、２級モノアミン化合物としては、芳香族を含む２級モノアミン化合物も適用できる。例えば、Ｎ−フェニルメタノールアミン、Ｎ−フェニルエタノールアミン、Ｎ−フェニルプロパノールアミン、Ｎ−（ｍ−メチルフェニル）エタノールアミン、Ｎ−（ｐ−メチルフェニル）エタノールアミン、Ｎ−（２’，６’−ジメチルフェニル）エタノールアミン、Ｎ−（ｐ−クロロフェニル）エタノールアミン、Ｎ−エチルアニリン、Ｎ−ブチルアニリン、Ｎ−メチル−２−メチルアニリン、Ｎ−メチル−２，６−ジメチルアニリン、ジフェニルアミン等が挙げられる。上述した２級モノアミン化合物は、単独で用いてもよく、２種以上を組み合わせて用いてもよい。２級モノアミン化合物の使用量は、特に限定されないが、重合するフェノール化合物１００モルに対して１５モル以下が好適である。 Since the polymerization reaction proceeds efficiently under some alkaline conditions, some alkali or further amine may be added thereto.
As a suitable catalyst in the production process of the polyphenylene ether used in the present embodiment, a catalyst containing a copper compound, a halogen compound and a diamine compound represented by the following formula (2) as constituent components can be given.

In the above formula _{(2), R 5, R} 6, R 7 and R ₈ are each independently selected from hydrogen atom, the group consisting of linear or branched alkyl group having 1 to 6 carbon atoms Indicates either. Note that all are not hydrogen at the same time. R ₉ represents a linear or branched alkylene group having 2 to 5 carbon atoms.
As a copper compound which comprises a catalyst component, a cuprous compound, a cupric compound, or a mixture thereof can be used. Examples of the cuprous compound include cuprous chloride, cuprous bromide, cuprous sulfate, and cuprous nitrate. Examples of the cupric compound include cupric chloride, cupric bromide, cupric sulfate, cupric nitrate, and the like. Among these, particularly preferred copper compounds are cuprous chloride, cupric chloride, cuprous bromide, and cupric bromide.
Moreover, you may synthesize | combine these copper compounds from the halogen or acid corresponding to an oxide (for example, cuprous oxide), carbonate, a hydroxide, etc.
For example, it can be synthesized by mixing cuprous oxide and a halogen compound (for example, a solution of hydrogen halide).
These copper compounds may be used alone or in combination of two or more.
Examples of the halogen compound constituting the catalyst component include hydrogen chloride, hydrogen bromide, hydrogen iodide, sodium chloride, sodium bromide, sodium iodide, potassium chloride, potassium bromide, potassium iodide, tetramethylammonium chloride, Tetramethylammonium bromide, tetramethylammonium iodide, tetraethylammonium chloride, tetraethylammonium bromide, tetraethylammonium iodide, and the like. These can be used as an aqueous solution or a solution using an appropriate solvent.
These halogen compounds may be used alone or in combination of two or more.
Preferred halogen compounds are an aqueous solution of hydrogen chloride and an aqueous solution of hydrogen bromide.
Although the usage-amount of these compounds is not specifically limited, As a halogen atom with respect to the molar amount of a copper atom, 2 times or more and 20 times or less are preferable, As a preferable usage-amount of a copper atom with respect to 100 mol of the phenolic compound used. Is in the range of 0.02 to 0.6 mol.
Examples of the diamine compound represented by the above formula (2) include N, N, N ′, N′-tetramethylethylenediamine, N, N, N′-trimethylethylenediamine, N, N′-dimethylethylenediamine, and N, N. -Dimethylethylenediamine, N-methylethylenediamine, N, N, N ', N'-tetraethylethylenediamine, N, N, N'-triethylethylenediamine, N, N'-diethylethylenediamine, N, N-diethylethylenediamine, N-ethyl Ethylenediamine, N, N-dimethyl-N′-ethylethylenediamine, N, N′-dimethyl-N-ethylethylenediamine, Nn-propylethylenediamine, N, N′-di-n-propylethylenediamine, Ni-propylethylenediamine N, N′-Di i-propylethylene di Min, Nn-butylethylenediamine, N, N′-di-n-butylethylenediamine, Ni-butylethylenediamine, N, N′-di-butylethylenediamine, Nt-butylethylenediamine, N, N′- Di-t-butylethylenediamine, N, N, N ′, N′-tetramethyl-1,3-diaminopropane, N, N, N′-trimethyl-1,3-diaminopropane, N, N′-dimethyl-1 , 3-diaminopropane, N-methyl-1,3-diaminopropane, N, N, N ′, N′-tetramethyl-1,3-diamino-1-methylpropane, N, N, N ′, N ′ -Tetramethyl-1,3-diamino-2-methylpropane, N, N, N ', N'-tetramethyl-1,4-diaminobutane, N, N, N', N'-tetramethyl-1, 5-diaminopentane And the like.
Preferred diamine compounds are those in which the alkylene group (R ₉ ) connecting two nitrogen atoms has 2 or 3 carbon atoms.
Although the usage-amount of these diamine compounds is not specifically limited, It is used in 0.01 mol-10 mol with respect to 100 mol of phenol compounds used normally.
The other components constituting the polymerization catalyst will be described.
In addition to the catalyst components described above, the polymerization catalyst used in the polymerization step may further contain, for example, a tertiary monoamine compound or a secondary monoamine compound, either alone or in combination.
The tertiary monoamine compound is an aliphatic tertiary amine containing an alicyclic tertiary amine.
Examples include trimethylamine, triethylamine, tripropylamine, tributylamine, triisobutylamine, dimethylethylamine, dimethylpropylamine, allyldiethylamine, dimethyl-n-butylamine, diethylisopropylamine, N-methylcyclohexylamine and the like.
These tertiary monoamines may be used alone or in combination of two or more. The amount used is not particularly limited, but is preferably 15 mol or less with respect to 100 mol of the phenol compound to be polymerized.
A secondary aliphatic amine can be applied as the secondary monoamine compound.
For example, dimethylamine, diethylamine, di-n-propylamine, di-i-propylamine, di-n-butylamine, di-i-butylamine, di-t-butylamine, dipentylamines, dihexylamines, dioctylamines , Didecylamines, dibenzylamines, methylethylamine, methylpropylamine, methylbutylamine, and cyclohexylamine.
Further, as the secondary monoamine compound, a secondary monoamine compound containing an aromatic can also be applied. For example, N-phenylmethanolamine, N-phenylethanolamine, N-phenylpropanolamine, N- (m-methylphenyl) ethanolamine, N- (p-methylphenyl) ethanolamine, N- (2 ′, 6 ′ -Dimethylphenyl) ethanolamine, N- (p-chlorophenyl) ethanolamine, N-ethylaniline, N-butylaniline, N-methyl-2-methylaniline, N-methyl-2,6-dimethylaniline, diphenylamine and the like Can be mentioned. The above-mentioned secondary monoamine compounds may be used alone or in combination of two or more. Although the usage-amount of a secondary monoamine compound is not specifically limited, 15 mol or less is suitable with respect to 100 mol of phenol compounds to superpose | polymerize.

The post-treatment method after completion of the polymerization reaction is not particularly limited. Usually, an acid such as hydrochloric acid or acetic acid, ethylenediaminetetraacetic acid (EDTA) and a salt thereof, nitrilotriacetic acid and a salt thereof are used as a reaction solution. In addition, there is a method of deactivating the catalyst.
Thereafter, since the polymerization solution at the end of the polymerization is in a state where polyphenylene ether is precipitated, repeated washing treatment is performed using a solution mainly composed of a solvent having low polyphenylene ether solubility for the purpose of washing and removing the catalyst. Preferably it is done.
Next, the polyphenylene ether can be recovered as a powder by performing a drying process using various dryers.

The drying treatment is performed at a temperature of at least 60 ° C., preferably 80 ° C. or higher, more preferably 120 ° C. or higher, further preferably 140 ° C. or higher, and even more preferably 150 ° C. or higher.
If the polyphenylene ether is dried at a temperature of less than 60 ° C., the aromatic hydrocarbon content in the polyphenylene ether may not be efficiently suppressed to less than 1.5% by mass.
In order to obtain polyphenylene ether with high efficiency, a method of increasing the drying temperature, a method of increasing the degree of vacuum in the drying atmosphere, a method of stirring during the drying, and the like are effective. In particular, the drying temperature is increased. The method is preferable from the viewpoint of production efficiency.
The drying process preferably uses a mixer. Examples of the mixer include a stirring type and a rolling type dryer. As a result, the processing amount can be increased and the productivity can be maintained high.

  The reduced viscosity (0.5 dl / g chloroform solution, measured at 30 ° C.) of the polyphenylene ether used in the present embodiment is not limited as long as the molecular weight is satisfied, but it is in the range of 0.20 to 0.40 dl / g. Is preferable, and the range of 0.25 dl / g to 0.35 dl / g is more preferable.

