JP6192623B2 - 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.

  For example, Patent Documents 1 to 3 propose a composition of a polyphenylene ether resin, a polypropylene resin, and a hydrogenated block copolymer. The hydrogenated block copolymer is a mixture of a polyphenylene ether resin and a polypropylene resin. It is disclosed that it is a component that acts as an agent and further imparts impact resistance.

  When attention is paid to the hydrogenated block copolymer used in the invention described in the above-mentioned patent document, it is described as follows.

  Patent Document 1 discloses a polymer block B mainly composed of a conjugated diene compound in which the ratio of the vinyl bond amount to the total bond amount of the polymer block A mainly composed of a vinyl aromatic compound and the conjugated diene compound is 30 to 95%. A hydrogenated block copolymer obtained by hydrogenating a block copolymer consisting of is described.

  Patent Document 2 discloses a polymer block B mainly composed of a conjugated diene compound in which the ratio of the vinyl bond amount to the total bond amount of the polymer block A mainly composed of a vinyl aromatic compound and the conjugated diene compound is 65 to 75%. A hydrogenated block copolymer obtained by hydrogenating a block copolymer composed of less than 65 to 80% is described.

  Patent Document 3 discloses a block copolymer comprising a polymer block A mainly composed of styrene and a polymer block B mainly composed of butadiene in which the ratio of the vinyl bond amount to the total bond amount of butadiene is 70 to 90%. Is a hydrogenated block copolymer obtained by hydrogenation, wherein the amount of bound styrene is 15 to 50% by mass, the number average molecular weight is 100,000 or less, and the number average molecular weight of the polymer block A is 8000 or more. A block copolymer is described.

International Publication No. 97/01600 Japanese Patent Laid-Open No. 09-12800 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 containing a polypropylene resin and a polyphenylene ether resin, which is more excellent in tensile elongation and impact resistance at low temperatures, and has a small molded piece warp and molded article thereof The purpose is to provide.

  As a result of intensive studies, the present inventors have further improved the tensile elongation and impact resistance at low temperatures by containing two specific hydrogenated block copolymer resins, and can prevent warping of the molded product. It has been found that a small resin composition can be obtained.

  That is, the present invention is as follows.

[1]
(A) a polypropylene resin, (b) a polyphenylene ether resin, (c) a first hydrogenated block copolymer resin, and (d) a second hydrogenated block copolymer resin,
The block copolymer comprising the components (c) and (d) 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,
In the total bond of the conjugated diene compound unit in the component (d), 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 (d), 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%.
[2]
[1] The resin composition according to [1], wherein a total ratio of 1,2-vinyl bonds and 3,4-vinyl bonds is 70 to 90% in all bonds of the conjugated diene compound unit in the component (c).
[3]
The resin composition according to [1] or [2], wherein the component (c) includes 30 to 50% by mass of a vinyl aromatic compound unit.
[4]
The resin composition according to any one of [1] to [3], wherein the component (d) includes 20 to 70% by mass of a vinyl aromatic compound unit.
[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], wherein a mass ratio ((c) :( d)) of the components (c) and (d) is 1:99 to 99: 1.
[6]
The resin composition according to any one of [1] to [5], wherein the component (d) includes 20 to 60% by mass of a vinyl aromatic compound unit.
[7]
In the component (d), any one of [1] to [6], wherein a hydrogenation ratio of the block copolymer to an ethylenic double bond (double bond in a conjugated diene compound unit) is 10 to 60%. The resin composition described in 1.
[8]
The resin composition according to any one of [1] to [7], wherein the polymer block A forming the component (d) has a number average molecular weight (MndA) of 5,000 to 25,000.
[9]
The resin composition according to any one of [1] to [8], wherein the number average molecular weight (Mnc) of the component (c) is 100,000 or less.
[10]
The resin composition according to any one of [1] to [9], wherein the number average molecular weight (Mnd) of the component (d) is 100,000 or less.
[11]
Any of [1] to [10], wherein the total proportion of 1,2-vinyl bonds and 3,4-vinyl bonds is 30 to 50% in all bonds of the conjugated diene compound unit in the component (d). The resin composition described in 1.
[12]
The component (a) is homopolypropylene and / or block polypropylene,
Any of [1] to [11], wherein the melt flow rate (MFR: measured in accordance with JIS K7210, 230 ° C., 2.16 kg load) of the component (a) is 0.1 to 100 g / 10 min. A resin composition according to claim 1.
[13]
The resin composition according to any one of [1] to [12], having a matrix phase containing the component (a) and a dispersed phase containing the component (b).
[14]
The ratio (−45 ° C. tan δ / 0 ° C. tan δ) of the loss tangent at −45 ° C. (−45 ° C. tan δ) obtained by the following measurement method to the loss tangent of 0 ° C. (0 ° C. tan δ) is 0.41 or more. , [1] to [13] a resin composition according to any one of the above;
<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 −45 ° C. and 0 ° C. when measured in a temperature sweep mode of 0.5 N, temperature rising rate: 3 ° C./min, temperature range: −100 ° C. to 160 ° C.
[15]
[1] A molded article comprising the resin composition according to any one of [14].

