JP6185442B2 - Resin composition and molded body thereof - Google Patents

Description

  The present invention relates to a resin composition and a molded body thereof.

  Polypropylene resin has excellent properties such as moldability, water resistance, oil resistance, acid resistance and alkali resistance. However, since a polypropylene resin has defects that are inferior in heat resistance, rigidity, and impact resistance, it is known to form a composition containing a polyphenylene ether resin. In the composition, it is known that a polypropylene resin forms a matrix phase and a polyphenylene ether resin forms a dispersed phase, thereby providing a resin composition with improved heat resistance and rigidity.

  Patent Documents 1 and 2 propose a composition of a polyphenylene ether resin and a polypropylene resin. Patent Document 3 proposes a composition of a polyphenylene ether resin, a polypropylene resin, and a hydrogenated block copolymer, and the hydrogenated block copolymer is an admixture of a polyphenylene ether resin and a polypropylene resin. It is disclosed that it is a component that acts as and further imparts impact resistance.

International Publication No. 97/01600 JP 2001-270968 A JP 2010-229348 A

  The composition containing the polyphenylene ether resin and the polypropylene resin disclosed in the above-mentioned Patent Documents 1 to 3 has drastically improved solvent resistance and heat resistance compared to the classic polyphenylene ether resin composition. Although excellent, there is room for improvement in terms of tensile elongation, warpage of molded pieces, and impact resistance at low temperatures.

  Therefore, the present invention is a resin composition comprising a polypropylene resin and a polyphenylene ether resin, which is more excellent in tensile elongation and impact resistance at low temperatures, and a resin composition having a small warping of a molded piece and its molding The purpose is to provide a body.

  As a result of intensive studies, the present inventors have found that in a resin composition containing a polypropylene resin and a polyphenylene ether resin, at least a specific hydrogenated block copolymer resin and an ethylene-α-olefin copolymer rubber are used. It has been found that by including each one, a resin composition that is more excellent in tensile elongation and low-temperature impact properties and that has a small warp of a molded piece can be obtained.

  That is, the present invention is as follows.

[1]
(A) a polypropylene resin, (b) a polyphenylene ether resin, (c) a hydrogenated block copolymer resin, and (d) a copolymer rubber of ethylene and 1-octene,
The component (c) is a hydrogenated block copolymer comprising at least one polymer block A mainly composed of a vinyl aromatic compound and at least one polymer block B mainly composed of a conjugated diene compound. A hydrogenated block copolymer and / or a modified product of the hydrogenated block copolymer,
In the total bond of the conjugated diene compound unit in the component (c), the total ratio of 1,2-vinyl bond and 3,4-vinyl bond is 45 to 90%,
The resin composition in which the component (c) contains 30 to 50% by mass of a vinyl aromatic compound unit (provided that the crosslinked product of the component (a) and the component (d) is excluded).
[2]
The above item [1], wherein the melt flow rate of the component (d) (MFR: measured in accordance with ASTM D-1238 at 190 ° C. under a load of 2.16 kg) is 0.1 to 4.5 g / 10 minutes. The resin composition described in 1.
[3]
The resin composition according to [1] or [2] above, wherein the component (d) has a Shore A hardness (according to ASTM D-2240) of 75 or less.
[4]
Any of [1] to [3] above, wherein in the component (c), the hydrogenation rate of the block copolymer with respect to the ethylenic double bond (double bond in the conjugated diene compound unit) is 50 to 100%. A resin composition according to claim 1.
[5]
The total content of the components (c) and (d) is 1 to 50 parts by mass with respect to 100 parts by mass of the total content of the components (a) and (b).
The mass ratio ((a) :( b)) of the components (a) and (b) is 25:75 to 99: 1,
The resin composition according to any one of [1] to [4] above, wherein a mass ratio ((c) :( d)) of the components (c) and (d) is 1:99 to 99: 1. .
[6]
Any of [1] to [5], wherein the total proportion of 1,2-vinyl bond and 3,4-vinyl bond is 70 to 90% in all bonds of the conjugated diene compound unit in component (c). A resin composition according to claim 1.
[7]
Any of [1] to [6] above, wherein in the component (c), the hydrogenation rate of the block copolymer with respect to the ethylenic double bond (double bond in the conjugated diene compound unit) is 80 to 100%. A resin composition according to claim 1.
[8]
(E) a second hydrogenated block copolymer resin and / or (f) a third hydrogenated block copolymer resin,
The total content of the components (e) and / or (f) is 1 to 15 parts by mass with respect to 100 parts by mass of the total content of the components (a) and (b).
A block copolymer comprising the components (e) and (f) comprising at least one polymer block A mainly composed of a vinyl aromatic compound and at least one polymer block B mainly composed of a conjugated diene compound. A hydrogenated block copolymer obtained by hydrogenating a polymer and / or a modified product of the hydrogenated block copolymer,
The component (e) contains 10% by mass or more and less than 30% by mass of a vinyl aromatic compound unit,
The component (f) contains 20 to 70% by mass of vinyl aromatic compound units,
In the total bond of the conjugated diene compound unit in the component (e), the total ratio of 1,2-vinyl bond and 3,4-vinyl bond is 25% or more and less than 70%,
In the total bond of the conjugated diene compound unit in the component (f), the total ratio of 1,2-vinyl bond and 3,4-vinyl bond is 25% or more and less than 60%,
In the component (c), the hydrogenation ratio of the block copolymer to the ethylenic double bond (double bond in the conjugated diene compound unit) is 80 to 100%,
In the component (e), the hydrogenation ratio of the block copolymer to the ethylenic double bond (double bond in the conjugated diene compound unit) is 80 to 100%,
In the component (f), the hydrogenation ratio of the block copolymer to the ethylenic double bond (double bond in the conjugated diene compound unit) is 10% or more and less than 80%,
The resin composition according to any one of [1] to [7], wherein the polymer block A forming the component (e) has a number average molecular weight (MneA) of 4,000 to 8,000.
[9]
The resin composition according to any one of [1] to [8], wherein a mass ratio ((a) :( b)) of the components (a) and (b) is 30:70 to 50:50. .
[10]
The resin composition according to any one of [1] to [9], wherein the number average molecular weight (Mnc) of the component (c) is 100,000 or less.
[11]
The component (a) is homopolypropylene and / or block polypropylene,
[1] to [10], wherein the melt flow rate (MFR: measured in accordance with JIS K7210, measured at 230 ° C. under a load of 2.16 kg) is 0.1 to 100 g / 10 minutes. The resin composition in any one of.
[12]
The resin composition according to any one of [1] to [11] above, which has a matrix phase containing the component (a) and a dispersed phase containing the component (b).
[13]
(A) a polypropylene resin, (b) a polyphenylene ether resin, (c) a hydrogenated block copolymer resin, and (d) a copolymer rubber of ethylene and 1-octene,
The component (c) is a hydrogenated block copolymer comprising at least one polymer block A mainly composed of a vinyl aromatic compound and at least one polymer block B mainly composed of a conjugated diene compound. A hydrogenated block copolymer and / or a modified product of the hydrogenated block copolymer,
The ratio (−50 ° C. tan δ / 0 ° C. tan δ) of the loss tangent at −50 ° C. (−50 ° C. tan δ) obtained by the following measurement method to the loss tangent at 0 ° C. (0 ° C. tan δ) is 0.39 or more. , A resin composition (excluding a crosslinked product of the component (a) and the component (d));
<Measurement of loss tangent (tan δ)>
About the ISO test piece obtained from a resin composition, using a viscoelasticity measuring machine, tension mode, vibration frequency: 10 Hz, static load strain: 0.2%, dynamic load strain: 0.1%, contact load: Loss tangent (tan δ) at −50 ° C. and 0 ° C. when measured in a temperature sweep mode of 0.5 N, temperature increase rate: 3 ° C./min, temperature range: −100 ° C. to 160 ° C.
[14]
A molded article comprising the resin composition according to any one of [1] to [13].

  According to the present invention, it is possible to obtain a resin composition that is more excellent in tensile elongation and low-temperature impact properties and has a small warp of a molded piece, and a molded body using the same.

FIG. 1 is a schematic view showing a position when measuring warpage of a molded piece in the embodiment of the present application.

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

≪Resin composition≫
The resin composition of the present embodiment is
(A) a polypropylene resin, (b) a polyphenylene ether resin, (c) a hydrogenated block copolymer resin, and (d) an ethylene-α-olefin copolymer rubber,
The component (c) is a hydrogenated block copolymer comprising at least one polymer block A mainly composed of a vinyl aromatic compound and at least one polymer block B mainly composed of a conjugated diene compound. A hydrogenated block copolymer and / or a modified product of the hydrogenated block copolymer,
In the total bond of the conjugated diene compound unit in the component (c), the total ratio of 1,2-vinyl bond and 3,4-vinyl bond is 45 to 90%,
Said (c) component contains 30-50 mass% of vinyl aromatic compound units.
The melt flow rate of the component (d) (MFR: based on ASTM D-1238, measured at 190 ° C. under a load of 2.16 kg) is preferably 0.1 to 4.5 g / 10 minutes.
The Shore A hardness (according to ASTM D-2240) of the component (d) is preferably 75 or less.

  In the present embodiment, the characteristic of the component (d) is the characteristic when the component (d) is used alone.

[(A) component]
(A) Polypropylene resin (hereinafter, also referred to as “component (a)”) used in the present embodiment is not particularly limited. For example, (a1) polypropylene resin and (a2) modified polypropylene resin described later are used. Can be mentioned.

<(A1) Polypropylene resin>
(A1) Polypropylene resin refers to a polymer in which 50 mol% or more of the constituent monomer is propylene, and the others are not particularly limited. For example, a crystalline propylene homopolymer; a crystalline propylene homopolymer portion obtained in the first step of polymerization, and propylene, ethylene and / or at least one other α-olefin (eg, butene- 1, propylene-α-olefin random copolymer portion obtained by copolymerizing hexene-1, etc.) and a crystalline propylene-α-olefin block copolymer such as a crystalline propylene-ethylene block copolymer Is mentioned. (A1) The proportion of propylene in the monomer constituting the polypropylene resin is preferably 70 mol% or more, more preferably 90 mol% or more. These (a1) polypropylene resins may be used individually by 1 type, and may use 2 or more types together. Examples of the combination of two or more types are not particularly limited. For example, a crystalline propylene homopolymer and a crystalline propylene-ethylene block copolymer (except for those having a Shore A hardness of 75 or less). A mixture is mentioned. (A1) The polypropylene resin is preferably homopolypropylene and / or block polypropylene.

  The method for producing the (a1) polypropylene resin is not particularly limited. For example, the polymerization temperature is 0 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. The method of superposing | polymerizing the monomer containing propylene in the range of 3-100 atmospheres of polymerization pressure in the range of -100 degreeC is mentioned. At this time, a chain transfer agent such as hydrogen may be added to adjust the molecular weight of the resulting polymer.

  The polymerization method is not particularly limited, and either a batch method or a continuous method may be used. Further, solution polymerization in a solvent such as butane, pentane, hexane, heptane, octane, etc .; slurry polymerization; bulk polymerization in a monomer without solvent; gas phase polymerization method in a gaseous monomer, etc. can also be applied.