  In the present embodiment, various known stabilizers can be suitably used for stabilizing the polyphenylene ether. Examples of the stabilizer include metal stabilizers such as zinc oxide and zinc sulfide, organic stabilizers such as hindered phenol stabilizers, phosphate ester stabilizers, and hindered amine stabilizers. A preferable blending amount of the stabilizer is less than 5 parts by mass with respect to 100 parts by mass of the polyphenylene ether. Among the stabilizers, an antioxidant having both a sulfur element and a hydroxyl group in the molecule is particularly preferable. Specific product names include Irganox 1520 or Irganox 1726 available from Ciba Specialty Chemicals. These stabilizers are extremely effective from the viewpoint of preventing discoloration of pellets due to oxidation reaction.

  Further, modified polyphenylene ether may be used as the polyphenylene ether. Examples of the modified polyphenylene ether include polyphenylene ether obtained by grafting or adding 0.01 to 10% by mass of a styrene monomer or a derivative thereof. The mixing ratio of polyphenylene ether and modified polyphenylene ether is not particularly limited, and can be mixed at an arbitrary ratio.

上記式（３）中、Ｒは水素、低級アルキルまたはハロゲンを示し、Ｚはビニル、水素、ハロゲンおよび低級アルキルよりなる群から選択され、ｐは０〜５の整数である。 [Component (b)]
(B) Polystyrene used in the present embodiment is a homopolymer composed of 50% by weight or more of an aromatic vinyl monomer unit represented by the following general formula (3) or other vinyl that can be copolymerized It is a copolymer with a system monomer or a rubbery polymer.

In the above formula (3), R represents hydrogen, lower alkyl or halogen, Z is selected from the group consisting of vinyl, hydrogen, halogen and lower alkyl, and p is an integer of 0-5.

  Specific examples of the aromatic vinyl monomer in these homopolymers include styrene, α-methylstyrene, 2,4-dimethylstyrene, monochlorostyrene, p-methylstyrene, p-tert-butylstyrene, ethylstyrene, and the like. Is mentioned. Other vinyl monomers that can be copolymerized with aromatic vinyl monomers include methacrylic esters such as methyl methacrylate and ethyl methacrylate, acid anhydrides such as maleic anhydride, and rubber. Examples of the polymer include conjugated diene rubbers, copolymers of conjugated dienes and aromatic vinyl compounds, and ethylene-propylene copolymer rubbers.

  The ratio of the above-mentioned (b) polystyrene and (a) polyphenylene ether is that the content of (b) polystyrene is less than 50% by mass with respect to 100% by mass in total of the (a) component and the (b) component. Is more preferable, it is more preferable that it is 45 weight% or less, and it is especially preferable that it is less than 40 mass%. By containing (b) polystyrene within the above range, the compatibility between the polyphenylene ether and the hydrogenated block copolymer of the component (c) described later can be appropriately controlled, and the resulting resin composition chips The rate tends to be good.

  Moreover, the tensile characteristic of the resin composition which consists of the below-mentioned (a)-(d) component improves by making the ratio of (b) polystyrene into the said range. This is because the compatibility between (a) polyphenylene ether and (c) hydrogenated block copolymer, which will be described later, is appropriately controlled, and more (c) hydrogenated block copolymer can be used as (a) polyphenylene. This is presumed to act as a compatibilizer between ether and (d) polypropylene.

[Component (c)]
The (c) hydrogenated block copolymer used in the present embodiment comprises at least two polymer blocks A mainly composed of vinyl aromatic compounds and at least one polymer block B mainly composed of conjugated diene compounds. And at least a part of the block copolymer containing hydrogenated, the number average molecular weight (Mnc) as a hydrogenated block copolymer is 100,000 or less, and the polymer block A The number average molecular weight (MncA) is 8,000 or more.

(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 of more than 50% by mass, and the vinyl aromatic compound is 70% by mass. It is preferable to contain above.

  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 the above, styrene is preferred.

  The number average molecular weight (MncA) of the polymer block A contained in the component (c) is 8,000 or more, preferably 9,000 or more. The upper limit of the number average molecular weight (MncA) of the polymer block A is not particularly limited, but is preferably 30,000 or less. In this embodiment, in order to provide fluidity and heat resistance, (a) the amount of components having a molecular weight of 50,000 or more is 5 to 20% by mass, and the amount of components having a molecular weight of 8,000 or less is 12 to 30% by mass. Although polyphenylene ether is used, the compatibility of both can be improved by using the (c) hydrogenated block copolymer that satisfies the above conditions, and the fluidity and mechanical properties of the resulting resin composition can be improved. Giving a great advantage. The number average molecular weight (MncA) of the polymer block A can be controlled by known means, for example, it can be controlled by the amount of the catalyst to be added.

(Polymer block B mainly composed of conjugated diene compound)
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% by mass, and contains 70% by mass or more of the conjugated diene compound. It is preferable.

  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. Among the above, butadiene, isoprene and combinations thereof are preferable.

The total amount of component (c) conjugated diene compounds bonded by 1,2-vinyl bonds or 3,4-vinyl bonds (hereinafter sometimes referred to as “total vinyl bond amount”) is a polymer block. It is preferable that it is 30-90 mass% with respect to all the conjugated diene compounds which comprise B, It is more preferable that it is 35-90 mass%, It is further more preferable that it is 45-90 mass%, 70-90 It is particularly preferable that the content is% by mass. When the total vinyl bond amount is within the above range, production tends to be good.
In the present embodiment, the total vinyl bond amount can be measured with an infrared spectrophotometer.

  The number average molecular weight (Mnc) of the component (c) is measured by Showa Denko Co., Ltd. Gel Permeation Chromatography System 21 (column: Showa Denko Co., Ltd. KG, one K-800RL one more. Standard polystyrene with K-800R connected in series in one column, column temperature: 40 ° C., solvent: chloroform, solvent flow rate: 10 ml / min, sample concentration: 1 g / liter of chloroform solution of hydrogenated block copolymer) (The molecular weight of standard polystyrene can be measured by preparing a calibration curve using 3650000, 217000, 1090000, 681000, 204000, 52000, 30200, 13800, 3360, 1300, 550). The UV (ultraviolet) wavelength of the detector is measured by setting both standard polystyrene and hydrogenated block copolymer to 254 nm. In addition, the number average molecular weight (MncA) of the polymer block A mainly composed of the vinyl aromatic compound of the hydrogenated block copolymer is, for example, the above-described hydrogenated block in the case of an ABA type structure. Based on the number average molecular weight (Mnc) of the copolymer, it is assumed that the molecular weight distribution of the hydrogenated block copolymer is 1, and that two polymer blocks A mainly composed of vinyl aromatic compounds exist as the same molecular weight. And (MncA) = (Mnc) × bonded vinyl aromatic compound amount ratio ÷ 2. Similarly, in the case of a hydrogenated block copolymer of the A-B-A-B-A type, it can be obtained by the following formula: (MncA) = (Mnc) × the ratio of the amount of bonded vinyl aromatic compounds ÷ 3. . In addition, in the step of synthesizing the vinyl aromatic compound-conjugated diene block copolymer, when the sequence of the block structure A and the block structure B described above is clear, the measurement was performed without depending on the above calculation formula. You may calculate from the ratio of the block structure A based on the number average molecular weight (Mnc) of a hydrogenated block copolymer.

  The number average molecular weight (Mnc) of the component (c) is 100,000 or less. When the number average molecular weight (Mnc) of the component (c) is 100,000 or less, a preferable dispersion state can be achieved without the component (c) being aggregated. (C) Although the minimum of the number average molecular weight (Mnc) of a component is not specifically limited, It is preferable that it is 30,000 or more. The number average molecular weight (Mnc) can be controlled by known means, and can be controlled, for example, by the amount of catalyst added in each step.

  Assuming that the block polymer A is “A” and the block polymer B is “B”, the component (c) may be, for example, ABA type, ABAB type, BAB -A type, (A-B-) n-X type (where n is an integer of 1 or more, X is a reaction residue of a polyfunctional coupling agent such as silicon tetrachloride, tin tetrachloride or polyfunctional organolithium) And a hydrogenated product of a vinyl aromatic-conjugated diene compound block copolymer having a structure in which block units such as ABABABA type are bonded. It is done. Among these, a hydrogenated block copolymer having an A-B-A-B type structure or a B-A-B-A type structure is more preferable because it has excellent fluidity as compared with an A-B-A type hydrogenated block copolymer. .

  In addition, the content of the bonded vinyl aromatic compound in the component (c) is preferably 15 to 50% by mass, more preferably 25 to 45% by mass, and still more preferably based on the entire component (c). Is 30-45 mass%. When the content of the vinyl aromatic compound is 15 to 50% by mass, the compatibility between the component (a) and the component (b) tends to be improved. In the present embodiment, the content of the bonded vinyl aromatic compound can be measured by NMR.