  According to the present invention, it is possible to obtain a resin composition that is more excellent in tensile elongation and impact resistance at low temperatures and has less warping 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 first hydrogenated block copolymer resin, and (d) a second hydrogenated block copolymer resin,
The block copolymer comprising the components (c) and (d) 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,
In the total bond of the conjugated diene compound unit in the component (d), 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 (d), 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%.

[(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. Although it does not specifically limit as an example in the case of using 2 or more types together, For example, the mixture of a crystalline propylene homopolymer and a crystalline propylene-ethylene block copolymer 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, in the presence of a titanium trichloride catalyst or a titanium halide catalyst supported on a carrier such as magnesium chloride and an alkylaluminum compound, a polymerization temperature of 0 to 100 is used. The method of superposing | polymerizing the monomer containing propylene in the range of 3-100 atmospheres of polymerization pressure in the range of ° C. 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.

  The (a1) polypropylene resin used in the present embodiment can be obtained by the above method or the like. Moreover, even if it is (a1) polypropylene resin which has what kind of crystallinity and melting | fusing point, you may use independently and may use 2 or more types together.

  (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 can be arbitrarily set. Can be determined.

[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>
The (b2) modified polyphenylene ether resin is, for example, the (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)]
The (c) first hydrogenated block copolymer resin (hereinafter also referred to as “component (c)”) used in the present embodiment is the (c1) first hydrogenated block copolymer and / or described later. Or (c2) a first modified hydrogenated block copolymer.

<(C1) component>
(C1) The first 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 a hydrogenation ratio of 80 to 100 with respect to the ethylenic double bond (double bond in a conjugated diene compound unit) of the block copolymer. % Hydrogenated block copolymer.

  In the total bond of the conjugated diene compound unit (hydrogenated block copolymer constituent unit derived from the conjugated diene compound) in the component (c1), the total ratio of 1,2-vinyl bond and 3,4-vinyl bond is 45. It is preferably ˜90%, more preferably 50 to 90%, and still more preferably 65 to 90%.

  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. There is a tendency.

  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.

  In this embodiment, the total ratio of 1,2-vinyl bond and 3,4-vinyl bond can be measured with an infrared spectrophotometer. Specifically, it can be measured by the method described in Examples described later.

(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%. More preferably. When the ratio of the total vinyl bond amount exceeds 90%, industrial production may be difficult.
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 first hydrogenated block copolymer (c1), 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%. , 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 1st 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>
In addition, (c2) the first modified hydrogenated block copolymer includes, for example, the above (c1) first hydrogenated block copolymer and an α, β-unsaturated carboxylic acid or derivative thereof (ester compound or An acid anhydride compound) is a modified hydrogenated block copolymer obtained by reacting an acid anhydride compound) 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 (c1) first hydrogenated block copolymer in a proportion of 0.01 to 10% by mass.

