JP2010229348A - Resin composition and molding thereof - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a resin composition including a polypropylene resin as a matrix and a polyphenylene ether resin as a disperse phase, the resin composition being excellent in processability, heat resistance, mechanical properties, and thermal stability of dispersed particles. <P>SOLUTION: The resin composition is prepared by focusing on the emulsification dispersion of a polymer alloy including a polypropylene resin as a matrix and a polyphenylene ether resin as a disperse phase and selecting a polyphenylene ether having a specific molecular weight and a hydrogenated block copolymer having a specific molecular weight and structure. <P>COPYRIGHT: (C)2011,JPO&INPIT

Description

  The resin composition is a polymer alloy that exhibits a thermally stable morphology in the dispersed phase, has an excellent balance of heat resistance, mechanical strength, and moldability, and is used in the electrical / electronic field, automotive field, and other various industrial material fields. It is related with the resin composition which can be performed. Taking advantage of this feature, the battery case (container) for secondary batteries, lithium-ion battery separators, other sheets / films or stretched sheets / films, automotive interior materials, automotive exterior materials, bumpers as automotive exterior materials, low Bumper stiffener, under hood parts, fuel tank protector, housing to protect electrical connectors, fender, instrument panel module, instrument panel upper lid, door module, cockpit module, front end module, deck board, Obtained by coating side step, door handle base, rear lamp housing, console box, trunk board, trim, roof sheet, etc., metal conductor or optical fiber Suitable as a molding material for electric wires and cables, fuel cases for solid methanol batteries, fuel cell water pipes and their fittings, water cooling tanks, boiler exterior cases, ink printer printer parts and components, chassis, water pipes and fittings, etc. The present invention relates to a resin composition that can be used.

Although polypropylene has excellent properties such as moldability, water resistance, oil resistance, acid resistance, alkali resistance, etc., it has drawbacks inferior in heat resistance, rigidity and impact resistance. It is known that a resin composition in which polypropylene is formed as a matrix and polyphenylene ether is used as an organic filler to form dispersed particles is a resin composition with improved heat resistance and rigidity.
However, since this known resin composition contains polyphenylene ether having poor fluidity, processability is inevitably deteriorated. For this reason, it is obvious that the processability of the resulting composition can be expected by reducing the molecular weight of the polyphenylene ether, which is the fluidity factor of the polyphenylene ether to be provided, but using a polyphenylene ether having a reduced molecular weight. From the viewpoints of mechanical properties, heat resistance, and thermal morphology stability of the polyphenylene ether in the dispersed phase, an admixture that emulsifies and disperses the polyphenylene ether in the dispersed phase and the polyphenylene ether in the dispersed phase. As for the optimal structure factor of a certain hydrogenated block copolymer, it is the actual condition that is not technically clear at all.

  As a prior art of a resin composition using polyphenylene ether, a resin composition having improved heat resistance and rigidity comprising a polyphenylene ether having an intrinsic viscosity lower than 0.30 dl / g, polypropylene and a hydrogenated block copolymer (patented) Document 1 and Patent Document 2) are proposed, and a resin composition comprising a polyphenylene ether having a reduced viscosity of 0.31 g / dl as a low molecular weight polyphenylene ether, a polyolefin and a hydrogenated block copolymer (Patent Document 3, Patent Document 5, Patent Document 6, Patent Document 7, and Patent Document 8) are described in Examples of these documents. A resin composition (Patent Document 4) comprising a polyphenylene ether, a polyolefin and a hydrogenated block copolymer, in which the weight average molecular weight and the low molecular weight component amount and the high molecular weight component amount of the molecular weight distribution are defined, is proposed. In Examples, a resin composition composed of polyphenylene ether having a weight average molecular weight of 20000, a hydrogenated block copolymer, and low-density polyethylene is proposed. Furthermore, resin compositions (Patent Document 9 and Patent Document 10) composed of polyphenylene ether having an intrinsic viscosity exceeding 0.25 dl / g, a specific hydrogenated block copolymer, and polyolefin have been proposed.

Japanese Patent Laid-Open No. 02-113060 US Pat. No. 5,262,480 Japanese Patent Laid-Open No. 06-57130 Japanese Patent Laid-Open No. 06-192561 International Publication No. 97/01600 Pamphlet Japanese Patent Laid-Open No. 09-12799 JP 09-12804 A JP 09-87450 A Special table 2008-524379 Special Table 2008-52481

These prior arts include a resin composition comprising a polyphenylene ether having a molecular weight in a wide range of low to high molecular weight expressed by intrinsic viscosity, intrinsic viscosity, and weight average molecular weight, a polyolefin, and a hydrogenated block copolymer as an admixture. Although a product is disclosed, it is not sufficient from the viewpoint of processability, heat resistance, mechanical properties and morphological stability of the obtained resin composition.
In other words, the processability, heat resistance, and mechanical properties of a polymer alloy in which polyphenylene ether incompatible with this is emulsified and dispersed in polypropylene are insufficient because of the selection of individual materials to be used for the polymer alloy. Due to being sufficient.

In general, in order to emulsify and disperse polyphenylene ether in polypropylene, it is known that a hydrogenated block copolymer is essential as an emulsifying dispersant (admixture).
However, the polymer alloy performance showing this emulsified dispersion structure is complemented by the structure of the polyphenylene ether emulsified in polypropylene to form the dispersed phase and the structure of the hydrogenated block copolymer of the emulsifying dispersant (admixture). Although it is dominated by the emulsification and dispersion technology, there are no technical suggestions or disclosures that clarify the interrelationship between the polyphenylene ether structure and the hydrogenated block copolymer structure, which are the control factors for emulsification and dispersion. is there.
An object of the present invention is to provide a resin composition which is excellent in processability, heat resistance and mechanical properties, and further shows a thermally stable dispersion form of polyphenylene ether which forms a dispersed phase as an incompatible polymer alloy. In addition, optimization of the molecular weight of the polyphenylene ether and optimization of the polymer structure factor of the hydrogenated block copolymer used as an emulsifying dispersant (admixture) for the optimized molecular weight of the polyphenylene ether is a problem. .

  In view of the current situation, in the design of polymer alloys composed of polypropylene / polyphenylene ether, the first step is to study diligently regarding (1) heat resistance and (2) processability, which are the manifestation effects of organic fillers as polyphenylene ether. Again, from these two characteristics, it was found that polyphenylene ether having a specific range of molecular weight and molecular weight distribution is preferable. In the second step, whether or not the polyphenylene ether having the molecular weight in the specific range found in the first step exhibits a thermally stable emulsified dispersion form in polypropylene, and the processability, heat resistance, As a result of intensive studies on mechanical properties, the hydrogenated block copolymer, which is an emulsifying dispersant (admixture) to be provided, has excellent processability, heat resistance and mechanical properties by controlling it to a specific structure. It has been found that polyphenylene ether forming a dispersed phase as a compatible polymer alloy results in a resin composition exhibiting a thermally stable dispersion form.

That is,
[1] (a) Polypropylene resin 25-99 mass%, (b) The weight average molecular weight (Mwppe) measured by polystyrene conversion using the gel permeation chromatography (GPC) of a chloroform solvent is 15000-25000, and In addition, at least 2 mainly composed of styrene per 100 parts by mass in total of the components (a) and (b) consisting of 75 to 1% by mass of a polyphenylene ether resin having a molecular weight distribution (Mwppe / Mnppe) of 1.5 to 3.0 It is obtained by hydrogenating a block copolymer comprising one polymer block A and at least one polymer block B mainly composed of butadiene having a 1,2-vinyl bond content of 70 to 90%. Hydrogenated block copolymer (c) A resin composition comprising 1 to 20 parts by mass of the hydrogenated block copolymer The amount of styrene bonded to the polymer (c) by (c-1) is 15 to 50% by mass,
(C-2) The number average molecular weight (Mnc) and the number average molecular weight (MncA) of the polymer block A mainly composed of styrene are measured in terms of polystyrene using gel permeation chromatography (GPC) in a chloroform solvent. Mnc ≦ 100,000, MncA ≧ 8000
A resin composition.

[2] (a) Polypropylene resin 25-99 mass%, (b) The weight average molecular weight (Mwppe) measured by polystyrene conversion using the gel permeation chromatography (GPC) of a chloroform solvent is 15000-25000, and In addition, at least 2 mainly composed of styrene per 100 parts by mass in total of the components (a) and (b) consisting of 75 to 1% by mass of a polyphenylene ether resin having a molecular weight distribution (Mwppe / Mnppe) of 1.5 to 3.0 It is obtained by hydrogenating a block copolymer comprising one polymer block A and at least one polymer block B mainly composed of butadiene having a 1,2-vinyl bond content of 70 to 90%. A hydrogenated block copolymer (c) and at least two polymer blocks A mainly composed of styrene; Hydrogenated block copolymer obtained by hydrogenating a block copolymer composed of at least one polymer block B mainly composed of butadiene having a 1,2-vinyl bond content of diene of less than 25 to 70% ( d) (c) Hydrogenated block copolymer / (d) Hydrogenated block copolymer = 1 to 99% by mass / 99 to 1% by mass of two hydrogenated block copolymers 1 to 20% by mass The hydrogenated block copolymer (c) is a resin composition comprising parts,
(C-1) The amount of bound styrene is 15 to 50% by mass,
(C-2) The number average molecular weight (Mnc) and the number average molecular weight (MncA) of the polymer block A mainly composed of styrene are measured in terms of polystyrene using gel permeation chromatography (GPC) in a chloroform solvent. Mnc ≦ 100,000, MncA ≧ 8000
And the hydrogenated block copolymer (d) is
(D-1) The amount of bound styrene is more than 50 to 70% by mass.
(D-2) The number average molecular weight (Mnd) and the number average molecular weight (MndA) of the polymer block A mainly composed of styrene are measured in terms of polystyrene using gel permeation chromatography (GPC) of a chloroform solvent. Mnd ≦ 150,000, MndA ≧ 8000
A resin composition.