  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. . Polymer block A and polymer block B are random and tapered distribution of vinyl aromatic compound or conjugated diene compound in the molecular chain in each polymer block (in which the monomer component increases or decreases along the molecular chain) ), Partly in the form of a block, or any combination thereof. When two or more polymer blocks A or polymer blocks B are present in the repeating unit, the polymer blocks may have the same structure or different structures.

  Further, the hydrogenation rate with respect to the conjugated diene compound in the component (c) is not particularly limited, but is preferably 50% or more, more preferably 80% or more of the double bond derived from the conjugated diene compound. Preferably it is 90% or more. In the present embodiment, the hydrogenation rate can be measured by NMR.

  (C) It does not specifically limit as a manufacturing method of the hydrogenated block copolymer of a component, It can obtain by a well-known manufacturing method. Known production methods include, for example, JP-A-47-11486, JP-A-49-66743, JP-A-50-75651, JP-A-54-126255, JP-A-56- No. 10542, JP-A-56-62847, JP-A-56-1000084, JP-A-2-300218, British Patent 1130770, US Pat. No. 3,281,383, US Pat. No. 3639517 No. 1, British Patent No. 1020720, US Pat. No. 3,333,024 and US Pat. No. 4,501,857.

  In addition, the hydrogenated block copolymer of component (c) is a hydrogenated block copolymer and an α, β-unsaturated carboxylic acid or derivative thereof (ester compound or acid anhydride compound) in the presence of a radical generator. The modified hydrogenated block copolymer obtained by making it react at 80-350 degreeC in a molten state, a solution state, or a slurry state in the bottom or absence. 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. Further, it may be a mixture of the hydrogenated block copolymer and the modified hydrogenated block copolymer in an arbitrary ratio.

  In the resin composition containing (a) polyphenylene ether, (b) polystyrene, and (c) hydrogenated block copolymer of the present embodiment, with respect to a total of 100% by mass of the components (a) to (c). The total content of (a) polyphenylene ether and (b) polystyrene is 1 to 99% by mass, preferably 5 to 95% by mass, and more preferably 7 to 93% by mass. The content of (c) hydrogenated block copolymer is 1 to 99% by mass, preferably 5 to 95% by mass, with respect to 100% by mass in total of the components (a) to (c). More preferably, it is 7-93 mass%.

  The present invention uses (a) a polyphenylene ether having a specific molecular weight in order to impart good fluidity and mechanical properties, and a vinyl aromatic having an appropriate molecular weight for good compatibility with the polyphenylene ether having the specific molecular weight. This is achieved by using (c) a hydrogenated block copolymer having a block composed mainly of a compound, and further by using (b) polystyrene in order to further control the compatibility of both in an appropriate range. By satisfying each requirement, it is possible to obtain a resin composition which is excellent in fluidity and mechanical properties and does not cause delamination, cracking or generation of chips.

Moreover, the resin composition which concerns on this Embodiment can improve the heat resistance of a polypropylene by adding to the below-mentioned (d) polypropylene.
When added to (d) polypropylene, usually an emulsifying dispersant (hereinafter abbreviated as an admixture) for compatibilizing the incompatible (a) polyphenylene ether and (d) polypropylene is essential. However, in this Embodiment, the hydrogenated block copolymer (c) which has a specific structure can be used as an admixture. When the component (c) is used as an admixture, at least two polymer blocks A mainly composed of styrene and at least one heavy mainly composed of butadiene having a 1,2-vinyl bond content of 70 to 90%. A hydrogenated block copolymer obtained by hydrogenating a block copolymer comprising the combined block B is preferred.

  The at least one polymer block B mainly composed of butadiene may be a single polymer block of butadiene having a 1,2-vinyl bond content of 70 to 90% before hydrogenation, At least one polymer block B1 mainly composed of butadiene having a 1,2-vinyl bond content of 70 to 90% and at least one polymer composed mainly of butadiene having a 1,2-vinyl bond content of 30 to 70%. The polymer block B having both the polymer block B2 may be used. A block copolymer showing such a block structure is, for example, a known A-B2-B1-A known in which 1,2-vinyl bond amount is controlled based on the adjusted feed sequence of each monomer unit. It can be obtained by a polymerization method. The bonding form of butadiene before hydrogenation can be known by an infrared spectrophotometer, NMR or the like.

[Component (d)]
When (d) polypropylene is included, the content of the component (d) is preferably 1 to 95% by mass, and preferably 10 to 95% by mass with respect to 100% by mass of the total amount of the components (a) to (d). % Is more preferable, and 20 to 90% by mass is even more preferable. The resin composition further containing (d) polypropylene within the above range tends to improve fluidity and workability.
(D) The polypropylene is a crystalline propylene homopolymer, or a crystalline propylene homopolymer portion obtained in the first step of polymerization and propylene, ethylene and / or at least one other α- A crystalline propylene-ethylene block copolymer having a propylene-ethylene random copolymer portion obtained by copolymerizing an olefin (for example, butene-1, hexene-1, etc.); It may be a mixture with a crystalline propylene-ethylene block copolymer.
(D) The polypropylene is preferably homopolypropylene and / or block polypropylene. In addition, the melt flow rate (MFR: measured at 230 ° C. under a load of 2.16 kg in accordance with ASTM D1238) of the component (d) is preferably 0.1 to 100 g / 10 minutes, and preferably 0.2 to 90 g / 10 minutes is more preferable, and 0.3 to 80 g / 10 minutes is even more preferable. Such a resin composition containing (d) polypropylene tends to be able to balance fluidity and rigidity.

  (D) Polypropylene is usually a titanium trichloride catalyst or a titanium halide catalyst supported on a carrier such as magnesium chloride and the like in the presence of an alkylaluminum compound and a polymerization temperature of 0 to 100 ° C., and a polymerization pressure of 3 to 100. It is obtained by polymerizing the monomer in the atmospheric pressure range. At this time, a chain transfer agent such as hydrogen can be added in order to adjust the molecular weight of the polymer. Also, the polymerization method can be either batch type or continuous type, and can be selected from methods such as solution polymerization in a solvent such as butane, pentane, hexane, heptane, and octane, and slurry polymerization. Below, bulk polymerization in monomers, gas phase polymerization methods in gaseous monomers, and the like can also be applied.

  Furthermore, in addition to the above polymerization catalyst, an electron donating compound can be used as an internal donor component or an external donor component as a third component in order to increase the isotacticity and polymerization activity of the resulting polypropylene. As these electron-donating compounds, known compounds can be used, for example, ester compounds such as ε-caprolactone, methyl methacrylate, ethyl benzoate, methyl toluate, triphenyl phosphite, tributyl phosphite and the like. Phosphoric acid derivatives such as phosphate esters and hexamethylphosphoric triamide, alkoxy ester compounds, aromatic monocarboxylic acid esters and / or aromatic alkyl alkoxy silanes, aliphatic hydrocarbon alkoxy silanes, various ether compounds, various alcohols And / or various phenols.

(D) Polypropylene is obtained, for example, by the method described above, and the polymer is characterized by having a homopolypropylene portion having a crystalline melting point of preferably 155 ° C or higher and a crystallization temperature of preferably 100 ° C to 130 ° C. It is. The crystalline melting point of this homopolypropylene part is the value of the melting point measured by a differential scanning calorimeter (DSC: for example, DSC-2 type manufactured by PerkinElmer Co., Ltd.) at a heating rate of 20 ° C./min and a cooling rate of 20 ° C./min. . More specifically, first, about 5 mg of a sample is kept at 20 ° C. for 2 minutes, then heated to 230 ° C. at 20 ° C./min, kept at 230 ° C. for 2 minutes, and then lowered to 20 ° C. at a rate of temperature drop of 20 ° C./min. After the temperature is lowered and kept at 20 ° C. for 2 minutes, the temperature of the top peak of the endothermic peak that appears when the temperature is raised at a rate of temperature rise of 20 ° C./min can be determined as the melting point. Polypropylene having a melting point of less than 155 ° C. tends to lower the rigidity and heat resistance (load deflection temperature: DTUL) of the resulting resin composition. More preferably, it is a polypropylene having a homopolypropylene portion having a crystalline melting point of 163 ° C. or higher, and gives a resin composition that is more excellent in rigidity and heat resistance (load deflection temperature: DTUL). In addition, at the time of measuring the crystal melting point by the differential scanning calorimeter (DSC), the crystallization temperature (solidification temperature) peak of the molten polypropylene can be known, and the crystallization temperature of the polypropylene can be confirmed in a temperature range of 100 ° C to 130 ° C. .
The melting point of (d) polypropylene is preferably 155 ° C. or higher, more preferably 158 ° C. or higher, and further preferably 163 ° C. or higher. When the melting point is within the above range, the resin composition tends to be more excellent in rigidity and heat resistance (load deflection temperature: DTUL). The melting point can be measured by the same method as the crystalline melting point of the homopolypropylene part.