  Furthermore, in order to increase the isotacticity and polymerization activity of the obtained (a1) polypropylene resin, an electron donating compound can be used as the third component of the catalyst in the polymerization catalyst as an internal donor component or an external donor component. The type of the electron donating compound is not particularly limited, and known compounds can be used. For example, ester compounds such as ε-caprolactone, methyl methacrylate, ethyl benzoate and methyl toluate; phosphorous acid esters such as triphenyl phosphite and tributyl phosphite; phosphoric acid derivatives such as hexamethylphosphoramide; Examples include alkoxy ester compounds, aromatic monocarboxylic acid esters, aromatic alkyl alkoxy silanes, aliphatic hydrocarbon alkoxy silanes, various ether compounds, various alcohols, and / or various phenols.

  (A1) Melt flow rate (MFR) of polypropylene resin (value measured at 230 ° C. under a load of 2.16 kg in accordance with JIS K7210) is preferably 0.1 to 100 g / 10 min, more preferably The range is 0.1 to 80 g / 10 minutes. (A1) By making MFR of a polypropylene resin into the said range, it exists in the tendency for the balance of the fluidity | liquidity and rigidity of a resin composition to become favorable.

  (A1) The method of controlling the MFR of the polypropylene resin within the above range is not particularly limited, and examples thereof include a method of controlling the ratio of hydrogen supply to the monomer.

<(A2) Modified polypropylene resin>
(A2) The modified polypropylene resin is, for example, the above (a1) polypropylene resin and an α, β-unsaturated carboxylic acid or a derivative thereof in a molten state or a solution state in the presence or absence of a radical generator. The resin obtained by making it react at 30-350 degreeC. The (a2) modified polypropylene resin is not particularly limited. For example, a modified polypropylene obtained by grafting or adding 0.01 to 10% by mass of an α, β-unsaturated carboxylic acid or a derivative thereof to the (a1) polypropylene resin. Resin. Examples of the α, β-unsaturated carboxylic acid or derivative thereof are not particularly limited, and examples thereof include maleic anhydride and N-phenylmaleimide.

  When (a1) polypropylene resin and (a2) modified polypropylene resin are used in combination, the mixing ratio of (a1) polypropylene resin and (a2) modified polypropylene resin in (a) polypropylene resin is not particularly limited and is arbitrarily determined. it can.

  The (a) polypropylene resin used in the present embodiment can be obtained by the above method or other known methods. Moreover, even if it is (a) polypropylene resin which has what kind of crystallinity and melting | fusing point, you may use independently and may use 2 or more types together.

[Component (b)]
The (b) polyphenylene ether-based resin (hereinafter, also simply referred to as “(b) component” or “PPE”) used in the present embodiment is not particularly limited. For example, (b1) polyphenylene ether resin and ( b2) Modified polyphenylene ether resin.

<(B1) Polyphenylene ether resin>
(B1) The polyphenylene ether resin is a homopolymer and / or copolymer containing a repeating unit structure represented by the following formula (1). (B1) The reduced viscosity (0.5 g / dL chloroform solution, measured at 30 ° C.) of the polyphenylene ether resin is preferably in the range of 0.15 to 2.50, more preferably 0.30 to 2.00. More preferably, it is in the range of 0.35 to 2.00.

In formula (1), R ₁ , R ₂ , R ₃ , and R ₄ each independently represent a hydrogen atom, a halogen atom, a primary or secondary alkyl group having 1 to 7 carbon atoms, or a phenyl group. , A haloalkyl group, an aminoalkyl group, a hydrocarbonoxy group, or a monovalent group selected from the group consisting of a halohydrocarbonoxy group in which at least two carbon atoms separate a halogen atom and an oxygen atom.

  Although (b1) polyphenylene ether resin used for this Embodiment is not specifically limited, Well-known polyphenylene ether resin can be used. (B1) Specific examples of the polyphenylene ether resin are not particularly limited, and examples thereof include poly (2,6-dimethyl-1,4-phenylene ether) and poly (2-methyl-6-ethyl-1,4-phenylene). Ether), poly (2-methyl-6-phenyl-1,4-phenylene ether), and poly (2,6-dichloro-1,4-phenylene ether) and other homopolymers, and 2,6-dimethylphenol And other phenols (for example, 2,3,6-trimethylphenol and 2-methyl-6-butylphenol).

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

  (B1) The manufacturing method of polyphenylene ether resin is not specifically limited, A conventionally well-known method can be used. (B1) The polyphenylene ether resin can be easily produced, for example, by oxidative polymerization of 2,6-xylenol using, for example, a complex of cuprous salt and amine described in US Pat. No. 3,306,874 as a catalyst. . Further, (b1) polyphenylene ether resins are disclosed in U.S. Pat. No. 3,306,875, U.S. Pat. No. 3,257,357, U.S. Pat. No. 3,257,358, JP-B-52-17880, JP-A-50-51197. It can also be produced by the method described in JP-A-63-152628.

<(B2) Modified polyphenylene ether resin>
(B2) The modified polyphenylene ether resin is, for example, the above (b1) polyphenylene ether resin and a styrene monomer and / or an α, β-unsaturated carboxylic acid or a derivative thereof (for example, maleic anhydride, N-phenylmaleimide, fumarate). And unsaturated dicarboxylic acids such as acids and their derivatives, vinyl compounds such as styrene, acrylic acid esters, and methacrylic acid esters)) in the presence or absence of a radical generator, Or the resin obtained by making it react at 80-350 degreeC in a slurry state. (B2) The modified polyphenylene ether resin is not particularly limited. For example, the (b1) polyphenylene ether resin contains 0.01 to 10 mass of a styrene monomer and / or an α, β-unsaturated carboxylic acid or a derivative thereof. % -Grafted or added modified polyphenylene ether resin. Here, the styrenic monomer means styrene, or a singular or plural hydrogen molecule of styrene, a halogen atom, a primary or secondary alkyl group having 1 to 7 carbon atoms, a phenyl group, a haloalkyl group, an amino group. An alkyl group, a hydrocarbon oxy group or a compound in which at least two carbon atoms are substituted with a substituent selected from the group consisting of a halo hydrocarbon oxy group separating a halogen atom and an oxygen atom.

  When (b1) polyphenylene ether resin and (b2) modified polyphenylene ether resin are used in combination, the mixing ratio of (b1) polyphenylene ether resin and (b2) modified polyphenylene ether resin in (b) polyphenylene ether resin is limited. It can be determined arbitrarily.

[Component (c)]
(C) Hydrogenated block copolymer resin (hereinafter also referred to as “component (c)”) used in the present embodiment is (c1) hydrogenated block copolymer and / or (c2) modified water described later. It is a block copolymer.

<(C1) component>
(C1) A hydrogenated block copolymer is a block copolymer comprising at least one polymer block A mainly composed of a vinyl aromatic compound and at least one polymer block B mainly composed of a conjugated diene compound. A hydrogenated block copolymer obtained by hydrogenating a polymer, wherein all the bonds of the conjugated diene compound unit (hydrogenated block copolymer constituent unit derived from the conjugated diene compound) are 1,2-vinyl bonds and Hydrogenated block copolymer having a total proportion of 3,4-vinyl bonds of 45 to 90% and 30 to 50% by mass of vinyl aromatic compound units (hydrogenated block copolymer-derived structural units derived from vinyl aromatic compounds) It is a coalescence.

(Polymer block A)
The polymer block A mainly composed of a vinyl aromatic compound is a homopolymer block of a vinyl aromatic compound or a copolymer block of a vinyl aromatic compound and a conjugated diene compound. In the polymer block A, “mainly composed of a vinyl aromatic compound” means that the polymer block A contains more than 50% by mass of vinyl aromatic compound units, and 70% by mass of vinyl aromatic compound units. % Or more is preferable.

  Although it does not specifically limit as said vinyl aromatic compound, For example, styrene, (alpha) -methyl styrene, vinyl toluene, p-tert- butyl styrene, diphenylethylene etc. are mentioned. These may be used alone or in combination of two or more. Of the above, styrene is preferred. Examples of the conjugated diene compound include the compounds described below, which may be used alone or in combination of two or more.

(Polymer block B)
The polymer block B mainly composed of a conjugated diene compound is a homopolymer block of a conjugated diene compound or a random copolymer block of a conjugated diene compound and a vinyl aromatic compound. In the polymer block B, “consisting mainly of a conjugated diene compound” means that the polymer block B contains more than 50% by mass of conjugated diene compound units, and contains 70% by mass or more of conjugated diene compound units. It is preferable to do.

  The conjugated diene compound is not particularly limited, and examples thereof include butadiene, isoprene, 1,3-pentadiene, 2,3-dimethyl-1,3-butadiene and the like. These may be used alone or in combination of two or more. Among the above, butadiene, isoprene and combinations thereof are preferable. Examples of the vinyl aromatic compound include the aforementioned compounds, and these may be used alone or in combination of two or more.

  When the polymer block B is a polymer block mainly composed of butadiene, the total ratio of 1,2-vinyl bonds and 3,4-vinyl bonds of butadiene in the polymer block B is 65 to 90%. It is preferable.

  In the polymer block B, the conjugated diene compound unit is bonded to an adjacent monomer unit by either a 1,2-vinyl bond, a 3,4-vinyl bond, or a 1,4-conjugated bond. . When the total amount of these three bonds is defined as “total bond amount”, the polymer block B includes a 1,2-vinyl bond amount and a 3,4-vinyl bond amount relative to the total bond amount of the conjugated diene compound unit. A single polymer block having a total amount (hereinafter also referred to as “total vinyl bond amount”) of 45 to 90% may be used, and the ratio of the total vinyl bond amount is 45 to 90%. It has at least one polymer block B1 mainly composed of a conjugated diene compound and at least one polymer block B2 mainly composed of a conjugated diene compound whose ratio of the total vinyl bond amount is 30% or more and less than 45%. It may be a polymer block mainly composed of a conjugated diene compound.

  A block copolymer having such a block structure is, for example, when the polymer block A is “A”, the polymer block B1 is “B1”, and the polymer block B2 is “B2”. It can be obtained by a known polymerization method in which the total vinyl bond amount is controlled based on the feed sequence of each monomer unit represented by -B2-B1-A.

  In the present embodiment, the ratio of the total vinyl bond amount to the total bond amount of the conjugated diene compound can be known with an infrared spectrophotometer.

(Block copolymer structure)
As the block copolymer, when the polymer block A is “A” and the polymer block B is “B”, for example, A-B-A type, A-B-A-B type, B-A -BA type, (AB-) nX type (where n is an integer of 1 or more, X is a reactive residue or polyfunctionality of a polyfunctional coupling agent such as silicon tetrachloride or tin tetrachloride) And a vinyl aromatic-conjugated diene compound block copolymer having a structure in which block units such as an A-B-A-B-A type are bonded. Among these, a block copolymer having an ABAB type or a BBABA type structure is compared with a block copolymer having an ABA type structure as a component (c). It is more preferable because of its excellent fluidity.