[3] (a) Polypropylene resin 25-99 mass%, (b) Weight average molecular weight (Mwppe) measured by polystyrene conversion using gel permeation chromatography (GPC) of chloroform solvent is 15000-25000, and Polyphenylene ether resin having a molecular weight distribution (Mwppe / Mnppe) of 1.5 to 3.0 At least two polyphenylene ether resins consisting mainly of styrene per 100 parts by mass of the total of (a) and (b) components Water obtained by hydrogenating a block copolymer consisting of a polymer block A of butadiene and at least one polymer block B mainly composed of butadiene having a 1,2-vinyl bond content of 70 to 90% A block copolymer (c), at least two polymer blocks A mainly composed of styrene, and pig Hydrogenated block copolymer obtained by hydrogenating a block copolymer composed of at least one polymer block B mainly composed of butadiene having an ene 1,2-vinyl bond content of less than 25 to 70% ( e) (c) Hydrogenated block copolymer / (e) Hydrogenated block copolymer = 1 to 99% by mass / 99 to 1% by mass of two hydrogenated block copolymers 1 to 20% by mass The hydrogenated block copolymer (c) is a resin composition comprising parts,
(C-1) The amount of bound styrene is 15 to 50% by mass,
(C-2) The number average molecular weight (Mnc) and the number average molecular weight (MncA) of the polymer block A mainly composed of styrene are measured in terms of polystyrene using gel permeation chromatography (GPC) in a chloroform solvent. Mnc ≦ 100,000, MncA ≧ 8000
And the hydrogenated block copolymer (e) is
(E-1) The amount of styrene bound is 15 to 50% by mass,
(E-2) Number average molecular weight (Mne) and number average molecular weight (MneA) of polymer block A mainly composed of styrene are measured in terms of polystyrene using gel permeation chromatography (GPC) in a chloroform solvent. Mne ≦ 100,000, MneA ≧ 8000
A resin composition.

[4] (a) Polypropylene resin 25-99 mass%, (b) Weight average molecular weight (Mwppe) measured in polystyrene conversion using gel permeation chromatography (GPC) of chloroform solvent is 15000-25000, and Polyphenylene ether resin having a molecular weight distribution (Mwppe / Mnppe) of 1.5 to 3.0 At least two polyphenylene ether resins consisting mainly of styrene per 100 parts by mass of the total of (a) and (b) components Water obtained by hydrogenating a block copolymer consisting of a polymer block A of butadiene and at least one polymer block B mainly composed of butadiene having a 1,2-vinyl bond content of 70 to 90% Added block copolymer (c), at least two polymer blocks A mainly composed of styrene, and butadiene Hydrogenated block copolymer (d) obtained by hydrogenating a block copolymer comprising at least one polymer block B mainly composed of butadiene having a 1,2-vinyl bond content of less than 25 to 70%. , And at least two polymer blocks A mainly composed of styrene, and at least one polymer block B mainly composed of butadiene in which the amount of 1,2-vinyl bonds of butadiene is less than 25 to 70%. The hydrogenated block copolymer (e) obtained by hydrogenating the copolymer is converted into (c) hydrogenated block copolymer / (d) hydrogenated block copolymer / (e) hydrogenated block copolymer = A resin composition comprising 1 to 20 parts by mass of three types of hydrogenated block copolymers at a ratio of 1 to 98% by mass / 98 to 1% by mass / 1 to 98% by mass, The polymer (c) is
(C-1) The amount of bound styrene is 15 to 50% by mass,
(C-2) The average molecular weight (Mnc) and the number average molecular weight (MncA) of the polymer block A mainly composed of styrene were measured in terms of polystyrene using gel permeation chromatography (GPC) in a chloroform solvent. , Mnc ≦ 100,000, MncA ≧ 8000
And the hydrogenated block copolymer (d) is
(D-1) The amount of bound styrene is more than 50 to 70% by mass.
(D-2) The number average molecular weight (Mnd) and the number average molecular weight (MndA) of the polymer block A mainly composed of styrene are measured in terms of polystyrene using gel permeation chromatography (GPC) of a chloroform solvent. Mnd ≦ 150,000, MndA ≧ 8000
And the hydrogenated block copolymer (e) is
(E-1) The amount of styrene bound is 15 to 50% by mass,
(E-2) The average molecular weight (Mne) and the number average molecular weight (MneA) of the polymer block A mainly composed of styrene are measured in terms of polystyrene using gel permeation chromatography (GPC) in a chloroform solvent. , Mne ≦ 100,000, MneA ≧ 8000
A resin composition.

[5] Resin in which the hydrogenated block copolymer (c) according to any one of the above [1] to [4] is a hydrogenated block copolymer having a block structure of ABAB Composition.
[6] The resin composition as described in any one of [1] to [5] above, containing 25 to 45% by mass of styrene bonded with the hydrogenated block copolymer (c).
[7] The resin composition as described in any one of [2] to [6] above, containing 51 to 70% by mass of styrene bonded with the hydrogenated block copolymer (d).
[8] The resin composition according to any one of the above [3] to [7], which contains 25 to 45% by mass of styrene bonded with the hydrogenated block copolymer (e).
[9] (a) The resin composition according to any one of [1] to [8], wherein the polypropylene resin has a melting point of 155 ° C. or higher.
[10] (a) The polypropylene resin is homopolypropylene and / or block polypropylene, and has a melt flow rate (measured in accordance with MFR: ASTM D1238 at 230 ° C. under a load of 2.16 Kg) of 0.1 to 100 g / 10. The resin composition according to any one of [1] to [9], which is a minute.

[11] The resin composition according to any one of [1] to [10], wherein (f) 0.1 to 300 parts by mass of a filler is contained per 100 parts by mass of the component (a) to the component (b). .
[12] The filler of component (f) is an inorganic salt, glass fiber (long glass fiber, chopped strand glass fiber), cellulose, glass flake, glass bead, long carbon fiber, chopped strand carbon fiber, whisker, mica, clay, Talc, magnesium hydroxide, magnesium sulfate and its fibers, silica, carbon black, titanium oxide, calcium carbonate, potassium titanate, wollastonite, thermal conductive materials (graphite, aluminum nitride, boron nitride, alumina, beryllium oxide, dioxide Silicon, magnesium oxide, aluminum nitrate, barium sulfate), conductive metal fibers, conductive metal flakes, carbon black indicating conductivity, carbon fibers indicating conductivity, and carbon nanotubes. The resin composition according to the above [11], wherein both are one kind.

[13] The resin composition according to any one of [1] to [12] above is further provided with a stabilizer, a release agent, a processing aid, a flame retardant, a drip inhibitor, a nucleating agent, and a UV blocking agent. A resin composition containing at least one additive selected from an agent, a dye, a pigment, an antioxidant, a plasticizer, and an antistatic agent.
[14] A secondary battery case obtained by molding the resin composition according to any one of [1] to [13].
[15] A lithium ion battery separator obtained by film-forming the resin composition according to any one of [1] to [13].
[16] A sheet film or a stretched sheet film obtained by molding the resin composition according to any one of [1] to [13]

[17] An automobile mechanism part, an automobile exterior product, or an automobile interior product obtained by molding the resin composition according to any one of [1] to [13].
[18] Automotive mechanism parts are air conditioner housing, heater housing, ducts, fuel tank protector, connector housing, fuel filter housing, fuel filter cap, cooling fan, fan shroud, timing belt cover, oil tank, oil tank cap, radiator tank [14] The automobile mechanism part according to [17], which is any one selected from undercovers.

[19] Automotive exterior products include bumpers, bumper beams, low bumper stiffeners, side spoilers, front grilles, rear garnishes, door outer handles, pillar covers, door mirror bodies, mat guards, splash boards, The automobile exterior product according to [17], which is any one selected from a cowl panel, a wheel cap, a clip, a fastener, and a lamp housing.
[20] Automotive interior parts include instrument panels, door trim panels, console boxes, pillar trims, differential grills, meter-related parts, visor cases, covers, rearview mirror bodies, seat bags, headrest guides, seat hinge covers, seat belts, [17] The automobile interior part according to [17], which is any one selected from a trunk room cover box, a steering wheel, a horn cover, a shift lever, a shift lever knob, and a pedal.

[21] An electric wire / cable obtained by coating the resin composition according to any one of [1] to [13] on a metal conductor or an optical fiber.
[22] A solid methanol battery fuel case, a fuel cell water pipe, or a joint thereof obtained by molding the resin composition according to any one of [1] to [13].
[23] A water cooling tank obtained by molding the resin composition according to any one of [1] to [13].
[24] A boiler outer case obtained by molding the resin composition according to any one of [1] to [13].
[25] A component / member or chassis around the ink of an ink jet printer obtained by molding the resin composition according to any one of [1] to [13].
[26] The present invention relates to a water pipe or a joint obtained by molding the resin composition according to any one of [1] to [13].

  The resin composition is a polymer alloy obtained by emulsifying and dispersing a polyphenylene ether having a matrix composed of a polypropylene resin and a dispersed phase having a specific molecular weight and a hydrogenated block copolymer having a specific polymer structure. The molecular weight of the hydrogenated block copolymer, which is an emulsifying dispersant (admixture), relative to the molecular weight of the polyphenylene ether and the polystyrene molecular weight thereof are controlled, and the butadiene of the polybutadiene chain before hydrogenation of the hydrogenated block copolymer is further controlled. By controlling the bonding form, polyphenylene ether that forms a dispersed phase as an incompatible polymer alloy is excellent in processability, heat resistance, and mechanical properties, and provides a resin composition that exhibits a thermally stable dispersed form. .

This will be specifically described below.
That is, as one of the techniques for improving the heat resistance of polypropylene resin, there is a technique for blending an amorphous thermoplastic resin having high heat resistance as an organic filler, and in particular, polypropylene has a high glass transition temperature (about 210 ° C. ) Compositions containing polyphenylene ether are well known. However, polypropylene and polyphenylene ether are incompatible, and it is very difficult to disperse the polyphenylene ether resin in the matrix of the polypropylene resin. Even if the dispersion technique is successful, the polyphenylene ether has high heat resistance. Degradation of workability due to the incorporation of, is an important problem that is very difficult to avoid and is not achieved by the prior art.

In a composition comprising a polypropylene resin / polyphenylene ether resin / hydrogenated block copolymer, a polyphenylene ether controlled to a specific molecular weight maintaining heat resistance and a hydrogenated block copolymer having a specific molecular structure with respect to the polyphenylene ether By providing the coalescence, the polyphenylene ether forming the processability, heat resistance, mechanical properties and dispersed phase gives a thermally stable dispersion form.
The component (a) polypropylene resin that forms the matrix of the resin composition is composed of a crystalline propylene homopolymer, a crystalline propylene homopolymer portion obtained in the first step of polymerization, and propylene, ethylene, and the second and subsequent steps of polymerization. A crystalline propylene-ethylene block copolymer having a propylene-ethylene random copolymer portion obtained by copolymerizing at least one other α-olefin (for example, butene-1, hexene-1, etc.) Further, it may be a mixture of these crystalline propylene homopolymer and crystalline propylene-ethylene block copolymer.