  (D) In addition to the above-mentioned polypropylene, (d) the polypropylene and the α, β-unsaturated carboxylic acid or derivative thereof in the presence or absence of a radical generator, in the molten state or in the solution state, It may be a known modified polypropylene obtained by reacting at a temperature of 350 ° C. (0.01 to 10% by mass of the α, β-unsaturated carboxylic acid or derivative thereof is grafted or added), and further It may be a mixture of any ratio of the prepared polypropylene and the modified polypropylene.

The resin composition of this Embodiment can also mix | blend another component from a viewpoint of the further physical-property improvement.
[(E) component]
The resin composition according to the present embodiment may contain a hydrogenated block copolymer (e) different from the component (c).
The hydrogenated block copolymer (e) is a block copolymer comprising at least two polymer blocks A mainly composed of vinyl aromatic compounds and at least one polymer block B mainly composed of conjugated diene compounds. A hydrogenated block copolymer (e) obtained by hydrogenating a polymer, wherein the number average molecular weight (Mne) of the hydrogenated block copolymer is 150,000 or less, and the polymer block A The number average molecular weight (MneA) is 8,000 or more, and the content of the polymer block A is more than 50% by mass and 70% by mass or less with respect to the whole component (e), and the polymer block B In the bonding form of the conjugated diene compound, the total amount of the conjugated diene compound bonded by 1,2-vinyl bond or 3,4-vinyl bond is 2 with respect to the whole conjugated diene compound. Is 70 wt%.
By using the component (e) in combination with the component (c), the rigidity of the resin composition containing (a) polyphenylene ether and (d) polypropylene can be improved.

  The blending ratio of (c) hydrogenated block copolymer and (e) hydrogenated block copolymer is preferably (c) / (e) = 1 to 99% by mass / 99 to 1% by mass.

[(F) Filler]
The resin composition according to the present embodiment may further contain (f) a filler.

  (F) Examples of the filler include inorganic salts, glass fibers (glass long fibers, chopped strand glass fibers), cellulose, glass flakes, glass beads, carbon long fibers, chopped strand carbon fibers, whiskers, mica, clay, talc, Kaolin, magnesium hydroxide, magnesium sulfate and its fibers, silica, carbon black, titanium oxide, calcium carbonate, fly ash (coal ash), potassium titanate, wollastonite, thermal conductive materials (graphite, aluminum nitride, boron nitride, Alumina, beryllium oxide, silicon dioxide, magnesium oxide, aluminum nitrate, barium sulfate, etc.), conductive metal fiber, conductive metal flake, carbon black indicating conductivity, carbon fiber indicating conductivity, carbon nano At least one selected from the group consisting of cube can be selected and used. These fillers are further treated with surface treatment agents such as silane coupling agents, titanate coupling agents, aliphatic carboxylic acids, and aliphatic metal salts, and organic treatments such as ammonium salts by an intercalation method. It may also be a product obtained by treating a resin such as urethane resin or epoxy resin as a binder.

  (F) It is preferable that the compounding quantity of a filler is 2-60 mass% with respect to the whole quantity of a resin composition, It is more preferable that it is 3-50 mass%, It is 5-45 mass% Is more preferable. When the blending amount is 2% by mass or more, in addition to improving the mechanical strength, the dimensional accuracy of a molded product obtained by molding using the obtained resin composition is improved, and the blending amount is 60% by mass. The molded product obtained by molding the resulting resin composition has less sink marks, a smaller linear expansion coefficient due to temperature change (-30 ° C to 120 ° C), and excellent dimensional accuracy and anisotropy thereof. It can be a molded product holding

[Hindered phenol stabilizer]
The resin composition according to the present embodiment preferably includes a hindered phenol stabilizer. The hindered phenol-based stabilizer can exhibit an effect over a long period of time as well as during processing as a heat stabilizer.
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. As a compounding quantity of a hindered phenol type stabilizer, it is 0.1-2.0 mass% with respect to 100 mass% of resin compositions. Moreover, when the resin composition contains an organic stabilizer including a hindered phenol stabilizer, the amount of the hindered phenol stabilizer in the organic stabilizer is 100% by mass of the total amount of the organic stabilizer. When it is, it is preferable that it is 40-100 mass%.

[Other ingredients]
Examples of other components that can be blended in the resin composition according to the present embodiment include stabilizers, mold release agents, processing aids, flame retardants, anti-drip agents, nucleating agents, UV blockers, and dyes. And additives such as pigments, antioxidants, antistatic agents, and foaming agents. These additives can be used as long as they are known in the art, and the lower limit of the blending amount is preferably 0.1 parts by mass or more, more preferably 100 parts by mass of all resin compositions. Is 0.2 parts by mass or more, more preferably 0.3 parts by mass or more. As an upper limit, Preferably it is 10 mass parts or less, More preferably, it is 5 mass parts or less, More preferably, it is 3 mass parts or less. However, in the case of a flame retardant, the upper limit of the blending amount is 100 parts by mass or less, more preferably 70 parts by mass or less, and still more preferably 50 parts by mass or less with respect to 100 parts by mass of all the resin mixtures. Such flame retardants include organophosphate compounds, metal phosphinates, magnesium hydroxide, ammonium polyphosphate flame retardants, melamine flame retardants, triazine flame retardants, aromatic halogen flame retardants, and silicone flame retardants. , At least one selected from the group consisting of fluoropolymers can be selected and used.

  The resin composition of the present embodiment can be produced by various methods using the above-described components. For example, the above components may be heated and kneaded by a single screw extruder, a twin screw extruder, a roll, a kneader, a Brabender plastograph, a Banbury mixer, etc. A kneading method is preferred. In this case, the melting temperature is not particularly limited, but can be arbitrarily selected from the range of usually 150 to 350 ° C.

The pellet of this Embodiment is formed from the resin composition mentioned above.
A particularly preferred method for easily obtaining the resin composition (and its pellets) of the present embodiment will be described below.
(1) A melt kneader for melting and kneading each of the above components is a multi-screw extruder having two or more screws that can incorporate a kneading block at an arbitrary position of a screw. In a multi-screw extruder, the total kneading block portion of the screw used is substantially (L / D) ≧ 1.5, more preferably (L / D) ≧ 5 [where L is the total length of the kneading blocks D is the maximum outside diameter of the kneading block] and (π · D · N / h) ≧ 50 [where π = 3.14, D = the outside of the screw corresponding to the metering zone Diameter, N = screw rotation speed (rotation / second), h = groove depth of metering zone].
(2) These extruders have at least a first raw material supply port on the upstream side with respect to the flow direction of the raw material, and at least a second raw material supply port on the downstream side, and if necessary, on the downstream side of the second raw material supply port. Further, one or more raw material supply ports may be provided, and a vacuum vent port may be provided between the raw material supply ports as necessary. The basic raw material supply method for producing a resin composition is as follows: (a) polyphenylene ether, (b) polystyrene, (c) hydrogenated block copolymer total amount, or (a) polyphenylene from the first raw material supply port. A second raw material supply port for supplying a total amount of ether, (b) polystyrene and (d) a portion of polypropylene in a range not exceeding 50% of the total amount of polypropylene and (c) the hydrogenated block copolymer of component (D) An extrusion method for supplying the entire amount of polypropylene or the remaining polypropylene distributed to the first raw material supply port is used. Usually, the extruder barrel set temperature is 200 to 370 ° C., preferably 250 to 320 ° C., screw rotation speed 100 Pellet is produced by melt-kneading under conditions of ˜1200 rpm, preferably 200-500 rpm.
(3) The hydrogenated block copolymer of the component (e) can be supplied to the first raw material supply port in a total amount or divided and supplied to the first raw material supply port and the second raw material supply port at an arbitrary ratio. .
(4) The supply of the filler component (f) is basically a method in which all the resin components (a) to (e) are melt-kneaded and supplied from the third raw material supply port and melt-kneaded. preferable. When the conveyance capability of the side feed extruder that is supplied to the extruder, which tends to occur when the filler is fine powder, etc., decreases (d) the total amount of polypropylene or the (d) component from the second raw material supply port. Melting and kneading is performed by an extrusion method in which the remaining (d) polypropylene distributed to one raw material supply port is supplied together.
(5) Supply of additives such as stabilizers, mold release agents, processing aids, flame retardants, anti-drip agents, nucleating agents, UV blockers, dyes, pigments, antioxidants, antistatic agents, foaming agents, etc. It may be supplied together with other components from any one of the first raw material supply port and the second raw material supply port. In the case of a liquid additive, a liquid addition jig to the press-fitting zone provided in the extruder Is melt-kneaded by an extrusion method using a plunger pump and a gear pump.