  When (c1) the first hydrogenated block copolymer and (c2) the first modified hydrogenated block copolymer are used in combination, (c1) in the (c) first hydrogenated block copolymer resin The mixing ratio of the first hydrogenated block copolymer and (c2) the first 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) first hydrogenated block copolymer resin in the resin composition is merely an emulsifying dispersant (admixture) between polymer (polypropylene) and polymer (polyphenylene ether). It tends to be a role as an agent. That is, at the time of emulsification of a polymer (polypropylene) -polymer (polyphenylene ether) having a high viscosity in a molten bulk state, (c) the first hydrogenated block copolymer resin as an emulsifying dispersant (admixture), In order to preferably diffuse in the melt mixing system, the number average molecular weight (Mnc) of the component (c) is 5,000 to 1,000 in consideration of the melt viscosity of the (c) first hydrogenated block copolymer. 1,000 is preferable and 100,000 or less is more preferable.

  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>
Further, the content of the vinyl aromatic compound unit (hydrogenated block copolymer constituent unit derived from the vinyl aromatic compound) in the component (c) is preferably 30 to 50% by mass, more preferably 30 to 30% by mass. It is 48 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 tends to be improved, and when the content of the vinyl aromatic compound unit is 50% by mass or less, There is a tendency to obtain a resin composition having an excellent balance between heat resistance and impact resistance. 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 first hydrogenated block copolymer resin is an emulsion dispersion between a polypropylene resin and a polyphenylene ether resin. It tends to give good emulsification and dispersion of the polyphenylene ether-based resin and give a great advantage to the heat resistance, mechanical properties and impact resistance of the resulting resin composition.

[Component (d)]
The resin composition of the present embodiment further includes at least one (d) second hydrogenated block copolymer resin different from the component (c) from the viewpoint of improving impact resistance. The (d) second hydrogenated block copolymer resin (hereinafter also referred to as “component (d)”) used in the present embodiment is a (d1) second hydrogenated block copolymer and / Or (d2) a second modified hydrogenated block copolymer.

<(D1) component>
(D1) 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 1,2-vinyl in all bonds of a conjugated diene compound unit (hydrogenated block copolymer constituent unit derived from a conjugated diene compound) The total proportion of bonds and 3,4-vinyl bonds is 25% or more and less than 60%. In the component (d1), 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 (d1), the total ratio of 1,2-vinyl bond and 3,4-vinyl bond is preferably 25 to 55%, and preferably 30 to 50%. It is more preferable.

  When the total ratio of 1,2-vinyl bond and 3,4-vinyl bond is less than 60%, the impact resistance at low temperature of the resin composition is improved. Further, the component (d1) having a total ratio of 1,2-vinyl bond and 3,4-vinyl bond of 25% or more improves compatibility with the component (a) in combination with the component (c). It is preferable from the viewpoint.

  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 (d1), 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.

  As in the case of component (c), “total vinyl bond amount relative to total bond amount of conjugated diene compound (total ratio of 1,2-vinyl bond and 3,4-vinyl bond relative to all bonds)” means the water This refers to the amount of vinyl bonds in the block copolymer before hydrogenation of the added block copolymer resin. 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 NMR from the block copolymer after hydrogenation.

((D1) Structure of second hydrogenated block copolymer)
(D1) 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”. 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 structure of a copolymer block 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. As said vinyl aromatic compound, the above-mentioned compound is mentioned, 1 type may be used individually and 2 or more types may be used.

  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 mainly composed of a conjugated diene compound having a proportion of 45% or more and less than 70% of at least one polymer block B1 mainly composed of a conjugated diene compound of 25 to 45%. It may be a polymer block B mainly composed of a conjugated diene compound having both the block 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 there are two or more polymer blocks A or B in the component (d1), 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 25% or more and less than 60%, more preferably 25 to 55%, more preferably 30 to 50%. More preferably. When the ratio of the total vinyl bond amount is less than 60%, the impact resistance at low temperature of the resin composition is improved.

(Hydrogen addition rate)
In the second hydrogenated block copolymer (d1), 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. The component (d1) having such a hydrogenation rate is, for example, a desired hydrogenation rate (for example, 10% or more and less than 80%) in the hydrogenation reaction of the ethylenic double bond of the block copolymer. ) Can be easily obtained by controlling to the range of

(Production method)
(D1) 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.