  The molecular structure of the block copolymer including the polymer block A and the polymer block B is not particularly limited, and may be, for example, linear, branched, radial, or any combination thereof. Also good. Polymer block A and polymer block B are random and tapered distributions of vinyl aromatic compounds and conjugated diene compounds in the molecular chains in each polymer block (in which monomer components increase or decrease along the molecular chain). ), Partly in the form of blocks, or any combination thereof. When there are two or more polymer blocks A or polymer blocks B in the repeating unit, each polymer block may have the same structure or a different structure.

  In the block copolymer, the ratio of the total vinyl bond amount to the total bond amount of the conjugated diene compound is preferably 45 to 90%, more preferably 50 to 90%, and 65 to 90%. Is more preferable, and 70 to 90% is particularly preferable. When the ratio of the total vinyl bond amount exceeds 90%, industrial production may be difficult.

(Vinyl bond amount)
In the total bond of the conjugated diene compound unit in the component (c1), the total ratio of 1,2-vinyl bond and 3,4-vinyl bond is 45 to 90%, preferably 50 to 90%. 65 to 90% is more preferable, and 70 to 90% is more preferable.

  The total proportion of 1,2-vinyl bonds and 3,4-vinyl bonds is within the above range. The component (c1) has excellent compatibility with the component (a), and the resulting resin composition has improved mechanical properties. .

  The method for controlling the total ratio of 1,2-vinyl bond and 3,4-vinyl bond within the above range is not particularly limited. For example, in the production of component (c1), the amount of 1,2-vinyl bond is adjusted. Examples thereof include a method of adding an agent and a method of adjusting the polymerization temperature.

  The “total vinyl bond amount relative to the total bond amount of the conjugated diene compound” (the total ratio of 1,2-vinyl bond and 3,4-vinyl bond with respect to the total bond) as used herein refers to the hydrogenated block copolymer resin. It refers to the amount of vinyl bonds in the block copolymer before hydrogenation. This can be calculated, for example, by measuring the block copolymer before hydrogenation with an infrared spectrophotometer and using the Hampton method. Moreover, it can calculate using a nuclear magnetic resonance (NMR) from the block copolymer after hydrogenation.

(Hydrogen addition rate)
In the (c1) hydrogenated block copolymer, the hydrogenation ratio of the block copolymer to the ethylenic double bond (double bond in the conjugated diene compound unit) is preferably 50 to 100%. More preferably, it is 80% or more, more preferably 85% or more, and particularly preferably 90% or more. It is preferable from the viewpoint of obtaining a resin composition having good heat resistance and weather resistance when the hydrogenation rate is within the above range.

  The method for controlling the hydrogenation rate within the above range is not particularly limited. For example, in the hydrogenation reaction of the ethylenic double bond of the block copolymer, the amount of hydrogen consumed is within the desired hydrogenation rate range. The method of controlling is mentioned.

  In this embodiment mode, the hydrogenation rate can be measured by nuclear magnetic resonance (NMR). Specifically, it can be measured by the method described in Examples described later.

(Production method)
(C1) It does not specifically limit as a manufacturing method of a hydrogenated block copolymer, A well-known manufacturing method can be used. Known production methods are not particularly limited. For example, JP-A-47-11486, JP-A-49-66743, JP-A-50-75651, JP-A-54-126255, JP-A-56-10542, JP-A-56-62847, JP-A-56-100840, JP-A-2-300218, British Patent 1130770, US Pat. No. 3,281,383 US Pat. No. 3,639,517, British Patent No. 1,020,720, US Pat. No. 3,330,024 and US Pat. No. 4,501,857.

<(C2) component>
The (c2) modified hydrogenated block copolymer includes, for example, the above (c1) hydrogenated block copolymer, an α, β-unsaturated carboxylic acid or a derivative thereof (an ester compound or an acid anhydride compound) Is a modified hydrogenated block copolymer obtained by reacting at a temperature of 80 to 350 ° C. in a molten state, a solution state or a slurry state in the presence or absence of a radical generator. In this case, the α, β-unsaturated carboxylic acid or derivative thereof is preferably grafted or added to the (c1) hydrogenated block copolymer in a proportion of 0.01 to 10% by mass.

  When (c1) hydrogenated block copolymer and (c2) modified hydrogenated block copolymer are used in combination, (c1) hydrogenated block copolymer and (c2) in (c) hydrogenated block copolymer resin ) The mixing ratio with the modified hydrogenated block copolymer is not particularly limited and can be arbitrarily determined.

<Number average molecular weight>
(C) The number average molecular weight (Mnc) of a component becomes like this. Preferably it is 5,000-1,000,000, More preferably, it is 100,000 or less. When Mnc is 1,000,000 or less, the role of the (c) hydrogenated block copolymer resin in the resin composition is only as an emulsifying dispersant (admixture) between polymer (polypropylene) and polymer (polyphenylene ether). It tends to be a role. That is, at the time of emulsification of a polymer (polypropylene) -polymer (polyphenylene ether) having a high viscosity in a molten bulk state, (c) a hydrogenated block copolymer resin as an emulsifying dispersant (admixture) is melt-mixed. In consideration of the melt viscosity of the (c) hydrogenated block copolymer, the number average molecular weight (Mnc) of the component (c) is 5,000 to 1,000,000. Preferably, it is 100,000 or less.

  The method for controlling the number average molecular weight (Mnc) of the component (c) to be within the above range is not particularly limited, and examples thereof include a method of adjusting the catalyst amount in the polymerization step of the component (c).

  In the present embodiment, the number average molecular weight (Mnc) of the component (c) can be measured under the following conditions using Showa Denko Co., Ltd. Gel Permeation Chromatography System 21. In this measurement, a column in which Showa Denko Co., Ltd. KG, one K-800RL, and one K-800R were connected in series was used as the column, and the column temperature was 40 ° C. The solvent is chloroform, the solvent flow rate is 10 mL / min, and the sample concentration is 1 g of hydrogenated block copolymer / 1 liter of chloroform solution. Moreover, a calibration curve is prepared using standard polystyrene (the molecular weight of standard polystyrene is 3650000, 217000, 1090000, 681000, 204000, 52000, 30200, 13800, 3360, 1300, 550). Further, the UV (ultraviolet) wavelength of the detection unit is measured by setting both standard polystyrene and hydrogenated block copolymer to 254 nm.

<Content of vinyl aromatic compound unit>
The content of the vinyl aromatic compound unit (hydrogenated block copolymer constituent unit derived from the vinyl aromatic compound) in the component (c) is 30 to 50% by mass, preferably 30 to 48% by mass, More preferably, it is 30-45 mass%, More preferably, it is 35-45 mass%. When the content of the vinyl aromatic compound unit is 30% by mass or more, the mechanical strength of the resin composition is improved, and when the content of the vinyl aromatic compound unit is 50% by mass or less, heat resistance and A resin composition having an excellent balance with impact resistance is obtained. In the present embodiment, the content of the vinyl aromatic compound unit can be measured by an ultraviolet spectrophotometer (UV). Specifically, it can be carried out by the method described in Examples described later.

  Further, the content of the vinyl aromatic compound unit is 30 to 50% by mass. (C) The hydrogenated block copolymer resin is a polyphenylene ether resin in an emulsified dispersion between a polypropylene resin and a polyphenylene ether resin. Good emulsification dispersion of the resin is given, and the resin composition obtained has a great advantage in heat resistance, mechanical properties and impact resistance.

[Component (d)]
The (d) ethylene-α-olefin copolymer rubber (hereinafter also referred to as “component (d)”) used in the present embodiment is a copolymer rubber of ethylene and α-olefin. (D) A component is not specifically limited, Although a well-known thing may be used, Melt flow rate (Based on MFR: ASTM D-1238 and measured at 190 degreeC and the load of 2.16 kg) is 0.1. It is preferable that it is -4.5g / 10min, and it is preferable that Shore A hardness (based on ASTM D-2240) is 75 or less.

  Although it does not specifically limit as (d) component, For example, the copolymer rubber etc. of ethylene and 1 type, or 2 or more types of C3-C20 alpha olefin are mentioned. (D) As a component, the copolymer rubber of ethylene and 1 type, or 2 or more types of C3-C10 alpha-olefin is preferable, and ethylene and 1 type, or 2 or more types of C4-C8 alpha-olefin are preferable. It is more preferable that it is a copolymer rubber, and one or more selected from the group consisting of ethylene and propylene, 1-butene, 1-hexene, 4-methyl-1-pentene and 1-octene. It is more preferable to use a copolymer rubber with a comonomer, and it is particularly preferable to use a copolymer rubber of ethylene and 1-octene. By using such a copolymer as the component (d), a resin composition having higher tensile elongation and higher impact resistance tends to be obtained.

  (D) The method for preparing the ethylene-α-olefin copolymer rubber is not particularly limited, and a catalyst that can easily obtain a high molecular weight α-olefin copolymer under normal processing conditions (for example, , Titanium, metallocene, or vanadium-based catalysts). Among these, a method using a metallocene catalyst and a titanium chloride catalyst is preferable from the viewpoint of stability of structure control. (D) As a method for producing the ethylene-α-olefin copolymer rubber, known methods described in JP-A-6-306121, JP-A-7-500622 and the like can be used.

  The shore A hardness (based on ASTM D-2240) of the component (d) alone is preferably 75 or less, more preferably 70 or less, and even more preferably 65 or less, from the viewpoint of low-temperature impact properties of the resin composition. The lower limit of the Shore A hardness of the component (d) alone is not particularly limited, but is 48 or more, for example.

  The method for controlling the Shore A hardness of the component (d) within the above range is not particularly limited, and examples thereof include a method of adjusting by controlling the content and density of ethylene units.

  The content of the α-olefin in the component (d) is not particularly limited, and is preferably 5% by mass or more and 20% by mass or more from the viewpoint of low temperature curability and flexibility of the resin composition. In view of the rigidity of the resin composition, it is preferably 50% by mass or less, and more preferably 48% by mass or less.

The density of the component (d) alone is not particularly limited, and is preferably 0.850 g / cm ³ or more and more preferably 0.855 g / cm ³ or more from the viewpoint of the rigidity of the resin composition. From the viewpoint of obtaining a resin composition having high impact resistance and high tensile elongation at break, 0.910 g / cm ³ or less is preferable, and 0.885 g / cm ³ or less is more preferable.

As the component (d), two or more kinds of ethylene-α-olefin copolymer rubber may be used. In this case, from the viewpoint of further improving the impact resistance, tensile elongation and rigidity of the resin composition, for example, it is preferable to use two or more kinds of ethylene-α-olefin copolymer rubbers having different densities. From the viewpoint of impact resistance, tensile elongation at break and rigidity of the product, ethylene-α-olefin copolymer rubber having a density of 0.857 g / cm ³ and ethylene-α-olefin copolymer having a density of 0.870 g / cm ³ A combined rubber can be used in combination.

  The melt flow rate of component (d) as a single component (MFR: measured in accordance with ASTM D-1238 at 190 ° C. and a load of 2.16 kg) is a morphological change due to dispersion of component (d) in the resin composition. From the viewpoint of stabilization and the impact resistance of the resin composition, 0.1 to 4.5 g / 10 min is preferable, and 0.3 to 3 g / 10 min is more preferable.