The thermoplastic resin composition according to the present embodiment is produced by producing pellets of a resin composition containing (a) polyphenylene ether, (b) polystyrene and (c) hydrogenated block polymer by the above-described method. It can also be obtained by melt mixing with a resin.
The blending amount of the thermoplastic resin is preferably 10 to 1000 parts by mass, more preferably 20 to 900 parts by mass, and still more preferably with respect to 100 parts by mass of the pellets of the resin composition obtained by the above method. 30 to 800 parts by mass.

  Examples of the thermoplastic resin include vinyl aromatic compound polymer, vinyl aromatic compound copolymer, polypropylene, polyethylene, ethylene-α-olefin copolymer, polyamide 6, polyamide 66, polyamide 66/6, polycarbonate, and polyacetal. Selected from the group consisting of polyethylene terephthalate, polybutylene terephthalate, polytrimethylene terephthalate, aromatic ring-containing polyamide, aliphatic ring-containing polyamide, polyphenylene sulfide, liquid crystal polymer, polyether ether ketone, polyarylate, polyether sulfone, and polysulfone. There may be at least one of them, and polypropylene is particularly preferable.

  The thermoplastic resin composition can be produced by various methods. In the method for producing a thermoplastic resin composition according to the present embodiment, the melt-mixing step is preferably performed with an extruder or an injection molding machine. Specific examples of the melt kneading method include a heat melt kneading method using a single screw extruder, a twin screw extruder, a roll, a kneader, a Brabender plastograph, a Banbury mixer, etc., among others, a single screw extruder or a twin screw extruder. A melt kneading method using a machine is preferred.

Furthermore, when obtaining a thermoplastic resin composition, you may knead | mix the said (f) filler component and another additive. When melt-kneading with a twin-screw extruder, and explaining the case of kneading pellets, thermoplastic resin, filler components as an example,
(1) A method of supplying pellets, thermoplastic resin and filler from the first raw material supply port,
(2) A method of supplying pellets from the first raw material supply port, a thermoplastic resin from the second raw material supply port, and (f) a filler component,
(3) A method of supplying pellets from the first raw material supply port, a thermoplastic resin from the second raw material supply port, and (f) a filler component from the third raw material supply port,
(4) A method of supplying a thermoplastic resin from the first raw material supply port, pellets from the second raw material supply port, and (f) a filler component from the third raw material supply port,
It can be selected appropriately according to the purpose, and it can be seen that the range of processing conditions is widened.
When melt-kneading polypropylene using pellets as a raw material, it is preferable to employ the method (3) from the viewpoint of fluidity and mechanical properties.

  For example, when components (a) to (e) are well melted and kneaded all at once as is well known, the set temperature of a processing machine represented by an extruder is set to 270 in order to plasticize polyphenylene ether. The temperature must be higher than ° C. However, if pellets containing (a) to (c) used in the present embodiment are made and used as raw materials, the set temperature of the processing machine can be set to 270 ° C. or lower, and melt kneading (compounding) can be performed. From the viewpoint of mechanical strength, the set temperature during the second stage compound is preferably 260 ° C. or lower, more preferably 250 ° C. or lower.

  Moreover, the thermoplastic resin composition of the present embodiment can be obtained, for example, by dry blending polypropylene, preferably 10 to 1000 parts by mass with respect to 100 parts by mass of the above-described pellets, and injection molding. In the case of this method, a thermoplastic resin composition having a greatly simplified process and excellent mechanical strength can be obtained.

The molded body of the present embodiment is obtained by molding the above resin composition or the above thermoplastic resin composition.
Molded bodies obtained by molding the above-described resin composition or thermoplastic resin composition by various conventionally known methods such as injection molding, extrusion molding (sheet, film), and hollow molding are used as various parts. it can. Examples of these various parts include automobile exterior / skin parts, automobile interior parts, automobile underhood parts, and specifically bumpers, fenders, door panels, moldings, emblems, engine hoods, wheel covers, roofs, spoilers. Suitable for exterior parts such as engine covers, exterior parts, under hood parts, interior parts such as instrument panels and console box trims. Furthermore, it can also be used as various computers and peripheral devices thereof, other OA devices, televisions, videos, various disk player cabinets, chassis, refrigerators, air conditioners, liquid crystal projectors, and the like. Further, the molded body using the resin composition is an electric wire / cable obtained by coating a metal conductor or an optical fiber, a fuel case for a solid methanol battery, a secondary battery cell, a fuel cell water pipe, a water cooling tank, a boiler outer case. It can be used as a separator for lithium ion batteries obtained by stretching an ink peripheral part / member and chassis of an ink jet printer, a molded body such as a water pipe and a joint, and a sheet / film.
The molded body of the present embodiment is preferably at least one selected from the group consisting of the following (1) to (4).
(1) Sheet / film or stretched sheet / film (2) Automotive exterior / outboard parts, automotive interior parts, or automotive underhood parts (3) Electric wires / cables obtained by coating a resin composition on a metal conductor or optical fiber (4) Ink peripheral parts / members or chassis of ink jet printer

The present embodiment will be described in more detail with reference to examples, but the present embodiment is not limited to these examples.
(Polyphenylene ether / hydrogenated block copolymer resin composition)
Each physical property was measured as follows.
[Number average molecular weight]
The number average molecular weight of each component, and the quantification of the component having a molecular weight of 8,000 or less and the component having a molecular weight of 50,000 or more were measured by gel permeation chromatography (mobile phase: chloroform, standard material: polystyrene).
Specific measurement conditions for gel permeation chromatography in the measurement of the molecular weight of polyphenylene ether include gel permeation chromatography system 21 manufactured by Showa Denko KK (column: two K-805L manufactured by Showa Denko KK in series, column Temperature: 40 ° C., solvent: chloroform, solvent flow rate: 1.0 ml / min, sample concentration: 1 g / L chloroform solution of polyphenylene ether, standard polystyrene (standard polystyrene has a molecular weight of 3,650,000, 2 , 170,000, 1,090,000, 681,000, 204,000, 52,000, 30,200, 13,800, 3,360, 1,300, 550) Condition. The UV wavelength of the detector was selected to be 254 nm for standard polystyrene and 283 nm for polyphenylene ether.
As specific measurement conditions of gel permeation chromatography in the molecular weight measurement of the hydrogenated block copolymer, Showa Denko Co., Ltd. Gel Permeation Chromatography System 21 (column: Showa Denko Co., Ltd. KG 1) One K-800RL and one K-800R are connected in series in this order, column temperature: 40 ° C., solvent: chloroform, solvent flow rate: 10 ml / min, sample concentration: 1 g of hydrogenated block copolymer / L / Chloroform solution) Standard polystyrene (Standard polystyrene molecular weight is 3650000, 217000, 1090000, 681000, 204000, 52000, 30200, 13800, 3360, 1300, 550) It was. The UV (ultraviolet) wavelength of the detection unit was set to 254 nm for both standard polystyrene and hydrogenated block copolymer. The number average molecular weight of the polymer block A mainly composed of the vinyl aromatic compound of the hydrogenated block copolymer was calculated from the ratio of the block structure A based on the measured number average molecular weight of the hydrogenated block copolymer. .
[Measurement of bound styrene content]
The amount of bound styrene was measured by NMR.
[Measurement of hydrogenation rate]
The hydrogenation rate was measured by NMR.
[Measurement of total vinyl bond content]
The total vinyl bond amount was measured with an infrared spectrophotometer.

[Manufacture of each component of resin composition]
(A) Production of polyphenylene ether (a-1): 40 liters equipped with a sparger for introducing an oxygen-containing gas, a stirring turbine blade and a baffle at the bottom of the polymerization tank, and a reflux condenser in the vent gas line at the top of the polymerization tank 4.02 g of cupric oxide, 29.876 g of a 47% by mass hydrogen bromide aqueous solution, 9.684 g of di-t-, while blowing nitrogen gas into the jacketed polymerization tank at a flow rate of 0.5 L / min. Put butylethylenediamine, 46.88 g di-n-butylamine, 144.28 g butyldimethylamine, 20.65 kg toluene, and 3.12 kg 2,6-dimethylphenol into a homogeneous solution, Stir until the temperature is 25 ° C.
Next, dry air was introduced into the polymerization tank at a rate of 32.8 NL / min from a sparger and polymerization was started. Dry air was passed through for 86 minutes to obtain a polymerization mixture. The internal temperature at the end of the polymerization was controlled to 40 ° C. The polymerization solution at the end of the polymerization was in a solution state.
Stop the aeration of dry air, add 10 kg of 2.5 mass% aqueous solution of ethylenediaminetetraacetic acid tetrasodium salt (a reagent manufactured by Dojindo Laboratories) to the polymerization mixture, and stir the polymerization mixture at 70 ° C. for 150 minutes. The organic phase and the aqueous phase were separated by liquid-liquid separation.
After the obtained organic phase was brought to 50 ° C., methanol was added in excess to precipitate polyphenylene ether. Thereafter, the solution containing the precipitated polyphenylene ether was filtered, the remaining polyphenylene ether was dispersed in excess methanol, stirred at 50 ° C. for 30 minutes, and then filtered again. This operation was repeated twice to obtain wet polyphenylene ether. Furthermore, it was kept at 150 ° C. and 1 mmHg for 1.5 hours to obtain a dried polyphenylene ether powder.
The same operations as the above polymerization, filtration and drying were repeated twice to obtain a total of about 6 kg of polyphenylene ether powder. This polyphenylene ether powder was designated as (a-1). Each measurement regarding molecular weight was performed by the method mentioned above about obtained (a-1). The results of GPC measurement were as follows.
Amount of components having a molecular weight of 50,000 or more: 12% by mass
Component amount of molecular weight 8,000 or less: 22% by mass
Number average molecular weight: 11000