  The (d1) second hydrogenated block copolymer is a resin in which 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 impact resistance at low temperature of the composition is improved, which is more preferable.

(Content of vinyl aromatic compound unit in component (d1))
(D1) It is preferable that a 2nd hydrogenated block copolymer contains 20-70 mass% of vinyl aromatic compound units (hydrogenated block copolymer structural unit derived from a vinyl aromatic compound). Further, not only one (d1) component having a vinyl aromatic compound unit content in these ranges, but also a (d1) component having two or more different vinyl aromatic compound unit contents can be used in combination. .

<(D2) component>
In addition, (d2) the second modified hydrogenated block copolymer includes, for example, the (d1) second hydrogenated block copolymer and 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 (d1) second hydrogenated block copolymer in a proportion of 0.01 to 10% by mass.

  When (d1) the second hydrogenated block copolymer and (d2) the second modified hydrogenated block copolymer are used in combination, (d1) in the second hydrogenated block copolymer resin (d1) The mixing ratio of the second hydrogenated block copolymer and (d2) the second modified hydrogenated block copolymer can be determined without any particular limitation.

<Number average molecular weight>
(D) The number average molecular weight (Mnd) of a component becomes like this. Preferably it is 5,000-1,000,000, More preferably, it is 100,000 or less. When Mnd is 1,000,000 or less, the role of (d) 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 resins selected from the group consisting of the first hydrogenated block copolymer resins. That is, when emulsifying a polymer (polypropylene) -polymer (polyphenylene ether) -polymer (first hydrogenated block copolymer) having a high viscosity in the melt bulk state, (d) second as an impact resistance imparting agent. (D) The number average molecular weight (Mnd) of the component (d) in consideration of the melt viscosity of the second hydrogenated block copolymer resin. ) Is preferably 5,000 to 1,000,000, and more preferably 100,000 or less.

  The method for controlling the number average molecular weight (Mnd) of the component (d) 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 (d).

  In addition, in this Embodiment, the number average molecular weight (Mnd) of (d) component can be 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 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.

  In addition, the number average molecular weight (MndA) of the polymer block A forming the second hydrogenated block copolymer resin (d) is, for example, as described above when the component (d) has an ABA structure. Based on the number average molecular weight (Mnd) of the component (d), it is assumed that the molecular weight distribution of the component (d) is 1, and that two polymer blocks A mainly composed of vinyl aromatic compounds exist as the same molecular weight. , (MndA) = (Mnd) × bonded vinyl aromatic compound amount ratio ÷ 2. Similarly, when the component (d) is an ABABABA type hydrogenated block copolymer, (MndA) = (Mnd) × 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 (Mnd) of the component (d).

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

<Content of vinyl aromatic compound unit>
Further, the content of the vinyl aromatic compound unit (hydrogenated block copolymer constituent unit derived from the vinyl aromatic compound) in the component (d) is preferably 20 to 70% by mass, more preferably 20 to 20%. 60 mass%, More preferably, it is 20-40 mass%. When the content of the vinyl aromatic compound unit in the component (d) 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 excellent in balance with property.

[Content ratio of each component]
In the resin composition of the present embodiment, (c) the mass ratio of (d) the second hydrogenated block copolymer resin and (d) the second hydrogenated block copolymer resin that can be used in combination with the first hydrogenated block copolymer resin ((c) : (D)) is preferably 1:99 to 99: 1 from the viewpoint of obtaining a polymer alloy in which (b) polyphenylene ether resin is stably emulsified and dispersed in (a) polypropylene resin matrix. More preferably, it is 10: 90-90: 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. It is preferable from the viewpoint of heat resistance of the resin composition that the total content of the components (c) and (d) is within the above range.

  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.

[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.). And constituting dispersed particles. 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).