Such a polypropylene resin is usually used in the presence of a titanium trichloride catalyst or a titanium halide catalyst supported on a carrier such as magnesium chloride and an alkylaluminum compound in a polymerization temperature range of 0 to 100 ° C. and a polymerization pressure of 3 to 100 atm. It is obtained by polymerization in the range of At this time, a chain transfer agent such as hydrogen can be added to adjust the molecular weight of the polymer, and the polymerization method can be either a batch type or a continuous type, butane, pentane, hexane, heptane. Further, methods such as solution polymerization in a solvent such as octane and slurry polymerization can also be selected. Furthermore, bulk polymerization in a monomer in the absence of a solvent, gas phase polymerization method in a gaseous monomer, and the like can be applied.
Furthermore, in addition to the polymerization catalyst described above, 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 polypropylene obtained.

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.
The polypropylene resin to be provided is obtained by the above-described method, and the polymer is characterized in that the homo-polypropylene portion has a crystalline melting point of 155 ° C. or higher, a crystallization temperature of 100 ° C. to 130 ° C., and a melt flow rate of 0. 0.1 to 100 g / 10 min polypropylene resin.

  The crystal melting point of this homo-polypropylene part is a melting point value measured with 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. is there. 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. is not preferable because the resulting resin composition has low rigidity and heat resistance (load deflection temperature: DTUL). A preferable polypropylene is a polypropylene having a homo-polypropylene portion having a crystal melting point of 163 ° C. or more, and gives a resin composition excellent in rigidity and heat resistance (load deflection temperature: DTUL). In addition, at the time of crystal melting point measurement by this differential scanning calorimeter (DSC), the crystallization temperature (solidification temperature) peak of molten polypropylene can be known, and the crystallization temperature of polypropylene can be confirmed at 100 to 130 ° C.

The polypropylene resin can usually be selected from the range of 0.1 to 100 g / 10 min in melt flow rate (MFR: measured at 230 ° C. under a load of 2.16 kg in accordance with ASTM D1238). In order to develop heat resistant creep resistance, it is important to select a polypropylene resin having a melt flow rate in the range of 0.1 to 2 g / 10 min. Moreover, when importance is attached to the workability of the composition obtained, a polypropylene resin having a melt flow rate of 10 g / 10 min or more can be selected.
In addition to the above-described polypropylene resin, the polypropylene resin is 30 to 30% in a molten state or a solution state in the presence or absence of a radical generator, and the polypropylene resin and an α, β-unsaturated carboxylic acid or a derivative thereof. Known modified (obtained by grafting or addition of 0.01 to 10% by mass of the α, β-unsaturated carboxylic acid or derivative thereof) polypropylene resin obtained by reacting at a temperature of 350 ° C. may be a polypropylene resin. It may be a mixture of any ratio of the prepared polypropylene resin and the modified polypropylene resin.

  Next, the polyphenylene ether resin of component (b) that forms dispersed particles of the resin composition is an essential component for imparting heat resistance (load deflection temperature: DTUL) and flame retardancy in the resin composition, Having a repeating unit represented by a bond unit of the following formula (1), having a weight average molecular weight (Mwppe) measured in terms of polystyrene using gel permeation chromatography (GPC) of a chloroform solvent, 15000 to 25000, and It is a homopolymer and / or copolymer polyphenylene ether resin (hereinafter abbreviated as PPE) having a molecular weight distribution (weight average molecular weight Mwppe / number average molecular weight Mnppe) in the range of 1.5 to 3.0. The position where the weight average molecular weight (Mwppe) of PPE as the component (b) is selected as 15000 to 25000 is such that the glass transition temperature is as high as about 200 ° C. and the fluidity is lower than that of polyphenylene ether generally used. This is due to the excellent fluidity. The polyphenylene ether generally used here has a weight average molecular weight of 35,000 to 50,000 and a molecular weight distribution of 2 to 3.

(Wherein R1, R2, R3 and R4 in the formula are each hydrogen, halogen, primary or secondary lower alkyl group having 1 to 7 carbon atoms, phenyl group, haloalkyl group, aminoalkyl group, A hydrocarbonoxy group or a halohydrocarbonoxy group in which at least two carbon atoms separate a halogen atom and an oxygen atom, and may be the same or different from each other)

  The molecular weight and molecular weight distribution of PPE were measured by Showa Denko KK 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 / liter of PPE / chloroform solution) and standard polystyrene (the molecular weight of standard polystyrene is 3650000, 217000, 1090000, 681000, 204000, 52000, 30200, 13800, 3360) 1300, 550) to create and measure a calibration curve. The UV (ultraviolet) wavelength of the detection unit is set to 254 nm for standard polystyrene and 283 nm for PPE.

  Specific examples of the PPE include poly (2,6-dimethyl-1,4-phenylene ether), poly (2-methyl-6-ethyl-1,4-phenylene ether), and poly (2-methyl ether). -6-phenyl-1,4-phenylene ether), poly (2,6-dichloro-1,4-phenylene ether) and the like, and 2,6-dimethylphenol and other phenols (for example, 2,6- Polyphenylene ether copolymers such as copolymers with 3,6-trimethylphenol and 2-methyl-6-butylphenol) may also be mentioned. Of these, poly (2,6-dimethyl-1,4-phenylene ether) and a copolymer of 2,6-dimethylphenol and 2,3,6-trimethylphenol are preferable, and poly (2,6-dimethyl-1 , 4-phenylene ether).

  The method for producing such PPE is not particularly limited as long as it can be obtained by a known method. For example, a complex of cuprous salt and amine by Hay described in US Pat. No. 3,306,874 is used as a catalyst, for example, 2 , 6-xylenol can be easily produced by oxidative polymerization. In addition, U.S. Pat. Nos. 3,306,875, 3,257,357 and 3,257,358, JP-B-52-17880, and JP-A-50-51197 and It can be easily produced by the method described in 63-152628.

  In addition to the above-mentioned PPE, the PPE used in the present invention includes the PPE and a styrenic monomer and / or an α, β-unsaturated carboxylic acid or a derivative thereof (for example, maleic anhydride, N-phenylmaleimide, malic acid). , Saturated or unsaturated dicarboxylic acids such as citric acid and fumaric acid and their derivatives, vinyl compounds such as styrene, acrylic acid esters and methacrylic acid esters, etc.) in the presence or absence of radical generators A known modification obtained by reacting at 80 to 350 ° C. in a state, a solution state or a slurry state (the styrenic monomer and / or α, β-unsaturated carboxylic acid or derivative thereof is 0.01 to 10%). (Mass% grafting or addition) may be PPE, and the above-mentioned PPE and the modified PPE It may be a fraction of a mixture of.

Various known stabilizers can also be suitably used for stabilizing PPE. Examples of the stabilizer include organic stabilizers such as metal stabilizers such as zinc oxide and zinc sulfide, hindered phenol stabilizers, phosphate ester stabilizers, and hindered amine stabilizers.
The preferable compounding quantity of these various stabilizers is less than 5 mass parts with respect to 100 mass parts of the mixture of all the resin components. Among these 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. In order to prevent the discoloration of the pellets due to the oxidation reaction and the like, an antioxidant having both a sulfur element and a hydroxyl group in the molecule is extremely effective.

When using the antioxidant which has a sulfur element and a hydroxyl group simultaneously in a molecule | numerator, the preferable mixing | blending minimum amount is 0.1 mass part with respect to 100 mass parts of all the resin mixtures. More preferably, it is 0.2 parts by mass, and most preferably 0.3 parts by mass. As an upper limit, it is 5 mass parts, More preferably, it is 3 mass parts, Most preferably, it is 2 mass parts.
The preferred blending amount of the antioxidant having both sulfur element and hydroxyl group in the molecule shown here is included in 5 parts by mass which is the upper limit of the preferred blending amount of the above-mentioned various known stabilizers.
Furthermore, you may add the other well-known additive etc. which can be added to PPE in the quantity of less than 10 mass parts with respect to 100 mass parts of PPE.
Furthermore, in addition to the PPE described above, the PPE used in the present invention is within a range not exceeding 500 parts by mass of polystyrene, high impact polystyrene, syndiotactic polystyrene, and rubber-reinforced syndiotactic polystyrene with respect to 100 parts by mass of these PPEs ( Those most preferably added at 200 parts by mass or less can also be suitably used.

The resin composition is a resin composition having a structure in which dispersed particles made of PPE (b) are dispersed in a matrix made of the polypropylene resin (a).
In order to be able to be a resin composition in which PPE is dispersed, naturally, an emulsifying dispersant (hereinafter abbreviated as an admixture) is essential in addition to the polypropylene resin (a) and PPE (b) to be provided. As the agent, a hydrogenated block copolymer (c) is used.
The hydrogenated block copolymer of component (c), which is this admixture, acts as a dispersant for emulsifying and dispersing PPE in the above-described polypropylene resin matrix, and further imparts impact resistance to the resin composition. From at least two polymer blocks A mainly composed of styrene and at least one polymer block B mainly composed of butadiene having a 1,2-vinyl bond content of 70 to 90%. This is a hydrogenated block copolymer (c) obtained by hydrogenating the block copolymer.

  The structure of the hydrogenated block copolymer (c) composed of these blocks is, for example, ABA type, ABAB type, (AB-) nX type (here n represents an integer of 1 or more, and X represents a reaction residue of a polyfunctional coupling agent such as silicon tetrachloride or tin tetrachloride or a residue of an initiator such as a polyfunctional organolithium compound.), AB- It is a hydrogenated product of a styrene-butadiene block copolymer having a structure in which block units such as A-B-A type are bonded. Among them, a hydrogenated block copolymer having a structure of A-B-A-B type is used. Since it is excellent in fluidity | liquidity compared with an ABA type hydrogenated block copolymer, it is more preferable. And the amount of styrene couple | bonded in the hydrogenated block copolymer (c) which shows these block structures contains 15-50 mass%, Preferably it is 25-45 mass%, More preferably, it contains 30-45 mass%. Further, referring to individual block structures, the polymer block A mainly composed of styrene is a homopolymer block of styrene or a copolymer of styrene and butadiene containing styrene in an amount of more than 50% by mass, preferably 70% by mass or more. The polymer block B having a polymer block structure and having butadiene as a main component is a butadiene homopolymer block or butadiene and styrene containing butadiene in an amount of more than 50% by mass, preferably 70% by mass or more. And a copolymer block structure.