  The method for controlling the melt flow rate of the component (d) within the above range is not particularly limited. For example, when the component (d) is produced, a method for adjusting the polymerization temperature and the polymerization pressure, ethylene in the polymerization system, and the like. And a method for adjusting the molar ratio between the monomer concentration of α-olefin and the hydrogen concentration.

  The molecular weight distribution of component (d) (Mw / Mn; Mw is the weight average molecular weight, and Mn is the number average molecular weight) is not particularly limited, but is preferably 1.3 to 5.0.

  When the MFR of the component (d) is 0.1 to 4.5 g / 10 minutes and the Shore A hardness is 75 or less, the (d) ethylene-α-olefin copolymer rubber in the resin composition is only (a) It is a component that serves as an impact resistance imparting agent between two or more resins selected from the group consisting of polypropylene resins, (b) polyphenylene ether resins, and (c) hydrogenated block copolymer resins.

  Furthermore, when the content of the vinyl aromatic compound unit in the (c) hydrogenated block copolymer resin is 30 to 50% by mass, and the Shore A hardness of the (d) ethylene-α-olefin copolymer rubber is 75 or less. In the emulsification dispersion between (a) a polypropylene resin and (b) a polyphenylene ether resin, (b) a good emulsification dispersion state of the polyphenylene ether resin is given, and the resulting resin composition has a tensile elongation and resistance to resistance. Giving great advantage to impact.

[Content ratio of each component]
In the resin composition of the present embodiment, the mass ratio ((c) :( d)) of (c) hydrogenated block copolymer resin and (d) ethylene-α-olefin copolymer rubber is (b) From the viewpoint of obtaining a polymer alloy in which the polyphenylene ether resin is stably emulsified and dispersed in a matrix containing (a) a polypropylene resin, the ratio is preferably 1:99 to 99: 1, more preferably 10:90. It is -90: 10, More preferably, it is 20: 80-80: 20, Most preferably, it is 30: 70-70: 30.

  In the resin composition of the present embodiment, the total content of the components (c) and (d) is preferably 1 with respect to 100 parts by mass of the total content of the components (a) and (b). It is -50 mass parts, More preferably, it is 2-45 mass parts, More preferably, it is 3-40 mass parts, Most preferably, it is 10-30 mass parts. When the total content of the components (c) and (d) is within the above range, a resin composition excellent in heat resistance and impact resistance tends to be obtained.

  Furthermore, in the resin composition of the present embodiment, the mass ratio ((a) :( b)) of the components (a) and (b) is preferably 25:75 to 99: 1, more preferably. 27:73 to 95: 5, more preferably 26:74 to 92: 8, and particularly preferably 30:70 to 50:50. It is preferable in terms of heat resistance and impact resistance of the resin composition that the mass ratio of the components (a) and (b) is within the above range.

[(E) component and (f) component]
In the resin composition of the present embodiment, from the viewpoint of improving impact resistance, as an optional component, (e) a second hydrogenated block copolymer resin (hereinafter also referred to as “component (e)”) and / or Alternatively, (f) a third hydrogenated block copolymer resin (hereinafter also referred to as “component (f)”) may be further included.

  In the resin composition of the present embodiment, the total content of the components (e) and / or (f) is 1 to 15 with respect to 100 parts by mass of the total content of the components (a) and (b). The mass is preferably 2 parts by mass, more preferably 2 to 12 parts by mass, and even more preferably 3 to 10 parts by mass.

  In the resin composition of the present embodiment, when the components (e) and (f) are used in combination, the mass ratio ((e) :( f)) of the components (e) and (f) is preferably Is 10:90 to 90:10, more preferably 20:80 to 80:20, and still more preferably 30:70 to 70:30.

<(E) component>
The component (e) used in the present embodiment is (e1) a second hydrogenated block copolymer and / or (e2) a second modified hydrogenated block copolymer described later.

<(E1) component>
(E1) The second hydrogenated block copolymer includes at least one polymer block A mainly composed of a vinyl aromatic compound and at least one polymer block B mainly composed of a conjugated diene compound. A hydrogenated block copolymer obtained by hydrogenating a block copolymer containing 10% by mass to 30% by mass of a vinyl aromatic compound unit (hydrogenated block copolymer-derived unit derived from a vinyl aromatic compound). In total bonds of conjugated diene compound units (hydrogenated block copolymer constituent units derived from conjugated diene compounds), the total proportion of 1,2-vinyl bonds and 3,4-vinyl bonds is 25% or more and less than 70% It is. Moreover, in the said (e) component, the hydrogenation rate with respect to the ethylenic double bond (double bond in a conjugated diene compound unit) of the said block copolymer is 80 to 100%. Furthermore, the number average molecular weight (Mne-1A) of the polymer block A forming the component (e1) is preferably 4,000 to 8,000.

  In the total bond of the conjugated diene compound unit in the component (e1), the total ratio of 1,2-vinyl bond and 3,4-vinyl bond is 25% or more and less than 70%, and is 30 to 60%. Preferably, it is 40 to 60%, more preferably 40 to 55%.

  In the total bond of the conjugated diene compound unit in the component (e1), when the total ratio of 1,2-vinyl bond and 3,4-vinyl bond is within the above range, the resulting resin composition has a tensile elongation or low temperature. The impact resistance at is improved.

  The method for controlling the total ratio of 1,2-vinyl bond and 3,4-vinyl bond within the above range is not particularly limited. For example, in the production of component (e1), the amount of 1,2-vinyl bond is adjusted. Examples thereof include a method of adding an agent and a method of adjusting the polymerization temperature.

  In this embodiment, the total ratio of 1,2-vinyl bond and 3,4-vinyl bond can be measured with an infrared spectrophotometer.

((E1) Structure of second hydrogenated block copolymer)
(E1) The structure of the second hydrogenated block copolymer is not particularly limited when the polymer block A is “A” and the polymer block B is “B”. For example, AB- A type, A-B-A-B type, (A-B-) n-X type (where n is an integer of 1 or more, X is a polyfunctional coupling agent such as silicon tetrachloride or tin tetrachloride) Reactive residues or initiator residues such as polyfunctional organolithium compounds are shown.), AABABA type vinyl aromatic compound-conjugated diene block having a structure in which block units are bonded Examples thereof include hydrogenated products of copolymers. Among these, a hydrogenated block copolymer having an A-B-A-B type structure is more preferable because it is excellent in fluidity as compared with an ABA type hydrogenated block copolymer.

(Polymer block A)
The polymer block A mainly composed of a vinyl aromatic compound is a homopolymer block of a vinyl aromatic compound or a copolymer block of a vinyl aromatic compound and a conjugated diene compound. In the polymer block A, “mainly composed of a vinyl aromatic compound” means that the polymer block A contains more than 50% by mass of vinyl aromatic compound units, and 70% by mass of vinyl aromatic compound units. % Or more is preferable.

  Although it does not specifically limit as said vinyl aromatic compound, For example, styrene, (alpha) -methyl styrene, vinyl toluene, p-tert- butyl styrene, diphenylethylene etc. are mentioned. These may be used alone or in combination of two or more. Of the above, styrene is preferred. Examples of the conjugated diene compound include the compounds described below, which may be used alone or in combination of two or more.

(Polymer block B)
The polymer block B mainly composed of a conjugated diene compound is a homopolymer block of a conjugated diene compound or a random copolymer block of a conjugated diene compound and a vinyl aromatic compound. In the polymer block B, “consisting mainly of a conjugated diene compound” means that the polymer block B contains more than 50% by mass of conjugated diene compound units, and contains 70% by mass or more of conjugated diene compound units. It is preferable to do.

  The conjugated diene compound is not particularly limited, and examples thereof include butadiene, isoprene, 1,3-pentadiene, 2,3-dimethyl-1,3-butadiene and the like. These may be used alone or in combination of two or more. Among the above, butadiene, isoprene and combinations thereof are preferable. Examples of the vinyl aromatic compound include the aforementioned compounds, and these may be used alone or in combination of two or more.

  The polymer block B may be a single polymer block in which the ratio of the total vinyl bond amount to the total bond amount of the conjugated diene compound unit is 25% or more and less than 70%, and the ratio is 25 to 45%. Conjugated diene compound having at least one polymer block B1 mainly composed of a conjugated diene compound and at least one polymer block B2 mainly composed of a conjugated diene compound whose ratio is 45% or more and less than 70% The polymer block B mainly composed of A block copolymer having such a block structure is, for example, when the polymer block A is “A”, the polymer block B1 is “B1”, and the polymer block B2 is “B2”. It can be obtained by a known polymerization method in which the total vinyl bond amount is controlled based on the feed sequence of each monomer unit represented by -B2-B1-A.

(Block copolymer structure)
As the structure of the block copolymer, when the polymer block A is “A” and the polymer block B is “B”, for example, A-B-A type, A-B-A-B type, B -A-B-A type, (A-B-) n-X type (where n is an integer of 1 or more, X is a reactive residue or a polyfunctional coupling agent such as silicon tetrachloride or tin tetrachloride) And a block copolymer of vinyl aromatic-conjugated diene compound having a structure in which block units such as ABABABA type are bonded. preferable. Among these, a block copolymer having an ABAB type or a BBABA type structure is used as a component (e1) as compared with a block copolymer having an ABA type structure. It is more preferable because of excellent fluidity.

  The molecular structure of the block copolymer including the polymer block A and the polymer block B is not particularly limited, and may be, for example, linear, branched, radial, or any combination thereof. Also good. Polymer block A and polymer block B are random and tapered distribution of vinyl aromatic compound or conjugated diene compound in the molecular chain in each polymer block (in which the monomer component increases or decreases along the molecular chain) ), Partly in the form of blocks, or any combination thereof. When there are two or more polymer blocks A or B in the component (e1), the polymer blocks may have the same structure or different structures.

  In the block copolymer, the ratio of the total vinyl bond amount to the total bond amount of the conjugated diene compound unit is preferably 25% or more and less than 70%, more preferably 30 to 60%, and more preferably 40 to 60 % Is more preferable, and 40 to 55% is particularly preferable.

(Hydrogen addition rate)
Moreover, (e1) 2nd hydrogenated block copolymer WHEREIN: As a hydrogenation rate with respect to the ethylenic double bond (double bond in a conjugated diene compound unit) in the said block copolymer, it is 80-100%. Yes, preferably 90% or more, more preferably 95% or more. When the hydrogenation rate is within the above range, a resin composition having good heat resistance and weather resistance can be obtained.

  The method for controlling the hydrogenation rate within the above range is not particularly limited. For example, in the hydrogenation reaction of the ethylenic double bond of the block copolymer, the amount of hydrogen consumed is within the desired hydrogenation rate range. The method of controlling is mentioned.

  In this embodiment mode, the hydrogenation rate can be measured by nuclear magnetic resonance (NMR). Specifically, it can be measured by the method described in Examples described later.

(Production method)
(E1) It does not specifically limit as a manufacturing method of a 2nd hydrogenated block copolymer, A well-known manufacturing method can be used. Known production methods are not particularly limited. For example, JP-A-47-11486, JP-A-49-66743, JP-A-50-75651, JP-A-54-126255, JP-A-56-10542, JP-A-56-62847, JP-A-56-100840, JP-A-2-300218, British Patent 1130770, US Pat. No. 3,281,383 US Pat. No. 3,639,517, British Patent No. 1,020,720, US Pat. No. 3,330,024 and US Pat. No. 4,501,857.