(A-2): 500 ml / min in a 10 liter jacketed polymerization tank equipped with a sparger for introducing an oxygen-containing gas at the bottom of the polymerization tank, a stirring turbine blade and a baffle, and a vent gas line at the top of the polymerization tank with a reflux condenser. 1.1164 g of cupric chloride dihydrate, 4.9172 g of 35% by mass hydrochloric acid, 42.642 g of N, N, N ′, N′-tetramethylpropanediamine, while blowing nitrogen gas at a flow rate of Charge 16.082 g di-n-butylamine, 2534.1 g xylene, 2534.1 g n-butanol, 1267.1 g methanol, and 1600.0 g 2,6-dimethylphenol to form a homogeneous solution and reaction The vessel was stirred until the internal temperature reached 30 ° C.
Subsequently, introduction of the oxygen-containing gas from the sparger was started at a rate of 1000 Nml / min into the vigorously stirred polymerization tank. An oxygen-containing gas was passed through for 420 minutes to obtain a polymerization mixture. The internal temperature of the reactor was controlled to 40 ° C. Further, after 135 minutes from the start of the supply of oxygen gas, polyphenylene ether was precipitated and showed a slurry form. The form of the polymerization liquid at the end of the polymerization was a precipitation polymerization liquid.
The aeration of the oxygen-containing gas was stopped, and 12.0 g of a 50 mass% aqueous solution of ethylenediaminetetraacetic acid tripotassium salt (a reagent manufactured by Dojindo Laboratories) was added to the polymerization mixture. Thereafter, the polymerization mixture was stirred for 60 minutes, then hydroquinone (a reagent manufactured by Wako Pure Chemical Industries, Ltd.) was added little by little, and stirring was continued until the slurry-like polyphenylene ether became white. The internal temperature of the reactor was controlled to 50 ° C. The slurry-like polyphenylene ether which became white was filtered, and methanol was added to the polyphenylene ether of the filtration residue, followed by washing. Then, it hold | maintained at 150 degreeC and 1 mmHg for 1.5 hours, and obtained the polyphenylene ether powder of the dried state.
The same operations as the above polymerization, filtration and drying were repeated 4 times to obtain a total of about 6 kg of polyphenylene ether powder. This polyphenylene ether powder was designated as (a-2). Each measurement regarding molecular weight was performed by the method mentioned above about obtained (a-2). The results of GPC measurement were as follows.
Amount of components having a molecular weight of 50,000 or more: 6% by mass
Component amount of molecular weight 8,000 or less: 12% by mass
Number average molecular weight: 11500

(A-3): The same as (a-2) above except that the amount of xylene placed in the polymerization tank was 4117.9 g, the amount of n-butanol was 950.3 g, and the amount of methanol was 1267.1 g. Thus, about 6 kg of polyphenylene ether powder was obtained. This polyphenylene ether powder was designated as (a-3). Each measurement regarding molecular weight was performed by the method mentioned above about obtained (a-3). The results of GPC measurement were as follows.
Amount of components having a molecular weight of 50,000 or more: 42% by mass
Component amount of molecular weight 8,000 or less: 4% by mass
Number average molecular weight: 24600

(A-4): A sparger for introducing an oxygen-containing gas, a stirring turbine blade and a baffle are provided at the bottom of the polymerization tank, a reflux condenser is provided in the vent gas line at the top of the polymerization tank, and the side of the polymerization tank is connected to the second polymerization tank. While blowing nitrogen gas at a flow rate of 500 mL / min into a 1.6 liter jacketed first polymerization tank equipped with an overflow line, 0.239 g of cupric chloride dihydrate, 1.122 g of 35% hydrochloric acid. 3.531 g di-n-butylamine, 18.154 g N, N, N ′, N′-tetramethylpropanediamine, 445.1 g xylene, 170.8 g n-butanol, and 509.5 g methanol Put.
Similarly, a sparger for introducing an oxygen-containing gas, a stirring turbine blade and a baffle are provided at the bottom of the polymerization tank, a reflux condenser is provided in the vent gas line at the top of the polymerization tank, and an overflow line to the washing tank is provided on the side of the polymerization tank. A 4.0 liter jacketed second polymerization vessel was charged with 1007.8 g of xylene, 378.4 g of n-butanol, and 509.5 g of methanol while blowing nitrogen gas at a flow rate of 1000 mL / min.
In addition, a 6.0 liter first raw material tank equipped with a reflux pump in a line that can be fed to the first polymerization tank by a plunger pump, a stirring turbine blade, and a vent gas line in the upper part of the tank, 0.642 g of cupric chloride dihydrate, 2.827 g of 35% by mass hydrochloric acid, 9.247 di-n-butylamine, 24.519 g of N, N, while blowing nitrogen gas at a flow rate of minutes. N ', N'-tetramethylpropanediamine, 1206.5 g of xylene, 454.5 g of n-butanol, 1362.2 g of methanol, and 920.0 g of 2,6-dimethylphenol were added, and the liquid was stirred. The polymerization solution was obtained by mixing. In addition, in order that the preparation liquid in a 1st raw material tank may reduce when it supplies to a superposition | polymerization tank, the thing of the said liquid composition was additionally added to the 1st raw material tank suitably.
Next, the polymerization solution is supplied from the first raw material tank to the vigorously stirred first polymerization tank at a flow rate of 19.42 g / min. At the same time, oxygen is contained from the sparger to the first polymerization tank at a rate of 329.42 mL / min. Introduced gas. Furthermore, simultaneously with the start of overflow from the first polymerization tank to the second polymerization tank, an oxygen-containing gas was introduced from the sparger into the second polymerization tank at a rate of 32.4 mL / min. The polymerization temperature was adjusted by passing a heating medium through the jacket so as to maintain 40 ° C. in both the first polymerization tank and the second polymerization tank. The overflow from the second polymerization tank was collected in a collection container.
Thereafter, the overflowed slurry began to be collected after 40 hours, and then polymerization was continued for 23 hours to complete the polymerization. The obtained polyphenylene ether slurry was about 26.8 kg.
A quarter-liter amount (6.7 kg) of the polyphenylene ether slurry obtained as described above was added to a 10 liter jacketed tank equipped with a reflux condenser in the vent gas line at the top of the stirred turbine blades and baffles and the tank. 70 g of a 10 mass% aqueous solution of ethylenediaminetetraacetic acid tripotassium salt (a reagent manufactured by Dojindo Laboratories) was added and warmed to 50 ° C.
Next, hydroquinone (a reagent manufactured by Wako Pure Chemical Industries, Ltd.) was added little by little, and the temperature was kept at 50 ° C. until the slurry polyphenylene ether became white. The white slurry-like polyphenylene ether was filtered, methanol was added to the remaining polyphenylene ether, and a washing treatment was performed to obtain a polyphenylene ether powder.
The same treatment was applied to the remaining polyphenylene ether slurry to obtain a total of about 6 kg of polyphenylene ether powder. This polyphenylene ether powder was designated as (a-4). Each measurement regarding molecular weight was performed by the method mentioned above about obtained (a-3). The results of GPC measurement were as follows.
Component amount with molecular weight of 50,000 or more: 8% by mass
Component amount of molecular weight 8,000 or less: 8% by mass
Number average molecular weight: 12500
(B): Styrene homopolymer (manufactured by PS Japan, PSJ polystyrene 685)

(C) Production of hydrogenated block copolymer Styrene was synthesized by anionic block copolymerization of styrene and butadiene using n-butyllithium as an initiator, cyclohexane solvent and tetrahydrofuran as a 1,2 bond amount regulator. -A butadiene block copolymer was polymerized. Next, the obtained styrene-butadiene block copolymer was hydrogenated at a hydrogen pressure of 5 kg / cm ² and a temperature of 50 ° C. using bis (η5-cyclopentadienyl) titanium dichloride and n-butyllithium as a hydrogenation catalyst. The addition was made. The polymer structure was controlled by changing the amount and order of the monomers, the molecular weight was the catalyst amount, the 1,2 bond amount was the 1,2 bond amount modifier and the polymerization temperature, and the hydrogenation rate was changed. .
(C-1) Hydrogenated polybutadiene-polystyrene- (1) -hydrogenated polybutadiene-polystyrene (2) hydrogenated block copolymer having a B-A-B-A type structure was synthesized by the method described above. The obtained hydrogenated block copolymer was defined as (c-1). The physical properties of (c-1) were as follows.
Bonded styrene content: 43%
1,2-vinyl bond content in polybutadiene block: 75%
Number average molecular weight of hydrogenated block copolymer: 97000
Number average molecular weight of polystyrene block (1): 22000
Number average molecular weight of polystyrene block (2): 20000
Polybutadiene block hydrogenation rate: 99.9%