  Further, the individual structures of the polymer block A mainly composed of styrene and the polymer block B mainly composed of butadiene have a random, tapered (molecular) distribution of styrene or butadiene in the molecular chain in each polymer block. The monomer component may increase or decrease along the chain), a part of the block structure may be 100% by weight of styrene, or a part of the block structure may be 100% by weight of butadiene. When there are two or more polymer blocks A mainly composed of styrene and two polymer blocks B mainly composed of butadiene, each polymer block may have the same structure or a different structure. .

  Then, when referring to the polymer block B mainly composed of butadiene, the hydrogenated block copolymer (c) provided in the present invention is obtained before at least one polymer block B mainly composed of butadiene is hydrogenated. The amount of 1,2-vinyl bonds of butadiene may be a single vinyl bond selected from 70 to 90%, and is mainly composed of butadiene having a 1,2-vinyl bond content of 70 to 90%. It is a polymer block B mainly composed of butadiene having at least one polymer block B1 and at least one polymer block B2 mainly composed of butadiene having a 1,2-vinyl bond content of less than 30 to 70%. May be. 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 is usually known by an infrared spectrophotometer, NMR or the like.
Then, the aliphatic double bond of the polymer block B mainly composed of butadiene in the block copolymer described above undergoes a hydrogenation reaction to produce a hydrogenated block copolymer (hydrogenated styrene-butadiene block copolymer). Can be used as the component (c). The hydrogenation rate of such aliphatic double bonds is 80% or more. This hydrogenation rate can usually be known by an infrared spectrophotometer, NMR or the like.
In addition to the above structure, the hydrogenated block copolymer (c) has a number average molecular weight (Mnc) of 100,000 or less, and the polymer block A mainly composed of styrene has a number average molecular weight (MncA) of 8000 or more. It is necessary to satisfy.

  The necessity of setting the number average molecular weight (Mnc) of the hydrogenated block copolymer (c) to 100000 or less is that the role of the hydrogenated block copolymer (c) in the resin composition is merely a polymer (polypropylene) -polymer ( It is to play a role as an emulsifying dispersant (admixture) between (polyphenylene ether). That is, when emulsifying a polymer (polypropylene) -polymer (polyphenylene ether) having a high viscosity in the melt bulk state, the hydrogenated block copolymer (c) of the emulsifying dispersant (admixture) is preferably used in the melt-mixing system. Need to spread. For this reason, the number average molecular weight (Mnc) is required to be 100,000 or less in consideration of the melt viscosity of the hydrogenated block copolymer (c).

  Furthermore, the inevitability that the number average molecular weight (MncA) of the polymer block A mainly composed of styrene of the hydrogenated block copolymer (c), which is an essential requirement, is 8000 or more is a hydrogenated block copolymer that satisfies this condition. Can well solubilize PPE (b) having a weight average molecular weight (Mwppe) of 15000 to 25000 and a molecular weight distribution (Mwppe / Mnppe) of 1.5 to 3.0, and a polymer (polypropylene) -polymer (polyphenylene ether) ) Is a condition that must be satisfied in order to give a good emulsified dispersion state of PPE in the emulsified dispersion during the process, and to give great advantages to the heat resistance, mechanical properties and processability of the resulting resin composition. The relationship between the molecular weight of the emulsified and dispersed PPE (b) and the number average molecular weight of the polymer block A mainly composed of styrene of the hydrogenated block copolymer (c) as the emulsifying dispersant (admixture) is polymer (polypropylene). ) -Polymer emulsification dispersion technology important in bringing about an optimal emulsification dispersion between the polymers (polyphenylene ether), and has been achieved by focusing on this unknown polymer emulsion dispersion technology.

  The measurement of the number average molecular weight (Mnc) of the hydrogenated block copolymer (c), which plays an important role as this emulsifying dispersant (admixture), is performed by Shower Denko Co., Ltd. Gel Permeation Chromatography System 21 (column : Showa Denko Co., Ltd., one KG, one K-800RL, and one K-800R in series, column temperature: 40 ° C., solvent: chloroform, solvent flow rate: 10 ml / min Sample concentration: 1 g / liter of hydrogenated block copolymer / chloroform solution) and standard polystyrene (the molecular weight of standard polystyrene is 3650000, 217000, 1090000, 681000, 204000,52000, 30200, 13800,3360, 1300,550) A calibration curve is created using and measured. The UV (ultraviolet) wavelength of the detection part is measured by setting both standard polystyrene and hydrogenated block copolymer to 254 nm.

  The number average molecular weight (MncA) of the polymer block A mainly composed of styrene of the hydrogenated block copolymer (c) is, for example, the above-described hydrogenated block copolymer in the case of an ABA type structure. Based on the number average molecular weight (Mnc) of the above, assuming that the molecular weight distribution of the hydrogenated block copolymer is 1, and that two polymer blocks A mainly composed of styrene exist as the same molecular weight, (MncA) = (Mnc) × bonded styrene content ratio ÷ 2. Similarly, in the case of an A-B-A-B-A type hydrogenated block copolymer (c), (MncA) = (Mnc) × bonded styrene content ratio ÷ 3. it can. When the sequence of the block structure A and the block structure B is clear at the stage of synthesizing the styrene-butadiene block copolymer, the measured hydrogenated block copolymer is not dependent on the above formula. You may calculate from the ratio of the block structure A based on the number average molecular weight (Mnc) of a polymer.

  These hydrogenated block copolymers of the component (c) may be obtained by any production method as long as they have the structure described above. Examples of known production methods include, for example, JP-A-47-11486, JP-A-49-66743, JP-A-50-75651, JP-A-54-126255, JP-A-54-126255. No. 56-10542, JP-A-56-62847, JP-A-56-1000084, JP-A-2004-269665, British Patent No. 1130770 and US Pat. Nos. 3,281,383 and 3639517 And methods described in British Patent No. 1020720 and US Pat. Nos. 3,333,024 and 4,501,857.

In addition to the above-mentioned hydrogenated block copolymer, the hydrogenated block copolymer of component (c) includes the hydrogenated block copolymer and an α, β-unsaturated carboxylic acid or derivative thereof (ester compound or Modification obtained by reacting an acid anhydride compound, such as maleic anhydride, in the presence or absence of a radical generator, in the molten state, in the solution state, or in the slurry state at a temperature of 80 to 350 ° C. , Β-unsaturated carboxylic acid or a derivative thereof may be 0.01 to 10% by mass grafted or added) hydrogenated block copolymer, and the hydrogenated block copolymer and the modified hydrogenated block copolymer described above may be used. It may be a mixture of any proportion of the polymer.
The resin composition is composed of components having the above-described characteristics, and is a resin composition having the following two characteristics.

< Feature 1 >
The resin composition has a morphology in which the matrix phase: polypropylene resin (a), dispersed phase: polyphenylene ether resin (b) and hydrogenated block copolymer (c) are dispersed.
< Feature 2 >
Furthermore, the equivalent circle average particle diameter (D1) of the polyphenylene ether resin (b) dispersed in this resin composition (resin pellet or resin molded product) The polyphenylene ether resin (b) dispersed in the resin composition after the test is smaller than the equivalent circle average particle diameter (D2), D2 / D1 ≦ 5, and has a thermally stable dispersion form. It is the resin composition shown.

This static heat melting test means that the mechanical dispersion factor between the polymer (polypropylene) and the polymer (polyphenylene ether) in the synthesis of the incompatible polymer alloy (mechanical mixing factor by an extruder or injection molding machine) Is a test for confirming the effect of emulsifying and dispersing with an emulsifying dispersant (admixture). In this stationary heat-melting test, resin pellets or resin molded product pieces were molded using a heat compression molding machine in a mold frame of 54 mm long × 41 mm wide × 2 mm thick at a temperature of 260 ° C. and a pressure of 10 kg / cm ² . The plate is heat compression molded for 10 minutes and immediately cooled for 5 minutes with a 10 ° C. cooling press to obtain a compression molded plate. Then, in order to confirm the dispersion state of the polyphenylene ether resin (b) dispersed in the compression molded plate, the central portion of the thickness of the central portion of the compression plate is cut parallel to the plate surface to confirm the dispersion form.

This method of confirming the dispersion form can be easily confirmed and measured using a transmission electron microscope. For example, a sample is oxidized with a heavy metal compound such as ruthenium tetrachloride, an ultrathin section is cut out with an ultramicrotome, etc., and the section is observed with a transmission electron microscope (for example, observed at a magnification of 10,000 times) It can be obtained as an image. The dispersion diameter of the polyphenylene ether resin (b) obtained here can be usually obtained as an equivalent circle average particle diameter using an image processing apparatus.
Here, the circle-equivalent average particle diameter is calculated as a circular particle diameter by measuring the entire circumference of the morphological dispersion particles obtained with a transmission electron microscope and regarding the value as the circumference. Specifically, in order to know such a dispersion form, an ultrathin section is prepared by a microtome (Ultracut E manufactured by Reichert) from a piece of resin pellet or resin molded product, stained with ruthenic acid, and then subjected to a transmission electron microscope ( JEOL's 1200EX) makes it easy to observe. Then, based on the obtained transmission electron micrograph, the equivalent circle diameter is obtained from the circumference of the dispersed phase using an image analyzer (for example, IP1000 manufactured by Asahi Kasei Co., Ltd.), and the average particle diameter and the particle size distribution are obtained. be able to.

  When the emulsion dispersion stability between the polymer (polypropylene) and the polymer (polyphenylene ether) that can be known by such a method is poor in the emulsion dispersion stability of the polyphenylene ether resin (b) (D2 / D1> 5), The physical properties of the resin composition are deteriorated and stable physical properties cannot be obtained. That is, a polyphenylene ether resin (b) having a polypropylene resin (a) -weight average molecular weight (Mwppe) of 15000 to 25000 and a molecular weight distribution (Mwppe / Mnppe) of 1.5 to 3.0 is obtained by emulsifying and dispersing. The polymer alloy in which the polypropylene resin (c) is a matrix and the dispersed phase is a polyphenylene ether resin is emulsified from the viewpoints of its emulsion dispersion stability and heat resistance, mechanical properties and processability, which are the performance of the composition. As a dispersant (admixture), at least two polymer blocks A mainly composed of styrene, and at least one polymer 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 block B, and The amount of bound styrene is 15 to 50% by mass, the number average molecular weight (Mnc), and the number average molecular weight (MncA) of the polymer block A mainly composed of styrene is a gel permeation chromatography (GPC) using a chloroform solvent. The hydrogenated block copolymer (c) having Mnc ≦ 100000 and MncA ≧ 8000 is an essential component.