<(E2) component>
In addition, (e2) the second modified hydrogenated block copolymer includes, for example, the (e1) second hydrogenated block copolymer, an α, β-unsaturated carboxylic acid or a derivative thereof (ester compound or acid). An anhydride compound) is a modified hydrogenated block copolymer obtained by reacting at 80 to 350 ° C. in a molten state, a solution state or a slurry state in the presence or absence of a radical generator. In this case, the α, β-unsaturated carboxylic acid or derivative thereof is preferably grafted or added to the (e1) second hydrogenated block copolymer in a proportion of 0.01 to 10% by mass.

  When (e1) the second hydrogenated block copolymer and (e2) the second modified hydrogenated block copolymer are used in combination, (e) (e1) in the second hydrogenated block copolymer resin The mixing ratio of the second hydrogenated block copolymer and (e2) the second modified hydrogenated block copolymer can be determined without particular limitation.

<Number average molecular weight>
(E) The number average molecular weight (Mne) of a component becomes like this. Preferably it is 5,000-1,000,000, More preferably, it is 100,000 or less. When Mne is 1,000,000 or less, the role of (e) the second hydrogenated block copolymer resin in the resin composition is only (a) polypropylene resin, (b) polyphenylene ether resin and (c ) It tends to serve as an impact resistance imparting agent between two or more kinds of resins selected from the group consisting of hydrogenated block copolymer resins. That is, during emulsification of a polymer (polypropylene) -polymer (polyphenylene ether) -polymer (hydrogenated block copolymer) having a high viscosity in the melt bulk state, (e) the second hydrogenation as an impact resistance imparting agent In order for the block copolymer resin to diffuse preferably in the melt-mixing system, the number average molecular weight (Mne) of the component (e) is (e) considering the melt viscosity of the second hydrogenated block copolymer resin. It is preferably 5,000 to 1,000,000, more preferably 100,000 or less.

  (E) Although the method of controlling the number average molecular weight (Mne) of a component to the said range is not specifically limited, For example, the method of adjusting the catalyst amount in the superposition | polymerization process of (e) component is mentioned.

  In the present embodiment, the number average molecular weight (Mne) of the component (e) can be measured using a gel permeation chromatography system 21 manufactured by Showa Denko KK under the following conditions. In this measurement, a column in which Showa Denko Co., Ltd. KG, one K-800RL, and one K-800R were connected in series was used as the column, and the column temperature was 40 ° C. The solvent is chloroform, the solvent flow rate is 10 mL / min, and the sample concentration is 1 g of hydrogenated block copolymer / 1 liter of chloroform solution. Moreover, a calibration curve is prepared using standard polystyrene (the molecular weight of standard polystyrene is 3650000, 217000, 1090000, 681000, 204000, 52000, 30200, 13800, 3360, 1300, 550). Further, the UV (ultraviolet) wavelength of the detection unit 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 forming the second hydrogenated block copolymer resin (e) is, for example, as described above when the component (e) has an ABA structure. Based on the number average molecular weight (Mne) of the component (e), it is assumed that the molecular weight distribution of the component (e) is 1, and that two polymer blocks A mainly composed of vinyl aromatic compounds exist as the same molecular weight. , (MneA) = (Mne) × bonded vinyl aromatic compound amount ratio ÷ 2. Similarly, when the component (e) is a hydrogenated block copolymer of the ABABABA type, (MneA) = (Mne) × the ratio of the amount of bonded vinyl aromatic compounds ÷ 3 Can be obtained. In addition, in the step of synthesizing the vinyl aromatic compound-conjugated diene compound block copolymer, when the sequence of the block structure A and the block structure B is clear, the measurement is performed without depending on the above formula. It may be calculated from the ratio of the block structure A based on the number average molecular weight (Mne) of the component (e).

  The number average molecular weight (MneA) of the polymer block A forming the component (e) is preferably 4,000 to 8,000, more preferably 4,500 to 7,000.

  The number average molecular weight (MneA) of the polymer block A mainly composed of a vinyl aromatic compound is 4,000 to 8,000. (E) The second hydrogenated block copolymer resin has good impact resistance. It has a function of imparting properties, and can give a great advantage to the impact resistance of the resulting resin composition.

  The method of controlling the number average molecular weight (MneA) within the above range is not particularly limited, and examples thereof include a method of adjusting with the amount of the polymerization initiator.

<Content of vinyl aromatic compound unit>
In addition, the content of the vinyl aromatic compound unit (hydrogenated block copolymer constituent unit derived from the vinyl aromatic compound) in the component (e) is 10% by mass or more and less than 30% by mass, preferably 12 to 25%. It is 13 mass%, More preferably, it is 13-22 mass%. When the content of the vinyl aromatic compound unit in the component (e) is 10% by mass or more, the mechanical strength of the resin composition tends to be improved, and when it is less than 30% by mass, the heat resistance and impact resistance are increased. There exists a tendency to obtain the resin composition which is excellent in balance with property.

<Component (f)>
The component (f) used in the present embodiment is (f1) a third hydrogenated block copolymer and / or (f2) a third modified hydrogenated block copolymer described later.

<(F1) component>
(F1) The third hydrogenated block copolymer includes at least one polymer block A mainly composed of a vinyl aromatic compound and at least one polymer block B mainly composed of a conjugated diene compound. A hydrogenated block copolymer obtained by hydrogenating a block copolymer containing 20 to 70% by mass of a vinyl aromatic compound unit (hydrogenated block copolymer-derived unit derived from a vinyl aromatic compound), In all the bonds of the conjugated diene compound unit (hydrogenated block copolymer constituent unit derived from the conjugated diene compound), the total ratio of 1,2-vinyl bond and 3,4-vinyl bond is 25% or more and less than 60%. In the component (f1), the hydrogenation ratio of the block copolymer to the ethylenic double bond (double bond in the conjugated diene compound unit) is 10% or more and less than 80%.

  In the total bond of the conjugated diene compound unit in the component (f1), the total ratio of 1,2-vinyl bond and 3,4-vinyl bond is 25% or more and less than 60%, and 30 to 50%. Is more preferable.

  (F1) In the total bond of the conjugated diene compound unit in the component, when the total ratio of 1,2-vinyl bond and 3,4-vinyl bond is within the above range, the impact resistance at low temperature of the resin composition is low. improves.

  The method for controlling the total ratio of 1,2-vinyl bond and 3,4-vinyl bond within the above range is not particularly limited. For example, in the production of component (f1), the amount of 1,2-vinyl bond is adjusted. Examples thereof include a method of adding an agent and a method of adjusting the polymerization temperature.

  In this embodiment, the total ratio of 1,2-vinyl bond and 3,4-vinyl bond can be measured with an infrared spectrophotometer.

((F1) Structure of third hydrogenated block copolymer)
(F1) The structure of the third hydrogenated block copolymer is not particularly limited when the polymer block A is “A” and the polymer block B is “B”. A-B-A type, B-A-B-A type, (A-B-) n-X type (where n is an integer of 1 or more, X is a polyfunctional cup such as silicon tetrachloride, tin tetrachloride) A reaction residue of a ring agent or a residue of an initiator such as a polyfunctional organolithium compound.), And a structure such as an ABABABA type. Further, referring to the block structure, the polymer block B mainly composed of a conjugated diene compound contains a homopolymer block of a conjugated diene compound or a conjugated diene compound in an amount of more than 50% by mass, preferably 70% by mass or more. A polymer block A having a copolymer block structure of a conjugated diene compound and a vinyl aromatic compound, and further comprising a vinyl aromatic compound as a main component is a homopolymer block of vinyl aromatic compound, or vinyl It preferably has a copolymer block structure of a vinyl aromatic compound and a conjugated diene compound containing an aromatic compound in an amount exceeding 50% by mass, preferably 70% by mass or more.

(Polymer block A)
The polymer block A mainly composed of a vinyl aromatic compound is a homopolymer block of a vinyl aromatic compound or a copolymer block of a vinyl aromatic compound and a conjugated diene compound. In the polymer block A, “mainly composed of a vinyl aromatic compound” means that the polymer block A contains more than 50% by mass of vinyl aromatic compound units, and 70% by mass of vinyl aromatic compound units. % Or more is preferable.

  Although it does not specifically limit as said vinyl aromatic compound, For example, styrene, (alpha) -methyl styrene, vinyl toluene, p-tert- butyl styrene, diphenylethylene etc. are mentioned. These may be used alone or in combination of two or more. Of the above, styrene is preferred. Examples of the conjugated diene compound include the compounds described below, which may be used alone or in combination of two or more.

(Polymer block B)
The polymer block B mainly composed of a conjugated diene compound is a homopolymer block of a conjugated diene compound or a random copolymer block of a conjugated diene compound and a vinyl aromatic compound. In the polymer block B, “consisting mainly of a conjugated diene compound” means that the polymer block B contains more than 50% by mass of conjugated diene compound units, and contains 70% by mass or more of conjugated diene compound units. It is preferable to do.

  The conjugated diene compound is not particularly limited, and examples thereof include butadiene, isoprene, 1,3-pentadiene, 2,3-dimethyl-1,3-butadiene and the like. These may be used alone or in combination of two or more. Among the above, butadiene, isoprene and combinations thereof are preferable. Examples of the vinyl aromatic compound include the above-mentioned compounds, and may be used alone or in combination of two or more.

  Regarding the microstructure of the polymer block B (bonded form of the conjugated diene compound), the ratio of the total vinyl bond amount to the total bond amount of the conjugated diene compound unit is preferably 25% or more and less than 60%. % Is more preferable, and 30 to 50% is more preferable. When the ratio of the total vinyl bond amount to the total bond amount of the conjugated diene compound unit is less than 60%, the impact resistance at low temperature of the resin composition is preferably improved.

  The polymer block B may be a single polymer block in which the ratio of the total vinyl bond amount to the total bond amount of the conjugated diene compound unit is 25% or more and less than 60%, and the ratio of the total vinyl bond amount is At least one polymer block B1 mainly composed of a conjugated diene compound whose main component is 25 to 45% and a conjugated diene compound whose proportion of total vinyl bonds is less than 45 to 60%. It may be a polymer block B mainly composed of a conjugated diene compound having B2. A block copolymer having such a block structure is, for example, when the polymer block A is “A”, the polymer block B1 is “B1”, and the polymer block B2 is “B2”. It can be obtained by a known polymerization method in which the total vinyl bond amount is controlled based on the feed sequence of each monomer unit represented by -B2-B1-A.

(Block copolymer structure)
The molecular structure of the block copolymer including the polymer block A and the polymer block B is not particularly limited, and may be, for example, linear, branched, radial, or any combination thereof. Also good. Polymer block A and polymer block B are random and tapered distribution of vinyl aromatic compound or conjugated diene compound in the molecular chain in each polymer block (in which the monomer component increases or decreases along the molecular chain) ), Partly in the form of blocks, or any combination thereof. When two or more polymer blocks A or B are present in the component (f1), the polymer blocks may have the same structure or different structures.