（ポリプロピレン／ポリフェニレンエーテル樹脂組成物）
［融点］
融点の測定は、示差走査熱量計によって測定した。
［ＭＦＲ］
ＭＦＲはＡＳＴＭ Ｄ１２３８に準拠し、２３０℃、２．１６ｋｇの荷重で測定した。
［樹脂組成物の各成分の製造］
（ａ）ポリフェニレンエーテル
（ａ−５）：前述の（ａ−１）と同様の製造方法で得られたポリフェニレンエーテルを（ａ−５）とした。
分子量５０，０００以上の成分量：１２質量％
分子量８，０００以下の成分量：２２質量％
数平均分子量：１１０００ (C-2) A hydrogenated block copolymer having an ABA type structure of polystyrene (1) -hydrogenated polybutadiene-polystyrene (2) was synthesized by the method described above. The obtained hydrogenated block copolymer was designated as (c-2). The physical properties of (c-2) were as follows.
Bonded styrene content: 55%
1,2-vinyl bond content in polybutadiene block: 36%
Number average molecular weight of hydrogenated block copolymer: 110000
Number average molecular weight of polystyrene block (1): 30000
Number average molecular weight of polystyrene block (2): 30500
Polybutadiene block hydrogenation rate: 99.9%
(C-3) Hydrogenated polybutadiene-polystyrene- (1) -hydrogenated polybutadiene-polystyrene (2) hydrogenated block copolymer having a B-A-B-A type structure was synthesized by the method described above. The obtained hydrogenated block copolymer was designated as (c-3). The physical properties of (c-3) were as follows.
Bonded styrene content: 13%
1,2-vinyl bond content in polybutadiene block: 73%
Number average molecular weight of hydrogenated block copolymer: 96000
Number average molecular weight of polystyrene block (1): 6000
Number average molecular weight of polystyrene block (2): 5520
Polybutadiene block hydrogenation rate: 99.9%
(C-4) Hydrogenated polybutadiene-polystyrene- (1) -hydrogenated polybutadiene-polystyrene (2) hydrogenated block copolymer having a B-A-B-A type structure was synthesized by the method described above. The obtained hydrogenated block copolymer was designated as (c-4). The physical properties of (c-4) were as follows.
Bonded styrene content: 25%
1,2-vinyl bond content in polybutadiene block: 36%
Number average molecular weight of hydrogenated block copolymer: 91000
Number average molecular weight of polystyrene block (1): 10800
Number average molecular weight of polystyrene block (2): 11950
Polybutadiene block hydrogenation rate: 99.9%
[Examples 1 to 6 and Comparative Examples 1 to 5]
The resin composition was manufactured as follows using the twin-screw extruder (Coperion company make, ZSK-25). In the twin-screw extruder, the first raw material supply port is provided on the upstream side with respect to the flow direction of the raw material, and the vacuum vent is provided downstream thereof. The above-described extruders (a) to (c) are introduced into the extruder set as described above with the composition shown in Table 1, and melted under conditions of an extrusion temperature of 230 to 320 ° C., a screw rotation speed of 300 rpm, and a discharge rate of 15 kg / hour. The resin composition was kneaded to obtain pellets. The physical properties of the obtained resin composition were measured and evaluated as follows. The results are shown in Table 1.
<Flowability MFR>
Based on JIS K7210, the measurement was performed at 250 ° C. and a load of 10 kg.
<Judgment criteria for suppression of scents>
During the production of the above pellets, extrusion was continued for 30 minutes each, and the amount of sag generated at the die mouth was observed. The following criteria were used to determine the suppression of the meander, and the results are shown in Table 1.
◯: There was no occurrence of mess at all for 30 minutes.
(Triangle | delta): Generation | occurrence | production of mayani was recognized slightly in 30 minutes.
X: Many occurrences of scouring were observed during 30 minutes.
<Presence / absence of delamination>
The pellets obtained above are supplied to a screw in-line injection molding machine set at 240 to 280 ° C. and injection molded under the conditions of a mold temperature of 60 ° C. Width = 150 mm × 20 mm, test part: thickness × width × length = 4 mm × 10 mm × 80 mm). The constricted part of the test piece for tensile test was cut with pruning scissors, the fracture surface was visually observed, and judged according to the following criteria. (N number 5)
○: No delamination was observed in all five samples.
Δ: 1 out of 5 layers was peeled off.
X: Two or more layers out of the five layers were peeled off.
<Chopping>
When obtaining pellets of the resin composition, adjust the temperature of the cooled strand bath and the length of the strands so that the resin temperature immediately before entering the strand cutter is 110 to 120 ° C. with a non-contact thermometer. Then, 20 kg of pellets were collected with a strand cutter. The pellets were sieved with a 50-mesh wire mesh, and the powder that passed through the wire mesh was collected, and its weight was measured to obtain the following values.
Chip rate (ppm) = (Weight of powder slipped through (kg)) / (Weight of pellet left in sieve (kg)) × 1,000,000
Furthermore, the small amount of chips was evaluated according to the following criteria.
○: Chip ratio is less than 20 ppm Δ: Chip ratio is 20 ppm or more and less than 500 ppm ×: Chip ratio is 500 ppm or more In the case of pellets with many chips, the feed amount is unstable during injection molding or extrusion molding As a result, the productivity of the molded product is reduced. Therefore, the chip rate is a very important characteristic, and the lower the chip rate, the better.

(Polypropylene / polyphenylene ether resin composition)
[Melting point]
The melting point was measured with a differential scanning calorimeter.
[MFR]
MFR was measured at 230 ° C. and a load of 2.16 kg in accordance with ASTM D1238.
[Manufacture of each component of resin composition]
(A) Polyphenylene ether (a-5): Polyphenylene ether obtained by the same production method as in the above (a-1) was defined as (a-5).
Component amount with molecular weight of 50,000 or more: 12% by mass
Component amount of molecular weight 8,000 or less: 22% by mass
Number average molecular weight: 11000

(A-6): Polyphenylene ether obtained by the same production method as in the above (a-2) was designated as (a-6).
Amount of components having a molecular weight of 50,000 or more: 6% by mass
Component amount of molecular weight 8,000 or less: 12% by mass
Number average molecular weight: 11500

(A-7): Polyphenylene ether obtained by the same production method as in the above (a-3) was designated as (a-7).
Amount of components having a molecular weight of 50,000 or more: 42% by mass
Component amount of molecular weight 8,000 or less: 4% by mass
Number average molecular weight: 24600

(A-8): Polyphenylene ether obtained by the same production method as in the above (a-4) was designated as (a-8).
Component amount with molecular weight of 50,000 or more: 8% by mass
Component amount of molecular weight 8,000 or less: 8% by mass
Number average molecular weight: 12500
(B): Styrene homopolymer (manufactured by PS Japan, PSJ polystyrene 685)

(C) Hydrogenated block copolymer (c-5) Hydrogenated block copolymer having a B-A-B-A structure of hydrogenated polybutadiene-polystyrene (1) -hydrogenated polybutadiene-polystyrene (2) Was synthesized by the method described above. The obtained hydrogenated block copolymer was designated as (c-5). The physical properties of (c-5) were as follows.
Bonded styrene content: 43%
1,2-vinyl bond content in polybutadiene block: 75%
Number average molecular weight of hydrogenated block copolymer: 97000
Number average molecular weight of polystyrene block (1): 22000
Number average molecular weight of polystyrene block (2): 20000
Polybutadiene block hydrogenation rate: 99.9%

(C-6) A hydrogenated block copolymer having an ABA type structure of polystyrene (1) -hydrogenated polybutadiene-polystyrene (2) was synthesized by the method described above. The resulting hydrogenated block copolymer was designated as (c-6). The physical properties of (c-6) were as follows.
Bonded styrene content: 28%
1,2-vinyl bond content in polybutadiene block: 28%
Number average molecular weight of hydrogenated block copolymer: 110000
Number average molecular weight of polystyrene block (1): 15000
Number average molecular weight of polystyrene block (2): 15800
Polybutadiene block hydrogenation rate: 99.9%