  This resin composition comprises 25 to 99% by mass of the above-described polypropylene resin as component (a) and 75 to 1% by mass of polyphenylene ether resin as component (b), and 100 parts by mass in total of components (a) and (b). On the basis of the resin composition containing 1 to 20 parts by mass of the hydrogenated block copolymer of component (c), water of component (c) is used as a method for further improving the physical properties of the resin composition obtained. The hydrogenated block copolymer (d) and / or the hydrogenated block copolymer (e) having a structure different from that of the hydrogenated block copolymer may be used in combination with the hydrogenated block copolymer of the component (c). it can.

  The hydrogenated block copolymer (d) that can be used in combination has, for example, ABA type, ABAB type, (AB-) nX type (where n is 1). The above integers and X represent reaction residues of polyfunctional coupling agents such as silicon tetrachloride and tin tetrachloride or residues of initiators such as polyfunctional organolithium compounds.), A-B-A-B -Hydrogenated product of a styrene-butadiene block copolymer having a structure in which block units such as A type are bonded, and among them, a hydrogenated block copolymer having a structure of ABBA type is AB. Since it is excellent in fluidity | liquidity compared with -A type hydrogenated block copolymer, it is more preferable. And the amount of styrene couple | bonded in the hydrogenated block copolymer (d) which shows these block structures contains 50 to 70 mass%, Preferably it is 53 to 68 mass%, More preferably, it contains 58 to 67 mass%. Further, referring to individual block structures, the polymer block A mainly composed of styrene is a homopolymer block of styrene or a copolymer of styrene and butadiene containing styrene in an amount of more than 50% by mass, preferably 70% by mass or more. The polymer block B having a polymer block structure and having butadiene as a main component is a butadiene homopolymer block or butadiene and styrene containing butadiene in an amount of more than 50% by mass, preferably 70% by mass or more. And a copolymer block structure.

  Further, the individual structures of the polymer block A mainly composed of styrene and the polymer block B mainly composed of butadiene have a random, tapered (molecular) distribution of styrene or butadiene in the molecular chain in each polymer block. The monomer component may increase or decrease along the chain), a part of the block structure may be 100% by weight of styrene, or a part of the block structure may be 100% by weight of butadiene. When there are two or more polymer blocks A mainly composed of styrene and two polymer blocks B mainly composed of butadiene, each polymer block may have the same structure or a different structure. .

  Then, when referring to the polymer block B mainly composed of butadiene, the hydrogenated block copolymer (d) provided in the present invention is obtained before at least one polymer block B mainly composed of butadiene is hydrogenated. The amount of 1,2-vinyl bonds of butadiene may be a single vinyl bond selected from 25 to 70%, and is mainly composed of butadiene having a 1,2-vinyl bond content of 25 to 45%. A polymer block B mainly composed of butadiene having at least one polymer block B1 and at least one polymer block B2 mainly composed of butadiene having a 1,2-vinyl bond content of more than 45 to less than 70%. There may be. A block copolymer having such a block structure is, for example, a known AB2-B1-A, in which the amount of 1,2-vinyl bond 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 is usually known by an infrared spectrophotometer, NMR or the like.
Then, the aliphatic double bond of the polymer block B mainly composed of butadiene in the block copolymer described above undergoes a hydrogenation reaction to produce a hydrogenated block copolymer (hydrogenated styrene-butadiene block copolymer). Can be used as the component (d). The hydrogenation rate of such aliphatic double bonds is 80% or more. This hydrogenation rate can usually be known by an infrared spectrophotometer, NMR or the like.
In addition to the above structure, the hydrogenated block copolymer (d) has a number average molecular weight (Mnd) of 150,000 or less, and the polymer block A mainly composed of styrene has a number average molecular weight (MndA) of 8000 or more. It is necessary to satisfy.

  The number average molecular weight (Mnd) of the hydrogenated block copolymer (d) was measured by using one gel permeation chromatography system 21 manufactured by Showa Denko KK (column: Showa Denko KK). , One K-800RL and one K-800R in series in order, column temperature: 40 ° C., solvent: chloroform, solvent flow rate: 10 ml / min, sample concentration: 1 g /% of hydrogenated block copolymer A calibration curve is prepared and measured using standard polystyrene (the molecular weight of standard polystyrene is 3650000, 217000, 1090000, 681000, 204000, 52000, 30200, 13800, 3360, 1300, 550) in a liter / chloroform solution. The UV (ultraviolet) wavelength of the detection part is measured by setting both standard polystyrene and hydrogenated block copolymer to 254 nm.

  In addition, the number average molecular weight (MndA) of the polymer block A mainly composed of styrene of the hydrogenated block copolymer (d) is, for example, the above-described hydrogenated block copolymer in the case of an ABA type structure. Based on the number average molecular weight (Mnd), the molecular weight distribution of the hydrogenated block copolymer is 1, and two polymer blocks A mainly composed of styrene exist as the same molecular weight, and (MndA) = (Mnd) × bonded styrene content ratio ÷ 2. Similarly, in the case of an A-B-A-B-A type hydrogenated block copolymer (d), (MndA) = (Mnd) × the proportion of the amount of bound styrene ÷ 3 it can. When the sequence of the block structure A and the block structure B is clear at the stage of synthesizing the styrene-butadiene block copolymer, the measured hydrogenated block copolymer is not dependent on the above formula. You may calculate from the ratio of the block structure A based on the number average molecular weight (Mnd) of a polymer.

  These hydrogenated block copolymers of the above component (d) may be obtained by any production method as long as they have the above structure. Examples of known production methods include, for example, JP-A-47-11486, JP-A-49-66743, JP-A-50-75651, JP-A-54-126255, JP-A-54-126255. No. 56-10542, JP-A-56-62847, JP-A-56-1000084, JP-A-2004-269665, British Patent No. 1130770 and US Pat. Nos. 3,281,383 and 3639517 And methods described in British Patent No. 1020720 and US Pat. Nos. 3,333,024 and 4,501,857.

In addition to the above-mentioned hydrogenated block copolymer, the hydrogenated block copolymer of component (d) includes the hydrogenated block copolymer and an α, β-unsaturated carboxylic acid or derivative thereof (ester compound or Modification obtained by reacting an acid anhydride compound, such as maleic anhydride, in the presence or absence of a radical generator, in the molten state, in the solution state, or in the slurry state at a temperature of 80 to 350 ° C. , Β-unsaturated carboxylic acid or a derivative thereof may be 0.01 to 10% by mass grafted or added) hydrogenated block copolymer, and the hydrogenated block copolymer and the modified hydrogenated block copolymer described above may be used. It may be a mixture of any proportion of the polymer.
The structure of the hydrogenated block copolymer (e) that can be used in combination is, for example, ABA type, ABBA type, (AB-) nX type (where n is An integer of 1 or more, X represents a reaction residue of a polyfunctional coupling agent such as silicon tetrachloride or tin tetrachloride or a residue of an initiator such as a polyfunctional organolithium compound.), A-B-A- It is a hydrogenated product of a styrene-butadiene block copolymer having a structure in which block units such as B-A type are bonded. Among them, a hydrogenated block copolymer having an A-B-A-B type structure is A- Since it is excellent in fluidity | liquidity compared with a B-A type hydrogenated block copolymer, it is more preferable.

  And the amount of styrene couple | bonded in the hydrogenated block copolymer (e) which shows these block structures contains 15-50 mass%, Preferably it is 20-50 mass%, More preferably, it contains 30-50 mass%. Further, referring to individual block structures, the polymer block A mainly composed of styrene is a homopolymer block of styrene or a copolymer of styrene and butadiene containing styrene in an amount of more than 50% by mass, preferably 70% by mass or more. The polymer block B having a polymer block structure and having butadiene as a main component is a butadiene homopolymer block or butadiene and styrene containing butadiene in an amount of more than 50% by mass, preferably 70% by mass or more. And a copolymer block structure.

  Further, the individual structures of the polymer block A mainly composed of styrene and the polymer block B mainly composed of butadiene have a random, tapered (molecular) distribution of styrene or butadiene in the molecular chain in each polymer block. The monomer component may increase or decrease along the chain), a part of the block structure may be 100% by weight of styrene, or a part of the block structure may be 100% by weight of butadiene. When there are two or more polymer blocks A mainly composed of styrene and polymer blocks B mainly composed of butadiene, each polymer block may have the same structure or a different structure. .

  Then, when referring to the polymer block B mainly composed of butadiene, the hydrogenated block copolymer (e) provided in the present invention is obtained before at least one polymer block B mainly composed of butadiene is hydrogenated. The amount of 1,2-vinyl bonds of butadiene may be a single vinyl bond selected from 25 to 70%, and is mainly composed of butadiene having a 1,2-vinyl bond content of 25 to 45%. A polymer block B mainly composed of butadiene having at least one polymer block B1 and at least one polymer block B2 mainly composed of butadiene having a 1,2-vinyl bond content of more than 45 to less than 70%. There may be. 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 is usually known by an infrared spectrophotometer, NMR or the like.
Then, the aliphatic double bond of the polymer block B mainly composed of butadiene in the block copolymer described above undergoes a hydrogenation reaction to produce a hydrogenated block copolymer (hydrogenated styrene-butadiene block copolymer). As the component (e). The hydrogenation rate of such aliphatic double bonds is 80% or more. This hydrogenation rate can usually be known by an infrared spectrophotometer, NMR or the like.