  In the block copolymer, the ratio of the total vinyl bond amount to the total bond amount of the conjugated diene compound unit is preferably 25% or more and less than 60%, more preferably 25 to 55%, and more preferably 30 to 50%. % Is more preferable.

(Hydrogen addition rate)
In the third hydrogenated block copolymer (f1), the hydrogenation rate relative to the ethylenic double bond (double bond in the conjugated diene compound unit) in the block copolymer is 10% or more and 80%. Less than, preferably 10 to 60%, more preferably 20 to 50%. It is preferable for the hydrogenation rate to be within the above range since the low temperature impact property of the resin composition is improved. In this way, the component (f1) having a hydrogenation rate, for example, in the hydrogenation reaction of the ethylenic double bond of the block copolymer, the amount of hydrogen consumed is a desired hydrogenation rate (for example, 10% or more and less than 80%) ) Can be easily obtained by controlling to the range of

(Production method)
(F1) It does not specifically limit as a manufacturing method of a 3rd hydrogenated block copolymer, A well-known manufacturing method can be used. Known production methods are not particularly limited. For example, JP-A-47-11486, JP-A-49-66743, JP-A-50-75651, JP-A-54-126255, JP-A-56-10542, JP-A-56-62847, JP-A-56-100840, JP-A-2-300218, British Patent 1130770, US Pat. No. 3,281,383 US Pat. No. 3,639,517, British Patent No. 1,020,720, US Pat. No. 3,330,024 and US Pat. No. 4,501,857.

  In this (f1) third hydrogenated block copolymer, when the ratio of the total vinyl bond amount to the total bond amount of the conjugated diene compound is less than 60% and / or the hydrogenation rate is less than 80%, the resin The impact resistance at low temperature of the composition is improved, which is more preferable.

(Content of vinyl aromatic compound unit in component (f1))
(F1) The third hydrogenated block copolymer contains 20 to 70% by mass of vinyl aromatic compound units (hydrogenated block copolymer constituent units derived from vinyl aromatic compounds) as described above. Further, not only one (f1) component having a vinyl aromatic compound unit content in these ranges but also two or more different (f1) components having a different vinyl aromatic compound unit content can be used in combination. .

<(F2) component>
(F2) The third modified hydrogenated block copolymer is the same as (f1) the third hydrogenated block copolymer, for example, α, β-unsaturated carboxylic acid or a derivative thereof (ester compound or acid). An anhydride compound) is a modified hydrogenated block copolymer obtained by reacting at 80 to 350 ° C. in a molten state, a solution state or a slurry state in the presence or absence of a radical generator. In this case, the α, β-unsaturated carboxylic acid or derivative thereof is preferably grafted or added to the (f1) third hydrogenated block copolymer in a proportion of 0.01 to 10% by mass.

  When (f1) the third hydrogenated block copolymer and (f2) the third modified hydrogenated block copolymer are used in combination, (f1) in the (f) third hydrogenated block copolymer resin The mixing ratio of the third hydrogenated block copolymer and (f2) the third modified hydrogenated block copolymer can be determined without any particular limitation.

<Number average molecular weight>
The number average molecular weight (Mnf) of the component (f) is preferably 5,000 to 1,000,000, more preferably 100,000 or less. When Mnf is 1,000,000 or less, the role of (f) the third hydrogenated block copolymer resin in the resin composition is only (a) polypropylene resin, (b) polyphenylene ether resin, (c It tends to serve as an impact resistance imparting agent between two or more kinds of resins selected from the group consisting of (a) hydrogenated block copolymer resin and (d) a second hydrogenated block copolymer resin. That is, during emulsification of a polymer (polypropylene) -polymer (polyphenylene ether) -polymer (hydrogenated block copolymer) having a high viscosity in the melt bulk state, (f) a third hydrogenation as an impact resistance imparting agent. In order for the block copolymer-based resin to diffuse preferably in the melt-mixed system, (f) considering the melt viscosity of the third hydrogenated block copolymer-based resin, the number average molecular weight (Mnf) of the component (f) is It is preferably 5,000 to 1,000,000, more preferably 100,000 or less.

  The method of controlling the number average molecular weight (Mnf) of the component (f) within the above range is not particularly limited, and examples thereof include a method of adjusting the catalyst amount in the polymerization step of the component (f).

  In the present embodiment, the number average molecular weight (Mnf) of the component (f) can be measured under the following conditions using Showa Denko Co., Ltd. Gel Permeation Chromatography System 21. In this measurement, a column in which Showa Denko Co., Ltd. KG, one K-800RL, and one K-800R were connected in series was used as the column, and the column temperature was 40 ° C. The solvent is chloroform, the solvent flow rate is 10 mL / min, and the sample concentration is 1 g of hydrogenated block copolymer / 1 liter of chloroform solution. Moreover, a calibration curve is prepared using standard polystyrene (the molecular weight of standard polystyrene is 3650000, 217000, 1090000, 681000, 204000, 52000, 30200, 13800, 3360, 1300, 550). Further, the UV (ultraviolet) wavelength of the detection unit is measured by setting both standard polystyrene and the selectively hydrogenated block copolymer to 254 nm.

  The number average molecular weight (MnfA) of the polymer block A forming the third hydrogenated block copolymer resin (f) is, for example, as described above when the component (f) has an ABA structure. Based on the number average molecular weight (Mnf) of the component (f), it is assumed that the molecular weight distribution of the component (f) is 1, and that two polymer blocks A mainly composed of vinyl aromatic compounds exist as the same molecular weight. , (MnfA) = (Mnf) × the ratio of the amount of bonded vinyl aromatic compound ÷ 2. Similarly, when the component (f) is a hydrogenated block copolymer of the ABABABA type, (MnfA) = (Mnf) × the proportion of the amount of bound vinyl aromatic compound ÷ 3 Can be obtained. In addition, in the step of synthesizing the vinyl aromatic compound-conjugated diene compound block copolymer, when the sequence of the block structure A and the block structure B is clear, the measurement is performed without depending on the above formula. It may be calculated from the ratio of the block structure A based on the number average molecular weight (Mnf) of the component (f).

  The number average molecular weight (MnfA) of the polymer block A forming the component (f) is preferably 5,000 to 25,000, more preferably 5,000 to 14,000.

<Content of vinyl aromatic compound unit>
Moreover, it is preferable that content of the vinyl aromatic compound unit (hydrogenated block copolymer structural unit derived from a vinyl aromatic compound) in (f) component is 20-70 mass%, More preferably, 20- 60 mass%, More preferably, it is 20-40 mass%. When the content of the vinyl aromatic compound unit in the component (f) is 20% by mass or more, the mechanical strength of the resin composition tends to be improved, and when it is 70% by mass or less, the heat resistance and impact resistance are increased. There exists a tendency to obtain the resin composition which is excellent in balance with property.

[Morphology]
The resin composition of the present embodiment preferably has a matrix phase containing the component (a) and a dispersed phase containing the component (b). Such a morphology can be confirmed by a transmission electron microscope.

  The matrix phase may be composed of component (a) alone. The dispersed phase may be the component (b) alone, or may be composed of, for example, the component (b), the component (c), and the component (d). In this case, the resin composition of the present embodiment includes a matrix phase (component (a)) and a dispersed phase (component (b) alone or component (b), component (c), component (d), etc.). It has dispersed particles to make up. The component (c) and the component (d) may be included not only in the dispersed phase but also in the matrix phase to the extent that the effects of the present embodiment are not impaired. In the resin composition of the present embodiment, by taking such a morphology, the component (c) and the component (d) contained in the matrix phase and / or the dispersed phase are more effectively dispersed to improve the impact resistance. It is presumed that the state can be taken and the effect of the present embodiment is further improved (however, the operation of the present embodiment is not limited to this).

[(H) Other ingredients]
In the resin composition of the present embodiment, a mixture of (b) a polyphenylene ether resin and at least one selected from the group consisting of polystyrene, syndiotactic polystyrene, and high impact polystyrene can also be used suitably. .
More preferably, at least one selected from the group consisting of polystyrene, syndiotactic polystyrene and high-impact polystyrene is preferably 400 parts by mass or less, more preferably 100 parts by mass of (b) polyphenylene ether resin. Can be used in the range of 100 parts by mass or less, more preferably 50 parts by mass or less, particularly preferably 10 parts by mass or less.

  In the resin composition of the present embodiment, in addition to the above components, other additional components may be added as necessary within the range not impairing the effects of the present embodiment. Examples of such other additional components include, but are not limited to, vinyl aromatic compounds-conjugated diene compound block copolymers, vinyl aromatics not corresponding to the components (c), (e), and (f). Compound-hydrogenated block copolymer of conjugated diene compound, olefin elastomer not corresponding to component (d), antioxidant, metal deactivator, heat stabilizer, flame retardant (organophosphate ester compound, polyphosphoric acid Ammonium compounds, melamine polyphosphate compounds, phosphinates, magnesium hydroxide, aromatic halogen flame retardants, silicone flame retardants, etc., fluoropolymers, plasticizers (low molecular weight polyethylene, epoxidized soybean oil, polyethylene glycol) Flame retardants such as antimony trioxide, weather resistance (light) improver, polyolefin Nucleating agent, slip agent, inorganic or organic filler or reinforcing material (chopped strand glass fiber, glass long fiber, CF long fiber, polyacrylonitrile fiber, glass flake, glass beads, carbon black, titanium oxide, calcium carbonate, talc Mica, whisker, clay, magnesium hydroxide, magnesium sulfate and its fiber, silica, wollastonite conductive metal fiber, conductive carbon black, etc.), various colorants, release agents and the like.

[Loss tangent (tan δ)]
The resin composition according to the present embodiment has a ratio (−50 ° C. tan δ /) of a loss tangent of −50 ° C. (−50 ° C. tan δ) obtained by the following measurement method and a loss tangent of 0 ° C. (0 ° C. tan δ). 0 ° C. tan δ) is preferably 0.39 or more, more preferably 0.41 or more, and further preferably 0.42 or more.
<Measurement of loss tangent (tan δ)>
About the ISO test piece obtained from a resin composition, using a viscoelasticity measuring machine, tension mode, vibration frequency: 10 Hz, static load strain: 0.2%, dynamic load strain: 0.1%, contact load: Loss tangent (tan δ) at −50 ° C. and 0 ° C. when measured in a temperature sweep mode of 0.5 N, temperature increase rate: 3 ° C./min, temperature range: −100 ° C. to 160 ° C.

  The higher the ratio (−50 ° C. tan δ / 0 ° C. tan δ), the better, but the upper limit is, for example, 1.50. By setting the ratio (−50 ° C. tan δ / 0 ° C. tan δ) to 0.39 or more, the low-temperature impact property of the resin composition at 0 ° C. or less can be improved.

≪Method for producing resin composition≫
The resin composition of the present embodiment is obtained, for example, by melt-kneading a raw material containing the above-described components (a) to (d). The melt kneader is not particularly limited, and a known kneader can be used. For example, a single screw extruder, a multi-screw extruder including a twin screw extruder, a roll, a kneader, a Brabender plastograph, a Banbury mixer, etc. And a hot melt kneader. Among the above, a twin screw extruder is preferable. Specifically, the ZSK series manufactured by Coperion, the TEM series manufactured by Toshiba Machine Co., Ltd., the TEX series manufactured by Nippon Steel Works, Ltd., and the like can be used.