(C-7) A hydrogenated block copolymer having an ABA type structure of polystyrene (1) -hydrogenated polybutadiene-polystyrene (2) was synthesized by the method described above. The resulting hydrogenated block copolymer was designated as (c-7). The physical properties of (c-7) were as follows.
Bonded styrene content: 42%
1,2-vinyl bond content in polybutadiene block: 65%
Number average molecular weight of hydrogenated block copolymer: 980000
Number average molecular weight of polystyrene block (1): 21000
Number average molecular weight of polystyrene block (2): 20000
Polybutadiene block hydrogenation rate: 99.9%

(C-8) A hydrogenated block copolymer having an ABA type structure of polystyrene (1) -hydrogenated polybutadiene-polystyrene (2) was synthesized by the method described above. The resulting hydrogenated block copolymer was designated as (c-8). The physical properties of (c-8) were as follows.
Bonded styrene content: 12%
1,2-vinyl bond content in polybutadiene block: 73%
Number average molecular weight of hydrogenated block copolymer: 96000
Number average molecular weight of polystyrene block (1): 6000
Number average molecular weight of polystyrene block (2): 5520
Polybutadiene block hydrogenation rate: 99.9%

  (D) Homo-polypropylene Melting point = 167 ° C., MFR = 0.5

(E) Polystyrene (1) -hydrogenated polybutadiene-polystyrene (2) hydrogenated block copolymer having an ABA type structure was synthesized by the method described above. The physical properties of the obtained hydrogenated block copolymer (e) are as follows.
Bonded styrene content: 60%
1,2-vinyl bond content in polybutadiene block: 35%
Number average molecular weight of hydrogenated block copolymer: 108,000
Number average molecular weight of polystyrene block (1): 33000
Number average molecular weight of polystyrene block (2): 31800
Hydrogenation rate of polybutadiene block: 99.9%

  (F): Talc with an average particle diameter of 11 microns (PK-C, Hayashi Kasei Co., Ltd.)

[Examples 7 to 13 and Comparative Examples 6 to 12]
Using a twin-screw extruder (manufactured by Coperion, ZSK-25), first to third raw material supply ports are provided in order from the upstream side with respect to the flow direction of the raw material, and the components (a) to (f) are represented. 2 was melt-kneaded with the composition shown in Fig. 2 to obtain a thermoplastic resin composition as pellets. The twin-screw extruder was set at a barrel temperature of 240 to 320 ° C., a screw rotation speed of 300 rpm, and a discharge rate of 15 kg / hour. Each physical property of the obtained thermoplastic resin composition was evaluated as follows. The measurement results are shown in Table 2.
<MFR>
According to ISO1133, the measurement was performed at a load of 10 kg at 250 ° C.
<Thin wall formability>
Using the pellets of the thermoplastic resin compositions of Examples and Comparative Examples obtained as described above, the pellets were supplied to a screw in-line injection molding machine set at 250 ° C., and the mold temperature was 60 ° C. A test piece having a thickness of 127 mm, a width of 12.7 mm, and a thickness of 0.4 mm was formed. The minimum injection pressure required for filling in the mold was measured to determine the thin-wall formability (unit: MPa (gauge pressure)). The smaller the required minimum injection pressure, the better the thin moldability.
<Tensile test>
Using the pellets of the thermoplastic resin compositions of Examples and Comparative Examples obtained as described above, the pellets were supplied to a screw in-line injection molding machine set at 240 to 280 ° C., and under a mold temperature of 60 ° C., Test specimens for tensile test measurement were injection molded. About the test piece for this tensile test measurement, it left still in an 80 degreeC environment for 24 hours using the gear oven, and performed the heat history process. Using the test specimen for tensile test measurement after the heat history treatment, the tensile test was performed according to ISO 527, and the tensile strength and the tensile elongation were measured.
<Bending elastic modulus>
Using the pellets of the thermoplastic resin compositions of Examples and Comparative Examples obtained as described above, the pellets were supplied to a screw in-line injection molding machine set at 240 to 280 ° C., and under a mold temperature of 60 ° C., A test piece for measuring the flexural modulus was injection molded. About the test piece for measuring the flexural modulus, using a gear oven, the test piece was left to stand in an environment of 80 ° C. for 24 hours to perform a heat history treatment. Using the test piece for measuring the flexural modulus after the heat history treatment, the flexural modulus was measured according to ISO178.
<Rigidity>
The resin pellets of the thermoplastic resin compositions of Examples and Comparative Examples obtained as described above were supplied to a screw in-line type injection molding machine set at 240 to 280 ° C., and the mold temperature was 60 ° C. A box-shaped molded product of 100 mm × width 75 mm × height 42 mm was molded. The both ends of the molded product were held, and the feeling of rigidity when bending deformation was applied was evaluated. The evaluation was performed according to the following criteria based on the amount of displacement (mm) at both ends with respect to the center of the molded product when bending deformation was applied.
○: Displacement amount 0 to less than 5 mm, Δ: Displacement amount 5 to less than 10 mm, ×: Displacement amount 10 mm or more

  The resin composition of the present invention can be used in a wide range of fields such as electric / electronic parts, OA parts, vehicle parts, and machine parts, and in particular, can be suitably used for automobile parts. Among these, it can be preferably used for an engine cover or the like that requires fluidity and rigidity.

Claims (15)

(A) polyphenylene ether,
A block copolymer comprising (b) polystyrene, and (c) at least two polymer blocks A mainly composed of a vinyl aromatic compound and at least one polymer block B mainly composed of a conjugated diene compound. A resin composition comprising a hydrogenated block copolymer formed by adding,
The (a) polyphenylene ether contains 5 to 20% by mass of a component having a molecular weight of 50,000 or more and 12 to 30% by mass of a component having a molecular weight of 8,000 or less with respect to the whole polyphenylene ether. Including
The number average molecular weight (Mnc) of the (c) hydrogenated block copolymer is 100,000 or less,
The number average molecular weight (MncA) of the polymer block A in the (c) hydrogenated block copolymer is 8,000 or more,
The content of the component (a) is 50% by mass or more with respect to a total of 100% by mass of the components (a) and (b),
The total content of the components (a) and (b) is 1 to 99% by mass with respect to a total of 100% by mass of the components (a) to (c), and the content of the component (c) is The resin composition which is 99-1 mass%.   The resin composition according to claim 1, wherein the content of the bonded vinyl aromatic compound in the (c) hydrogenated block copolymer is 15 to 50% by mass with respect to the total component (c).   (C) All conjugated diene compounds in which the total amount of conjugated diene compounds bonded by 1,2-vinyl bonds or 3,4-vinyl bonds in the hydrogenated block copolymer constitutes the polymer block B The resin composition according to claim 1, wherein the resin composition is 70 to 90% by mass relative to the mass.   Use of the resin composition which improves the heat resistance of a polypropylene by adding the resin composition of any one of Claims 1-3 to a polypropylene.   Furthermore, (d) polypropylene is included, Content of this (d) component is 1-95 mass% with respect to 100 mass% of total amounts of (a)-(d) component, The Claims 1-3 The resin composition according to any one of the above.   The resin composition according to claim 5, wherein the melting point of (d) polypropylene is 155 ° C. or higher.   The (d) polypropylene is a homopolypropylene and / or a block polypropylene, and the melt flow rate of the component (d) (MFR: measured at 230 ° C. under a load of 2.16 kg in accordance with ASTM D1238) is 0.1 to 0.1. The resin composition according to claim 5 or 6, which is 100 g / 10 minutes.   The pellet formed from the resin composition of any one of Claims 1-3. 100 parts by mass of the pellet according to claim 8;
Vinyl aromatic compound polymer, vinyl aromatic compound copolymer, polypropylene, polyethylene, ethylene-α-olefin copolymer, polyamide 6, polyamide 66, polyamide 66/6, polycarbonate, polyacetal, polyethylene terephthalate, polybutylene terephthalate, One or more thermoplastic resins selected from the group consisting of polytrimethylene terephthalate, aromatic ring-containing polyamide, aliphatic ring-containing polyamide, polyphenylene sulfide, liquid crystal polymer, polyether ether ketone, polyarylate, polyether sulfone, and polysulfone The manufacturing method of a thermoplastic resin composition including the process of melt-mixing 10-1000 mass parts.   The method for producing a thermoplastic resin composition according to claim 9, wherein the thermoplastic resin is polypropylene.   The method for producing a thermoplastic resin composition according to claim 9 or 10, wherein the melt-mixing step is performed by an extruder or an injection molding machine.   A thermoplastic resin composition obtained by the production method according to claim 11.   The molded object obtained by shape | molding the thermoplastic resin composition of Claim 12.   The molded object obtained by shape | molding the resin composition of any one of Claims 1-3 or Claims 5-7. The molded article according to claim 13 or 14, wherein the molded article is at least one selected from the group consisting of the following (1) to (4).
(1) Sheet / film or stretched sheet / film (2) Automotive exterior / outboard parts, automotive interior parts, or automotive underhood parts (3) Electric wires / cables obtained by coating a resin composition on a metal conductor or optical fiber (4) Ink peripheral parts / members or chassis of ink jet printer