In addition to the above structure, the hydrogenated block copolymer (e) has a number average molecular weight (Mne) of 100,000 or less, and the polymer block A mainly composed of styrene has a number average molecular weight (MneA) of 8000 or more. It is necessary to satisfy.
The number average molecular weight (Mne) of the hydrogenated block copolymer (e) is measured by using one gel permeation chromatography system 21 manufactured by Showa Denko KK (column: KG manufactured by Showa Denko KK). , One K-800RL and one K-800R in series in order, column temperature: 40 ° C., solvent: chloroform, solvent flow rate: 10 ml / min, sample concentration: 1 g /% of hydrogenated block copolymer A calibration curve is prepared and measured using standard polystyrene (the molecular weight of standard polystyrene is 3650000, 217000, 1090000, 681000, 204000, 52000, 30200, 13800, 3360, 1300, 550) in a liter / chloroform solution.

  The UV (ultraviolet) wavelength of the detection part is measured by setting both standard polystyrene and hydrogenated block copolymer to 254 nm. The number average molecular weight (MneA) of the polymer block A mainly composed of styrene of the hydrogenated block copolymer (e) is, for example, the above-described hydrogenated block copolymer in the case of an ABA type structure. Based on the number average molecular weight (Mne), the molecular weight distribution of the hydrogenated block copolymer is 1, and two polymer blocks A mainly composed of styrene are present as the same molecular weight, and (MneA) = (Mne) × bonded styrene content ratio ÷ 2. Similarly, in the case of the A-B-A-B-A type hydrogenated block copolymer (e), it can be obtained by the following formula: (MneA) = (Mne) × bonded styrene content ratio ÷ 3. it can. When the sequence of the block structure A and the block structure B is clear at the stage of synthesizing the styrene-butadiene block copolymer, the measured hydrogenated block copolymer is not dependent on the above formula. You may calculate from the ratio of the block structure A based on the number average molecular weight (Mne) of a polymer.

  These hydrogenated block copolymers of the above component (e) may be obtained by any production method as long as they have the above structure. Examples of known production methods include, for example, JP-A-47-11486, JP-A-49-66743, JP-A-50-75651, JP-A-54-126255, JP-A-54-126255. No. 56-10542, JP-A-56-62847, JP-A-56-1000084, JP-A-2004-269665, British Patent No. 1130770 and US Pat. Nos. 3,281,383 and 3639517 And methods described in British Patent No. 1020720 and US Pat. Nos. 3,333,024 and 4,501,857.

  In addition to the above-mentioned hydrogenated block copolymer, the hydrogenated block copolymer of component (e) includes the hydrogenated block copolymer and an α, β-unsaturated carboxylic acid or derivative thereof (ester compound or Modification obtained by reacting an acid anhydride compound, such as maleic anhydride, in the presence or absence of a radical generator, in the molten state, in the solution state, or in the slurry state at a temperature of 80 to 350 ° C. , Β-unsaturated carboxylic acid or a derivative thereof may be 0.01 to 10% by mass grafted or added) hydrogenated block copolymer, and the hydrogenated block copolymer and the modified hydrogenated block copolymer described above may be used. It may be a mixture of any proportion of the polymer.

  And the compounding ratio of said hydrogenated block copolymer (d) and / or hydrogenated block copolymer (e) which can be used together with a hydrogenated block copolymer (c) is (c) / (d) = 1-99 mass% / 99-1 mass%, (c) / (e) = 1-99 mass% / 99-1 mass% and (c) / (d) / (e) = 1-98 mass% / It is 98-1 mass% / 1-98 mass%. Among them, the polyphenylene ether resin (b) having a weight average molecular weight (Mwppe) of 15000 to 25000 and a molecular weight distribution (Mwppe / Mnppe) of 1.5 to 3.0 provided in the present invention is added to the polypropylene resin (a) matrix. In order to obtain a thermally stable polymer dispersion in an emulsified dispersion state, the ratio of the hydrogenated block copolymer (c) contained in the total amount of the combined hydrogenated block copolymers (c) to (e) is: 3 mass% or more is required. More preferably, it is 5 mass% or more.

  Furthermore, the filler used as the component (f) is a component that gives a number of functions to the resin composition comprising the components (a) to (e) described above. For example, imparting rigidity, imparting heat resistance, heat It is possible to select according to the purpose such as imparting conductivity, imparting conductivity, improving molding shrinkage rate, improving linear expansion coefficient, etc. As the inorganic filler of component (f) that brings out these effects, for example, an inorganic salt , Glass fibers (long glass fibers, chopped strand glass fibers), cellulose, glass flakes, glass beads, carbon long fibers, chopped strand carbon fibers, whiskers, mica, clay, talc, magnesium hydroxide, magnesium sulfate and its fibers, silica , Carbon black, titanium oxide, calcium carbonate, fly ash (coal ash), potassium titanate, Ruthenite, thermally conductive material (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 showing conductivity , At least one selected from the group consisting of carbon fibers and carbon nanotubes exhibiting electrical conductivity 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.

The blending amount of the filler of the component (f) is 0.1 to 300 parts by weight, more preferably 1 to 250 parts by weight with respect to 100 parts by weight of the total of the components (a) to (b). Preferably it is 5-200 mass parts. If the blending amount is 10 parts 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 150 parts by weight. In the following, molded products obtained by molding the resulting resin composition have less sink marks, a smaller linear expansion coefficient due to temperature change (-30 ° C to 120 ° C), and excellent dimensional accuracy and anisotropy. Can be a molded product.
Further, as components to be blended in the resin composition, for example, stabilizers, mold release agents, processing aids, flame retardants, anti-drip agents, nucleating agents, UV blockers, dyes, pigments, antioxidants, antistatic agents, A foaming agent etc. can be mentioned. These additives can be used as long as they are known in the art, and the lower limit of the blending amount is 0.1 parts by mass with respect to 100 parts by mass of all the resin mixtures. More preferably, it is 0.2 parts by mass, and most preferably 0.3 parts by mass. As an upper limit, it is 10 mass parts, More preferably, it is 5 mass parts, Most preferably, it is 3 mass parts.

  However, the upper limit of the blending amount of the flame retardant is 100 parts by mass with respect to 100 parts by mass of all the resin mixtures. More preferably, it is 70 parts by mass, and most preferably 50 parts by mass. Such flame retardants include organophosphate compounds, phosphinic acid metal salts, magnesium hydroxide, ammonium polyphosphate flame retardants, melamine flame retardants, triazine flame retardants, aromatic halogen flame retardants, silicone flame retardants, At least one selected from the group consisting of fluorine-based polymers can be selected and used.

Hereinafter, the manufacturing method of a resin composition is demonstrated.
As a most preferable embodiment as a method for industrially easily obtaining a stable emulsified dispersion state between polypropylene and polyphenylene ether as a polymer alloy as a polymer alloy,
(1) The above-mentioned melt kneader for melt kneading each component is a multi-screw extruder of two or more axes capable of incorporating a kneading block at an arbitrary position of the screw, and the entire kneading of the screw to be used The block portion is substantially (L / D) ≧ 1.5, more preferably (L / D) ≧ 5 [where L is the total length of the kneading block, and D is the maximum outer diameter of the kneading block. And (π · D · N / h) ≧ 50 (where π = 3.14, D = screw outer diameter corresponding to the metering zone, N = screw rotation speed (rev / sec)) , H = groove depth of the 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 thereof, and if necessary, on the downstream side of the second raw material supply port. Furthermore, 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 raw material supply method for producing the resin composition is based on the total amount of the (b) component polyphenylene ether resin or the (b) component polyphenylene ether resin and the (a) polypropylene resin from the first raw material supply port. A part of the polypropylene resin as the component (a) and the total amount of the hydrogenated block copolymer as the component (c) within a range not exceeding 50% of the total amount are supplied together, and from the second raw material supply port, the component (a) The extrusion method of supplying the entire amount of the polypropylene resin or the remainder of the polypropylene resin of the component (a) distributed to the first raw material supply port is used. Usually, the extruder barrel set temperature is 200 to 370 ° C, preferably 250 to 310 ° C, screw It is produced by melt-kneading under the conditions of a rotational speed of 100 to 1200 rpm, preferably 200 to 500 rpm.

(3) A hydrogenated block copolymer in which the hydrogenated block copolymer has a vinyl bond content of less than 25 to 70% in the polymer block B mainly composed of a conjugated diene compound in the block copolymer before hydrogenation. (D) The hydrogenated block copolymer (e) can be supplied in a total amount to the first raw material supply port or dividedly 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 (f) component is basically a method in which all the resin components (a) to (e) are supplied from the third raw material supply port and melt-kneaded in a state of being melt-kneaded. Although it is preferable, when the conveying ability in the side feed extruder that is supplied to the extruder, which tends to occur when the filler is fine powder, is reduced, the filler (f) component is added from the second raw material supply port (a) Melting and kneading are carried out by an extrusion method in which the total amount of the component polypropylene resin or the remainder of the component (a) polypropylene resin distributed to the first raw material supply port is supplied.

(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 resin composition thus obtained can be molded as a molded article of various parts by various conventionally known methods such as compression molding, injection molding, extrusion molding, multilayer extrusion molding, profile extrusion molding, and hollow molding. .

The specific molded body using the resin composition is
Secondary battery batteries, sheets / films, stretched sheets / films, lithium ion battery separators obtained by stretching sheets / films, automobile mechanism parts, automobile exterior parts, and automobile interior parts. And as automotive parts, air conditioner housing, heater housing, ducts, fuel tank protector, connector housing, fuel filter housing, fuel filter cap, cooling fan, fan shroud, timing belt cover, oil tank, oil tank cap, radiator tank , Under cover and the like. Automotive exterior parts include bumpers and bumper beams, low bumper stiffeners, side spoilers, front grilles, rear garnishes, door outer handles, pillar covers, door mirror bodies, mat guards, splash boards, cowl panels. , Wheel caps, various clips, various fasteners, lamp housings and the like. Automotive interior products include instrument panels, door trim panels, console boxes, pillar trims, differential grills, meter-related parts (visors and cases), covers, rearview mirror bodies, seat bags, headrest guides, seat hinge covers, seats Examples include belts, trunk room covers / boxes, steering wheels, horn covers, shift levers, shift lever knobs, and pedals. Further, the molded body using the resin composition is an electric wire / cable obtained by coating a metal conductor or optical fiber, a fuel case for a solid methanol battery, a fuel cell water pipe, a water cooling tank, a boiler outer case, an ink jet printer. Ink peripheral parts / members and chassis, and water pipes, joints and other molded articles can be used.
Next, examples and comparative examples will be described in more detail.