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

  The extruder is provided with a first raw material supply port on the upstream side with respect to the flow direction of the raw material, a first vacuum vent on the downstream side, a second raw material supply port on the downstream side, and a second vacuum vent on the downstream side. An extruder having a first raw material supply port upstream, a first vacuum vent downstream thereof, a second and third raw material supply ports downstream thereof, and a second vacuum vent downstream thereof; preferable.

  Among these, a kneading section is provided upstream of the first vacuum vent, a kneading section is provided between the first vacuum vent and the second raw material supply port, and the second raw material supply port and the second vacuum vent are further connected. Extruder with a kneading section in between, a kneading section upstream of the first vacuum vent, a kneading section between the first vacuum vent and the second raw material supply port, and a second raw material supply More preferred is an extruder in which a kneading section is provided between the mouth and the third raw material supply port, and a kneading section is provided between the second raw material supply port and the second vacuum vent.

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

  (A)-(d) As a method of melt-kneading the raw material containing a component, the following (1-1) process and (1-2) process are used using the twin-screw extruder which has several feed ports. Including method 1 is preferred.

(1-1): Melt-knead the total amount of component (b), a part or total amount of component (a), a part or total amount of component (c), and a part or total amount of component (d). Step (however, only a part of at least one component selected from the group consisting of (a) component, (c) component and (d) component is used)).
(1-2): The remaining amount of at least one component selected from the group consisting of the component (a), the component (c) and the component (d) with respect to the kneaded product obtained in the step (1-1). Process of melt-kneading.

  Moreover, the following (2-1) process-(2-3) process is included as a method of melt-kneading the raw material containing (a)-(d) component using the twin-screw extruder which has several feed ports. Method 2 is more preferred.

(2-1): A step of melt-kneading the total amount of the component (b), the part or the total amount of the component (a), and the part or the total amount of the component (c).
(2-2): With respect to the kneaded material obtained in the step (2-1), the remaining amount of at least one component selected from the group consisting of the component (a) and the component (c), and the component (d) A step of adding a part or all of the above and melt-kneading.
(2-3): A step of adding the remaining amount of component (d) to the kneaded product obtained in step (2-2) and melt-kneading (however, component d) in step (2-2) Except when all the amount of is added. ).

  Moreover, as a method of melt kneading the raw materials containing the components (a) to (d), the following steps (3-1) to (3-3) are included using a twin screw extruder having a plurality of feed ports. Method 3 is more preferred.

(3-1): A step of melt-kneading the total amount of the component (b), the part or the total amount of the component (a), and the part or the total amount of the component (c).
(3-2): The remaining amount of at least one component selected from the group consisting of the component (a) and the component (c) is added to the kneaded product obtained in the step (3-1), and melt-kneaded. Process.
(3-3): A step of adding the entire amount of the component (d) to the kneaded product obtained in the step (3-2) and melt-kneading.

  The melt kneading temperature and the screw rotation speed are not particularly limited, but can be appropriately selected from a melt kneading temperature of 200 to 370 ° C. and a screw rotation speed of 100 to 1200 rpm. In addition, when (e), (f), and (h) components are included in the raw material, the method of adding these components is not particularly limited, but the (e) and (f) components are the second raw material supply port and / or It is preferable to supply from the third raw material supply port.

≪Molded body≫
The molded body of the present embodiment includes the above-described resin composition.

  Moreover, the molded object of this Embodiment can be obtained by shape | molding the resin composition mentioned above, for example. The molding method is not particularly limited, and includes various conventionally known methods such as injection molding, extrusion molding, extrusion profile forming, and hollow molding. The molded body of the present embodiment obtained by such a molding method can be used as a molded product of various parts, a sheet, or a film. These various parts are not particularly limited, but include, for example, automobile parts. Specifically, bumpers, fenders, door panels, various moldings, emblems, engine hoods, wheel caps, roofs, spoilers, various aero parts, etc. Suitable for exterior parts and interior parts such as instrument panels, console boxes and trims.

  Furthermore, the molded body of the present embodiment can be suitably used as an interior / exterior part of an electric device. Specifically, various computers and peripheral devices thereof, other OA devices, televisions, videos, various disc players, etc. Examples include cabinets, chassis, refrigerators, air conditioners, and liquid crystal projectors. Moreover, it is suitable also for the electric wire and cable obtained by coat | covering the separator of a lithium ion battery for electrical devices, a metal conductor, or an optical fiber. Furthermore, the molded body of the present embodiment is suitable for parts such as various pump casings and boiler casings in industrial parts.

  Next, the present embodiment will be described more specifically with reference to examples and comparative examples. However, the present embodiment is not limited to the following examples unless it exceeds the gist.

  Each physical property of each material was measured as follows.

[Number average molecular weight]
The number average molecular weight of each component was measured by gel permeation chromatography (GPC) (mobile phase: chloroform, standard substance: polystyrene). Specifically, it measured on condition of the following using the gel permeation chromatography System21 by Showa Denko KK. In this measurement, a column in which Showa Denko Co., Ltd. KG, one K-800RL, and one K-800R were connected in series was used as the column, and the column temperature was 40 ° C. The solvent was chloroform, the solvent flow rate was 10 mL / min, and the sample concentration was 1 g of hydrogenated block copolymer / 1 liter of chloroform solution. In addition, calibration curves were prepared using standard polystyrene (the molecular weight of standard polystyrene is 3650000, 217000, 1090000, 681000, 204000, 52000, 30200, 13800, 3360, 1300, 550). Further, the UV (ultraviolet) wavelength of the detection part was measured by setting both standard polystyrene and hydrogenated block copolymer to 254 nm.

[Measurement of bound styrene content]
The amount of bound styrene (content of vinyl aromatic compound unit) in the hydrogenated block copolymer resin was measured using an ultraviolet spectrophotometer (UV-2450, manufactured by Shimadzu Corporation) for the hydrogenated block copolymer resin.

[Measurement of total vinyl bond content]
The total amount of vinyl bonds in the conjugated diene compound unit in the hydrogenated block copolymer resin (the total ratio of 1,2-vinyl bonds and 3,4-vinyl bonds to the total bonds) is the value of the hydrogenated block copolymer resin. The block copolymer before hydrogenation was measured with an infrared spectrophotometer (manufactured by JASCO Corporation, FT / IR-230) and calculated by the Hampton method.

[Measurement of hydrogenation rate]
The hydrogenation rate of the block copolymer with respect to the ethylenic double bond (double bond in the conjugated diene compound unit) is determined by nuclear magnetic resonance (NMR) (device name: DPX-400 BRUKER) Manufactured).

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

[Melt flow rate (MFR)]
The MFR of the component (a) was measured under the conditions of 230 ° C. and a load of 2.16 kg in accordance with JIS K7210.

  The MFR of the component (d) was measured under the conditions of 190 ° C. and a load of 2.16 kg in accordance with ASTM D-1238.

[Reduced viscosity]
The reduced viscosity of the polyphenylene ether resin was measured under conditions of 0.5 g / dL chloroform solution and 30 ° C.

[Shore A hardness]
(D) The Shore A hardness of the component was measured based on ASTM D-2240.

[density]
(D) The density of the component was measured based on ASTM D-792.

[Production of resin composition]
1. Component (a) (polypropylene resin)
The following components (a-1) and (a-2) were used as the component (a).
(A-1) Propylene homopolymer (melting point: 167 ° C., MFR: 0.4 g / 10 min)
(A-2) Propylene homopolymer (melting point: 165 ° C., MFR: 6.0 g / 10 min)

2. Component (b) (polyphenylene ether resin)
2,6-xylenol was oxidatively polymerized to obtain a polyphenylene ether homopolymer. The obtained polyphenylene ether homopolymer was used as component (b). The reduced viscosity of the polyphenylene ether homopolymer was 0.42.

3. Component (c) (hydrogenated block copolymer resin)
The following components (c-1) to (c-3) were used as the component (c).

(C-1)
A hydrogenated block copolymer having a B-A-B-A type structure of hydrogenated polybutadiene-polystyrene (1) -hydrogenated polybutadiene-polystyrene (2) was synthesized by a conventional method. The characteristics of the hydrogenated block copolymer (c-1) are shown below.
Bonded styrene content: 43% by mass
Total vinyl bond content in polybutadiene units in the hydrogenated block copolymer (total ratio of 1,2-vinyl bond and 3,4-vinyl bond to all bonds): 75%
Number average molecular weight (Mnc): 98,000
Number average molecular weight (MncA) of polystyrene block (1): 20,000
Number average molecular weight (MncA) of polystyrene block (2): 22,000
Hydrogenation ratio of block copolymer to ethylenic double bond (double bond in polybutadiene unit): 99.9%

(C-2)
A hydrogenated block copolymer (Tough Tech H1043 manufactured by Asahi Kasei Chemicals Corporation) was used as the component (c-2). The amount of bound styrene in component (c-2) was 67% by mass. The total vinyl bond content in the conjugated diene compound unit in the hydrogenated block copolymer was 40%.

(C-3)
A hydrogenated block copolymer (Tuftec H1051 manufactured by Asahi Kasei Chemicals Corporation) was used as the component (c-3). The amount of bound styrene in component (c-3) was 42% by mass. The total vinyl bond content in the conjugated diene compound unit in the hydrogenated block copolymer was 36%.

4). Component (d) (ethylene-α-olefin copolymer rubber)
The following components (d-1) to (d-4) were used as the component (d).