(A) High crystalline polypropylene component a-1: Homo-polypropylene
Melting point = 167 ° C., MFR = 0.5
a-2: Homo-polypropylene
Melting point = 164 ° C., MFR = 2.5
a-3: Homo-polypropylene
Melting point = 163 ° C., MFR = 6.0
a-4: Homo-polypropylene
Melting point = 165 ° C., MFR = 16.0
a-5: Homo-polypropylene
Melting point = 166 ° C., MFR = 50
The MFR (melt flow rate) of polypropylene was measured at 230 ° C. under a load of 2.16 kg in accordance with ASTM D1238.

(B) Component PPE
b-1: Oxidative polymerization of polyphenylene ether b-2: 2,6-xylenol having a weight average molecular weight (Mwppe) of 23,000 and a molecular weight distribution (Mwppe / Mnppe) of 2.3 obtained by oxidative polymerization of 2,6-xylenol Weight average molecular weight (Mwppe) 16000, molecular weight distribution (Mwppe / Mnppe) 2.0 polyphenylene ether b-3: 2,6-xylenol obtained by oxidative polymerization, weight average molecular weight (Mwppe) 37000, molecular weight distribution (Mwppe / Mnppe) 2.0 polyphenylene ether b-4: Polyphenylene ether having a weight average molecular weight (Mwppe) of 52,000 obtained by oxidative polymerization of 2,6-xylenol and a molecular weight distribution (Mwppe / Mnppe) of 2.2

(C) Component hydrogenated block copolymer c-1: Hydrogenated polybutadiene-polystyrene-hydrogenated polybutadiene-polystyrene structure (B-A-B-A) with a bound styrene content of 44% The number average molecular weight of the whole polymer is 90,000, the molecular weight distribution is 1.06, the number average molecular weight of the polystyrene part (A) is 19800, the 1,2-vinyl bond amount of the polybutadiene before hydrogenation is 75%, and the hydrogenation of the polybutadiene part A hydrogenated block copolymer having a ratio of 99.9% was synthesized, and this polymer was designated as (c-1).
c-2: Polystyrene-hydrogenated polybutadiene-polystyrene structure (ABA), 44% bonded styrene, number average molecular weight 87,000 of the whole polymer, molecular weight distribution 1.07, polystyrene part A hydrogenated block copolymer having a number average molecular weight of 19000 (A), a polybutadiene before hydrogenation of 1,2-vinyl bond content of 85%, and a hydrogenation rate of the polybutadiene part of 99.9% was synthesized. (C-2).

c-3: Polystyrene-hydrogenated polybutadiene-polystyrene-hydrogenated polybutadiene structure (ABAB) having a bound styrene content of 32%, a number average molecular weight of the whole polymer of 52,000, Both hydrogenated blocks having a molecular weight distribution of 1.07, a number average molecular weight of polystyrene part (A) of 8300, a 1,2-vinyl bond amount of polybutadiene before hydrogenation of 74%, and a hydrogenation rate of polybutadiene part of 99.9% A polymer was synthesized and this polymer was designated as (c-3).
c-4: Polystyrene-hydrogenated polybutadiene-polystyrene-hydrogenated polybutadiene structure (ABAB), bonded styrene content 44%, number average molecular weight of the whole polymer 34,000, The hydrogenated block has a molecular weight distribution of 1.07, a number average molecular weight of 7500 in the polystyrene part (A), a 1,2-vinyl bond content of polybutadiene before hydrogenation of 73%, and a hydrogenation rate of 99.9% in the polybutadiene part. A polymer was synthesized and this polymer was designated as (c-4).

c-5: Polystyrene-hydrogenated polybutadiene-polystyrene-hydrogenated polybutadiene structure (ABAB) having a bound styrene content of 44%, a number average molecular weight of the whole polymer of 120,000, The hydrogenated block has a molecular weight distribution of 1.07, a number average molecular weight of polystyrene part (A) of 26400, a 1,2-vinyl bond amount of polybutadiene before hydrogenation of 75%, and a hydrogenation rate of polybutadiene part of 99.9%. A polymer was synthesized and this polymer was designated as (c-5).
c-6: Polystyrene-hydrogenated polybutadiene-polystyrene structure (ABA), bound styrene content 29%, overall polymer number average molecular weight 98,500, molecular weight distribution 1.03, polystyrene part Kraton G1650 (Clayton Polymer Co., Ltd.) having a number average molecular weight of 14,000 (A) and a 1,2-vinyl bond content of polybutadiene before hydrogenation of 33% was defined as (c-6).

(D) Component hydrogenated block copolymer d-1: Polystyrene-hydrogenated polybutadiene-polystyrene structure (ABA), bound styrene content 60%, number average molecular weight of the whole polymer 108 1,000, molecular weight distribution 1.08, number average molecular weight 32,000 of polystyrene part (A), 1,2-vinyl bond content of polybutadiene before hydrogenation is 35%, hydrogenation rate of polybutadiene part is 99.9%, A hydrogenated block copolymer was synthesized, and this polymer was defined as (d-1).
d-2: Polystyrene-hydrogenated polybutadiene-polystyrene structure (ABA), bound styrene content 65%, number average molecular weight of the whole polymer 49,000, molecular weight distribution 1.04, polystyrene part A hydrogenated block copolymer of (A) having a number average molecular weight of 16000, a 1,2-vinyl bond amount of polybutadiene before hydrogenation of 38%, and a hydrogenation ratio of polybutadiene part of 99.9% was synthesized. The polymer was designated as (d-2).

Component (e) : Hydrogenated block copolymer e-1: Polystyrene-hydrogenated polybutadiene-polystyrene-hydrogenated polybutadiene structure (ABAB), bound styrene content 30% The number average molecular weight of the whole polymer is 75,000, the molecular weight distribution is 1.05, the number average molecular weight of the polystyrene part (A) is 11000, the 1,2-vinyl bond amount of the polybutadiene before hydrogenation is 33%, and the hydrogenation of the polybutadiene part A hydrogenated block copolymer having a rate of 99.9% was synthesized, and this polymer was designated as (e-1).
(F) Component filler f-1: Talc with an average particle size of 7 microns

[Examples 1 to 19 and Comparative Examples 1 to 11]
Each component of polypropylene, polyphenylene ether, hydrogenated block copolymer and filler shown in Tables 1-2 is set at a temperature of 240 to 310 ° C. and a screw rotation speed of 300 rpm, and a first raw material supply port and a second raw material supply port Using a twin screw extruder (ZSK-40; manufactured by WERNER & PFLIDEERER, Germany) having (located almost at the center of the extruder), the composition and the first composition of the first raw material supply port of the extruder shown in Tables 1-2 It supplied with the composition of the two raw material supply ports, and melt-kneaded to obtain a resin composition as pellets.
Using this pellet, it is supplied to a screw inline type injection molding machine set at 240 to 280 ° C., and a test piece for tensile test under the condition of a mold temperature of 60 ° C. (Thickness × width × length = 4 mm × 10 mm × 80 mm) was injection molded. Tensile strength test (ISO 527) is performed using this test piece, tensile strength is measured, bending elastic modulus (ISO 178), Charpy impact strength (ISO 179), and deflection temperature under load (ISO 75: 0.46 MPa load) ) Was measured.

In addition, in order to confirm the thermal stability of the polyphenylene ether-dispersed particles dispersed in the pellets of the resin composition obtained here, the resin pellets not containing the filler obtained above and the pellets were compression molded (length 54 mm × width 41 mm). X A 2 mm thick mold frame was subjected to heat compression molding for 10 minutes at a temperature of 260 ° C. and a pressure of 10 kg / cm ² and immediately cooled for 5 minutes with a cooling press at 10 ° C.). The state of the dispersed phase of each sample was obtained as an image using TEM). From the morphology of this image, the dispersion diameter of polyphenylene ether was calculated as an equivalent circle average particle diameter using an image processing apparatus, and the equivalent circle average particle diameter (D2) of the compression-molded plate / the equivalent circle average particle diameter of the resin pellet ( The ratio of D1) was determined.

These results are shown in Tables 1-2.
From these results, in a resin composition in which the matrix is a polypropylene resin / the dispersed phase is a polyphenylene ether resin, the vinyl bond amount between the polyphenylene ether resin having a weight average molecular weight (Mwppe) of 15,000 to 25000 and butadiene before hydrogenation is 70 The bonded styrene content is 15 to 50% by mass, the number average molecular weight (Mnc) and the number average molecular weight (MncA) of the polymer block A mainly composed of styrene are Mnc ≦ 100000, MncA ≧ 8000. It has been clarified that the resin composition obtained by the combination of the hydrogenated block copolymers is a resin composition excellent in processability, heat resistance, mechanical properties and thermal stability of the dispersed particles.

  Since the resin composition is excellent in processability, heat resistance, and mechanical properties, it is a secondary battery battery case, a sheet / film, a stretched sheet / film, a separator for a lithium ion battery obtained by stretching a sheet / film, and an automotive mechanism component. Can be molded and used for automobile exterior parts, automobile interior parts, electric wire / cable covering materials, various containers, pipes and joints around water, etc.

Claims (26)

(A) Polypropylene resin 25-99 mass%, (b) The weight average molecular weight (Mwpe) measured in polystyrene conversion using the gel permeation chromatography (GPC) of a chloroform solvent is 15000-25000, and molecular weight distribution Polyphenylene ether resin (Mwppe / Mnppe) of 1.5 to 3.0 At least two heavy components mainly composed of styrene per 100 parts by mass in total of components (a) and (b) consisting of 75 to 1% by mass Hydrogenated block copolymer (c) obtained by hydrogenating a block copolymer comprising a combined block A and at least one polymer block B mainly composed of butadiene having a butadiene vinyl bond content of 70 to 90%. ) A resin composition comprising 1 to 20 parts by mass, wherein the hydrogenated block copolymer (c) is (c 1) the amount of styrene bound is 15 to 50 wt%,
(C-2) The number average molecular weight (Mnc) and the number average molecular weight (MncA) of the polymer block A mainly composed of styrene are measured in terms of polystyrene using gel permeation chromatography (GPC) in a chloroform solvent. And Mnc ≦ 100,000 and MncA ≧ 8000. (A) Polypropylene resin 25-99 mass%, (b) The weight average molecular weight (Mwpe) measured in polystyrene conversion using the gel permeation chromatography (GPC) of a chloroform solvent is 15000-25000, and molecular weight distribution Polyphenylene ether resin (Mwppe / Mnppe) of 1.5 to 3.0 At least two heavy components mainly composed of styrene per 100 parts by mass in total of components (a) and (b) consisting of 75 to 1% by mass Hydrogenated block copolymer (c) obtained by hydrogenating a block copolymer comprising a combined block A and at least one polymer block B mainly composed of butadiene having a butadiene vinyl bond content of 70 to 90%. ), And at least two polymer blocks A mainly composed of styrene and a vinyl bond of butadiene. A hydrogenated block copolymer (d) obtained by hydrogenating a block copolymer comprising at least one polymer block B mainly composed of butadiene having an amount of less than 25 to 70% is (c) a hydrogenated block. Copolymer / (d) Hydrogenated block copolymer = 1 to 99% by mass / 99 to 1% by mass of a resin composition comprising 1 to 20 parts by mass of two hydrogenated block copolymers. The hydrogenated block copolymer (c)
(C-1) The amount of bound styrene is 15 to 50% by mass,
(C-2) The number average molecular weight (Mnc) and the number average molecular weight (MncA) of the polymer block A mainly composed of styrene are measured in terms of polystyrene using gel permeation chromatography (GPC) in a chloroform solvent. Mnc ≦ 100,000, MncA ≧ 8000
And the hydrogenated block copolymer (d) is
(D-1) The amount of bound styrene is more than 50 to 70% by mass.
(D-2) The number average molecular weight (Mnd) and the number average molecular weight (MndA) of the polymer block A mainly composed of styrene are measured in terms of polystyrene using gel permeation chromatography (GPC) of a chloroform solvent. Mnd ≦ 150,000, MndA ≧ 8000
A resin composition characterized by the above. (A) Polypropylene resin 25-99 mass%, (b) Weight average molecular weight (Mwppe) measured in polystyrene conversion using the gel permeation chromatography (GPC) of a chloroform solvent is 15000-25000, and molecular weight distribution ( Polyphenylene ether resin having Mwppe / Mnppe) of 1.5 to 3.0 At least two polymers mainly composed of styrene per 100 parts by mass in total of components (a) and (b) consisting of 75 to 1% by mass Hydrogenated block copolymer (c) obtained by hydrogenating a block copolymer comprising block A and at least one polymer block B mainly composed of butadiene having a butadiene vinyl bond content of 70 to 90%. And at least two polymer blocks A mainly composed of styrene and a vinyl bond of butadiene A hydrogenated block copolymer (e) obtained by hydrogenating a block copolymer comprising at least one polymer block B mainly composed of butadiene having a content of less than 25 to 70% is (c) a hydrogenated block copolymer. Polymer / (e) Hydrogenated block copolymer = 1-99% by mass / 99-1% by mass A resin composition comprising 1-20 parts by mass of two hydrogenated block copolymers. The hydrogenated block copolymer (c)
(C-1) The amount of bound styrene is 15 to 50% by mass,
(C-2) The number average molecular weight (Mnc) and the number average molecular weight (MncA) of the polymer block A mainly composed of styrene are measured in terms of polystyrene using gel permeation chromatography (GPC) in a chloroform solvent. Mnc ≦ 100,000, MncA ≧ 8000
And the hydrogenated block copolymer (e) is
(E-1) The amount of styrene bound is 15 to 50% by mass,
(E-2) Number average molecular weight (Mne) and number average molecular weight (MneA) of polymer block A mainly composed of styrene are measured in terms of polystyrene using gel permeation chromatography (GPC) in a chloroform solvent. Mne ≦ 100,000, MneA ≧ 8000
A resin composition characterized by the above. (A) Polypropylene resin 25-99 mass%, (b) Weight average molecular weight (Mwppe) measured in polystyrene conversion using the gel permeation chromatography (GPC) of a chloroform solvent is 15000-25000, and molecular weight distribution ( Polyphenylene ether resin having Mwppe / Mnppe) of 1.5 to 3.0 At least two polymers mainly composed of styrene per 100 parts by mass in total of components (a) and (b) consisting of 75 to 1% by mass Hydrogenated block copolymer (c) obtained by hydrogenating a block copolymer comprising block A and at least one polymer block B mainly composed of butadiene having a butadiene vinyl bond content of 70 to 90%. , At least two polymer blocks A mainly composed of styrene, and butadiene has a vinyl bond content of 2 Hydrogenated block copolymer (d) obtained by hydrogenating at least one block copolymer composed of at least one polymer block B mainly composed of butadiene which is less than 70%, and at least two composed mainly of styrene Hydrogenated block copolymer obtained by hydrogenating a polymer block A and a block copolymer comprising at least one polymer block B mainly composed of butadiene having a butadiene vinyl bond content of less than 25 to 70% The blend (e) is converted into (c) hydrogenated block copolymer / (d) hydrogenated block copolymer / (e) hydrogenated block copolymer = 1 to 98% by mass / 98 to 1% by mass / 1 to 98. A resin composition comprising 1 to 20 parts by mass of three types of hydrogenated block copolymers in a proportion by mass, wherein the hydrogenated block copolymer (c) is:
(C-1) The amount of bound styrene is 15 to 50% by mass,
(C-2) The average molecular weight (Mnc) and the number average molecular weight (MncA) of the polymer block A mainly composed of styrene were measured in terms of polystyrene using gel permeation chromatography (GPC) in a chloroform solvent. , Mnc ≦ 100,000, MncA ≧ 8000
And the hydrogenated block copolymer (d) is
(D-1) The amount of bound styrene is more than 50 to 70% by mass.
(D-2) The number average molecular weight (Mnd) and the number average molecular weight (MndA) of the polymer block A mainly composed of styrene are measured in terms of polystyrene using gel permeation chromatography (GPC) of a chloroform solvent. Mnd ≦ 150,000, MndA ≧ 8000
And the hydrogenated block copolymer (e) is
(E-1) The amount of styrene bound is 15 to 50% by mass,
(E-2) The average molecular weight (Mne) and the number average molecular weight (MneA) of the polymer block A mainly composed of styrene are measured in terms of polystyrene using gel permeation chromatography (GPC) in a chloroform solvent. , Mne ≦ 100,000, MneA ≧ 8000
A resin composition characterized by the above.   The hydrogenated block copolymer (c) according to any one of claims 1 to 4, wherein the hydrogenated block copolymer (c) is a hydrogenated block copolymer having a AB-A-B block structure. object.   The resin composition according to any one of claims 1 to 5, comprising 25 to 45% by mass of styrene bonded with the hydrogenated block copolymer (c).   The resin composition according to any one of claims 2 to 6, comprising 51 to 70% by mass of styrene bonded with the hydrogenated block copolymer (d).   The resin composition according to any one of claims 3 to 7, comprising 25 to 45% by mass of styrene bonded with the hydrogenated block copolymer (e).   (A) Melting | fusing point of polypropylene resin is 155 degreeC or more, The resin composition of any one of Claims 1-8 characterized by the above-mentioned.   (A) The polypropylene resin is homopolypropylene and / or block polypropylene, and the melt flow rate (measured according to MFR: ASTM D1238 at 230 ° C. under a load of 2.16 Kg) is 0.1 to 100 g / 10 min. The resin composition of any one of Claims 1-9 characterized by the above-mentioned.   The resin composition according to any one of claims 1 to 10, wherein the resin composition is contained in an amount of 0.1 to 300 parts by mass of (f) filler per 100 parts by mass in total of the components (a) to (b).   (F) Component filler is inorganic salt, glass fiber (glass long fiber, chopped strand glass fiber), cellulose, glass flake, glass bead, carbon long fiber, chopped strand carbon fiber, whisker, mica, clay, talc, water Magnesium oxide, magnesium sulfate and its fiber, silica, carbon black, titanium oxide, calcium carbonate, potassium titanate, wollastonite, thermal conductive material (graphite, aluminum nitride, boron nitride, alumina, beryllium oxide, silicon dioxide, oxidation Magnesium, aluminum nitrate, barium sulfate), conductive metal fiber, conductive metal flake, carbon black exhibiting conductivity, carbon fiber exhibiting conductivity, and at least one selected from the group consisting of carbon nanotubes The resin composition according to one claim 11.   The resin composition according to any one of claims 1 to 12, further comprising a stabilizer, a mold release agent, a processing aid, a flame retardant, an anti-drip agent, a nucleating agent, a UV blocking agent, a dye, a pigment, an oxidation A resin composition containing at least one additive selected from an inhibitor, a plasticizer, and an antistatic agent.   The secondary battery battery case obtained by shape | molding the resin composition of any one of Claims 1-13.   The separator for lithium ion batteries obtained by film-molding the resin composition of any one of Claims 1-13.   A sheet film or a stretched sheet film obtained by molding the resin composition according to claim 1.   An automobile mechanism part, an automobile exterior product, or an automobile interior product obtained by molding the resin composition according to any one of claims 1 to 13.   Automotive mechanism parts are air conditioner housing, heater housing, ducts, fuel tank protector, connector housing, fuel filter housing, fuel filter cap, cooling fan, fan shroud, timing belt cover, oil tank, oil tank cap, radiator tank, under cover The vehicle mechanism part according to claim 17, which is any one selected from the group consisting of:   Automotive exterior parts include bumpers, bumper beams, low bumper stiffeners, side spoilers, front grilles, rear garnishes, door outer handles, pillar covers, door mirror bodies, mat guards, splash boards, cowl panels, The automobile exterior product according to claim 17, wherein the vehicle exterior product is one selected from a wheel cap, a clip, a fastener, and a lamp housing.   Automotive interior parts are instrument panels, door trim panels, console boxes, pillar trims, differential grills, meter-related parts, visor cases, covers, room mirror bodies, seat bags, headrest guides, seat hinge covers, seat belts, trunk room covers, etc. The automobile interior part according to claim 17, which is any one selected from a box, a steering wheel, a horn cover, a shift lever, a shift lever knob, and a pedal.   The electric wire and cable obtained by coat | covering the metal composition or optical fiber with the resin composition of any one of Claims 1-13.   A fuel case for a solid methanol battery, a fuel cell water pipe or a joint thereof obtained by molding the resin composition according to any one of claims 1 to 13.   A water cooling tank obtained by molding the resin composition according to claim 1.   The boiler exterior case obtained by shape | molding the resin composition of any one of Claims 1-13.   A component / member or chassis around an ink of an ink jet printer obtained by molding the resin composition according to claim 1.   The water piping or joint obtained by shape | molding the resin composition of any one of Claims 1-13.