(D-1)
Ethylene-1-octene copolymer rubber was synthesized by a conventional method. The characteristics of the ethylene-1-octene copolymer rubber (d-1) are shown below.
Shore A hardness: 50, MFR: 1.0, density: 0.857

(D-2)
Ethylene-1-octene copolymer rubber was synthesized by a conventional method. The characteristics of the ethylene-1-octene copolymer rubber (d-2) are shown below.
Shore A hardness: 66, MFR: 0.5, density: 0.863

(D-3)
Ethylene-1-octene copolymer rubber was synthesized by a conventional method. The characteristics of the ethylene-1-octene copolymer rubber (d-3) are shown below.
Shore A hardness: 75, MFR: 1.0, density: 0.870

(D-4)
Ethylene-1-octene copolymer rubber was synthesized by a conventional method. The characteristics of the ethylene-1-octene copolymer rubber (d-4) are shown below.
Shore A hardness: 75, MFR: 5.0, density: 0.870

5. Component (e) (second hydrogenated block copolymer resin)
A hydrogenated block copolymer having an ABAB type structure of polystyrene (1) -hydrogenated polybutadiene-polystyrene (2) -hydrogenated polybutadiene was synthesized by a conventional method. The synthesized hydrogenated block copolymer was used as component (e). The characteristics of the hydrogenated block copolymer are shown below.
Bonded styrene content: 17% by mass
Total vinyl bond content in polybutadiene units in the hydrogenated block copolymer (total ratio of 1,2-vinyl bond and 3,4-vinyl bond to all bonds): 50%
Hydrogenation ratio of block copolymer to ethylenic double bond (double bond in polybutadiene unit): 99.9%
Number average molecular weight (Mne): 65,000
Number average molecular weight (MneA) of polystyrene block (1): 5,300
Number average molecular weight of polystyrene block (2): (MneA) 5,700

6). Component (f) (third hydrogenated block copolymer resin)
A hydrogenated block copolymer having a structure of polystyrene (1) -hydrogenated polybutadiene-polystyrene (2) ABA type was synthesized by a conventional method. The synthesized hydrogenated block copolymer was used as the component (f). The characteristics of the hydrogenated block copolymer are shown below.
Bonded styrene content: 30% by mass
Total vinyl bond content in polybutadiene units in the hydrogenated block copolymer (total ratio of 1,2-vinyl bond and 3,4-vinyl bond to all bonds): 40%
Hydrogenation ratio of block copolymer to ethylenic double bond (double bond in polybutadiene unit): 45%
Number average molecular weight (Mnf): 72,000
Number average molecular weight (MnfA) of polystyrene block (1): 10,700
Number average molecular weight (MnfA) of polystyrene block (2): 11,000

7). (H) Component (Other block copolymer resin)
(H-1)
A block copolymer having an ABA type structure of polystyrene (1) -polybutadiene-polystyrene (2) was synthesized by a conventional method. The characteristics of the block copolymer (h-1) are shown below.
Bonded styrene content: 30% by mass
Total vinyl bond content in polybutadiene units (total ratio of 1,2-vinyl bond and 3,4-vinyl bond to all bonds): 12%
Number average molecular weight (Mnh): 91,000
Number average molecular weight (MnhA) of polystyrene block (1): 13,300
Number average molecular weight (MnhA) of polystyrene block (2): 14,000

(H-2)
A block copolymer having an ABA type structure of polystyrene (1) -polybutadiene-polystyrene (2) was synthesized by a conventional method. The characteristics of the block copolymer (h-2) are shown below.
Bonded styrene content: 30%
Total vinyl bond content in polybutadiene units (total ratio of 1,2-vinyl bond and 3,4-vinyl bond to all bonds): 11%
Number average molecular weight (Mnh): 136,000
Number average molecular weight (MnhA) of polystyrene block (1): 20,800
Number average molecular weight (MnhA) of polystyrene block (2): 20,000

[Examples 1 to 12 and Comparative Examples 1 to 6]
Using the twin-screw extruder (ZSK-25 manufactured by Coperion Co., Ltd.) having a first raw material supply port, a second raw material supply port (located at substantially the center of the extruder) and a third raw material supply port, the above (a) to ( Each component such as f) was supplied to the first to third raw material supply ports of the extruder at the composition shown in Table 1 and melt kneaded to obtain a resin composition as pellets. The twin screw extruder was set to a barrel temperature of 270 to 320 ° C. and a screw rotation speed of 300 rpm. Each physical property of the obtained resin composition was evaluated as follows. The measurement results are shown in Table 1.

<Tensile elongation>
The resin composition pellets obtained in Examples and Comparative Examples are supplied to a screw in-line type injection molding machine set at 240 to 280 ° C. and injection molded under the conditions of a mold temperature of 60 ° C. A test piece was prepared. The prepared test piece was allowed to stand in an environment of 80 ° C. for 24 hours using a gear oven and subjected to a heat history treatment. About the test piece which performed the heat history process, tensile elongation was measured according to ISO527. At this time, the standard deviation was calculated from the tensile elongation values of 10 test pieces. A smaller standard deviation indicates a more stable morphology.

<Charpy impact strength>
Charpy impact strength measurement was performed by supplying pellets of the resin compositions obtained in Examples and Comparative Examples to a screw in-line type injection molding machine set at 240 to 280 ° C. and injection molding at a mold temperature of 60 ° C. For test piece. The obtained test piece was left to stand in an environment of 80 ° C. for 24 hours using a gear oven to perform a heat history treatment. About the test piece after a heat history process, the Charpy impact strength was measured according to ISO179 in 23 degreeC and -40 degreeC environment.

<Measurement of loss tangent (tan δ)>
The resin composition pellets obtained in the examples and comparative examples are supplied to a screw in-line injection molding machine set at 240 to 280 ° C. and injection molded under the conditions of a mold temperature of 60 ° C. to produce an ISO test piece. did. The test piece is mounted on a viscoelasticity measuring device “EPLEXOR500N (manufactured by GABO)”. Tensile mode, vibration frequency is 10 Hz, static load strain is 0.2%, dynamic load strain is 0.1%, contact load Tan δ ratio (−50 ° C. tan δ) from tan δ values read at −50 ° C. and 0 ° C. in a temperature sweep mode of 0.5 N, temperature rising rate of 3 ° C./min, and temperature range of −100 ° C. to 160 ° C. / 0 ° C. tan δ) was calculated.

<War of molded piece>
The resin composition pellets obtained in the examples and comparative examples were supplied to a screw in-line injection molding machine set at 240 to 280 ° C. and injection molded at a mold temperature of 60 ° C. A 2 mm flat plate was obtained. From the 15 points shown in FIG. 1, a virtual plane is set by the least square method using a three-dimensional measuring instrument manufactured by Mitutoyo Corporation, and the deviation of the position of 15 points from the plane is obtained. The value obtained by subtracting the minimum value from the value was defined as the flatness of the flat plate. The smaller this value, the less the warp of the molded piece.

  The resin composition and molded product of the present invention have industrial applicability as automotive parts, heat-resistant parts, electronic device parts, industrial parts, and coating materials.

Claims (14)

(A) a polypropylene resin, (b) a polyphenylene ether resin, (c) a hydrogenated block copolymer resin, and (d) a copolymer rubber of ethylene and 1-octene ,
The component (c) is a hydrogenated block copolymer comprising at least one polymer block A mainly composed of a vinyl aromatic compound and at least one polymer block B mainly composed of a conjugated diene compound. A hydrogenated block copolymer and / or a modified product of the hydrogenated block copolymer,
In the total bond of the conjugated diene compound unit in the component (c), the total ratio of 1,2-vinyl bond and 3,4-vinyl bond is 45 to 90%,
The resin composition in which the component (c) contains 30 to 50% by mass of a vinyl aromatic compound unit (provided that the crosslinked product of the component (a) and the component (d) is excluded).   The melt flow rate of the component (d) (MFR: based on ASTM D-1238, measured at 190 ° C. under a load of 2.16 kg) is 0.1 to 4.5 g / 10 min. The resin composition as described.   The resin composition according to claim 1 or 2, wherein the component (d) has a Shore A hardness (according to ASTM D-2240) of 75 or less.   In the said (c) component, the hydrogenation rate with respect to the ethylenic double bond (double bond in a conjugated diene compound unit) of the said block copolymer is 50-100%, Any one of Claims 1-3. The resin composition described in 1. The total content of the components (c) and (d) is 1 to 50 parts by mass with respect to 100 parts by mass of the total content of the components (a) and (b).
The mass ratio ((a) :( b)) of the components (a) and (b) is 25:75 to 99: 1,
The resin composition of any one of Claims 1-4 whose mass ratio ((c) :( d)) of said (c) and (d) component is 1: 99-99: 1.   6. The total proportion of 1,2-vinyl bonds and 3,4-vinyl bonds in the total bond of the conjugated diene compound unit in the component (c) is 70 to 90%. The resin composition described in 1.   In the said (c) component, the hydrogenation rate with respect to the ethylenic double bond (double bond in a conjugated diene compound unit) of the said block copolymer is 80 to 100%, Any one of Claims 1-6. The resin composition described in 1. (E) a second hydrogenated block copolymer resin and / or (f) a third hydrogenated block copolymer resin,
The total content of the components (e) and / or (f) is 1 to 15 parts by mass with respect to 100 parts by mass of the total content of the components (a) and (b).
A block copolymer comprising the components (e) and (f) comprising at least one polymer block A mainly composed of a vinyl aromatic compound and at least one polymer block B mainly composed of a conjugated diene compound. A hydrogenated block copolymer obtained by hydrogenating a polymer and / or a modified product of the hydrogenated block copolymer,
The component (e) contains 10% by mass or more and less than 30% by mass of a vinyl aromatic compound unit,
The component (f) contains 20 to 70% by mass of vinyl aromatic compound units,
In the total bond of the conjugated diene compound unit in the component (e), the total ratio of 1,2-vinyl bond and 3,4-vinyl bond is 25% or more and less than 70%,
In the total bond of the conjugated diene compound unit in the component (f), the total ratio of 1,2-vinyl bond and 3,4-vinyl bond is 25% or more and less than 60%,
In the component (c), the hydrogenation ratio of the block copolymer to the ethylenic double bond (double bond in the conjugated diene compound unit) is 80 to 100%,
In the component (e), the hydrogenation ratio of the block copolymer to the ethylenic double bond (double bond in the conjugated diene compound unit) is 80 to 100%,
In the component (f), the hydrogenation ratio of the block copolymer to the ethylenic double bond (double bond in the conjugated diene compound unit) is 10% or more and less than 80%,
The resin composition according to any one of claims 1 to 7, wherein the polymer block A forming the component (e) has a number average molecular weight (MneA) of 4,000 to 8,000. The resin composition according to any one of claims 1 to 8, wherein a mass ratio ((a) :( b)) of the components (a) and (b) is 30:70 to 50:50. .   The resin composition according to any one of claims 1 to 9, wherein the number average molecular weight (Mnc) of the component (c) is 100,000 or less. The component (a) is homopolypropylene and / or block polypropylene,
The melt flow rate of the component (a) (MFR: based on JIS K7210, measured at 230 ° C. under a load of 2.16 kg) is 0.1 to 100 g / 10 min. 2. The resin composition according to item 1.   The resin composition according to any one of claims 1 to 11, which has a matrix phase containing the component (a) and a dispersed phase containing the component (b). (A) a polypropylene resin, (b) a polyphenylene ether resin, (c) a hydrogenated block copolymer resin , and (d) a copolymer rubber of ethylene and 1-octene ,
The component (c) is a hydrogenated block copolymer comprising at least one polymer block A mainly composed of a vinyl aromatic compound and at least one polymer block B mainly composed of a conjugated diene compound. A hydrogenated block copolymer and / or a modified product of the hydrogenated block copolymer,
The ratio (−50 ° C. tan δ / 0 ° C. tan δ) of the loss tangent at −50 ° C. (−50 ° C. tan δ) obtained by the following measurement method to the loss tangent at 0 ° C. (0 ° C. tan δ) is 0.39 or more. A resin composition (excluding a crosslinked product of the component (a) and the component (d)) ;
<Measurement of loss tangent (tan δ)>
About the ISO test piece obtained from a resin composition, using a viscoelasticity measuring machine, tension mode, vibration frequency: 10 Hz, static load strain: 0.2%, dynamic load strain: 0.1%, contact load: Loss tangent (tan δ) at −50 ° C. and 0 ° C. when measured in a temperature sweep mode of 0.5 N, temperature increase rate: 3 ° C./min, temperature range: −100 ° C. to 160 ° C.   The molded object containing the resin composition of any one of Claims 1-13.

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