<(E) 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, (b) at least one selected from the group consisting of polystyrene, syndiotactic polystyrene and high impact polystyrene, preferably 400 parts by mass or less, more preferably 100 parts by mass of 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 compound-conjugated diene compound block copolymers, vinyl aromatic compounds-conjugated dienes not corresponding to components (c) and (d) Hydrogenated block copolymers of compounds, olefin elastomers (ethylene-α-olefin copolymers, etc.), antioxidants, metal deactivators, heat stabilizers, flame retardants (organic phosphate ester compounds, 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 is a ratio (−45 ° C. tan δ /) of a loss tangent (−45 ° C. tan δ) of −45 ° C. obtained by the following measurement method and a loss tangent of 0 ° C. (0 ° C. tan δ). 0 ° C. tan δ) is preferably 0.41 or more, more preferably 0.45 or more, and further preferably 0.50 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 −45 ° C. and 0 ° C. when measured in a temperature sweep mode of 0.5 N, temperature rising rate: 3 ° C./min, temperature range: −100 ° C. to 160 ° C.

  The higher the ratio (−45 ° C. tan δ / 0 ° C. tan δ), the better, but the upper limit is, for example, 1.50. By setting the ratio (−45 ° C. tan δ / 0 ° C. tan δ) to 0.41 or more, the low temperature impact property of the resin composition at 0 ° C. or less can be improved.

  The resin composition in which the ratio (−45 ° C. tan δ / 0 ° C. tan δ) is within the above range includes, for example, (a) a polypropylene-based resin and (b) a polyphenylene ether-based resin, as described above. It can be obtained by adding block copolymer resins (c) and (d).

≪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) component is included in the raw material, the charging method of the (e) component is not particularly limited, but it is charged from the first raw material supply port, the second raw material supply port, and / or the third raw material supply port. Is preferred.

≪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 polypropylene resin was measured under the conditions of 230 ° C. and a load of 2.16 kg in accordance with JIS K7210.

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

[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) (first hydrogenated block copolymer resin)
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 synthesized hydrogenated block copolymer was used as the component (c). The characteristics of the hydrogenated block copolymer resin 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%

4). Component (d) (second hydrogenated block copolymer resin)
The following components (d-1) to (d-4) were used as the component (d).

(D-1)
A hydrogenated block copolymer having an ABA type structure of polystyrene (1) -hydrogenated polybutadiene-polystyrene (2) was synthesized by a conventional method. The characteristics of the hydrogenated block copolymer resin (d-1) are shown below.
Bonded styrene content: 30% by mass
Total vinyl bond content in the polybutadiene unit in the hydrogenated block copolymer (total ratio of 1,2-vinyl bond and 3,4-vinyl bond to all bonds): 41%
Hydrogenation ratio of block copolymer to ethylenic double bond (double bond in polybutadiene unit): 43%
Number average molecular weight (Mnd): 72,000
Number average molecular weight (MndA) of polystyrene block (1): 10,700
Number average molecular weight (MndA) of polystyrene block (2): 11,000

(D-2)
A hydrogenated block copolymer having an ABA type structure of polystyrene (1) -hydrogenated polybutadiene-polystyrene (2) was synthesized by a conventional method. The characteristics of the hydrogenated block copolymer resin (d-2) are shown below.
Bonded styrene content: 66% 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): 36%
Hydrogenation rate of block copolymer to ethylenic double bond (double bond in polybutadiene unit): 57%
Number average molecular weight (Mnd): 61,000
Number average molecular weight (MndA) of polystyrene block (1): 19,000
Number average molecular weight (MndA) of polystyrene block (2): 21,000

(D-3)
A hydrogenated block copolymer having an ABA type structure of polystyrene (1) -hydrogenated polybutadiene-polystyrene (2) was synthesized by a conventional method. The characteristics of the hydrogenated block copolymer resin (d-3) are shown below.
Bonded styrene content: 64% 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%
Hydrogenation ratio of block copolymer to ethylenic double bond (double bond in polybutadiene unit): 68%
Number average molecular weight (Mnd): 99,000
Number average molecular weight (MndA) of polystyrene block (1): 32,000
Number average molecular weight (MndA) of polystyrene block (2): 31,000

(D-4)
A block copolymer having an ABA type structure of polystyrene (1) -hydrogenated polybutadiene-polystyrene (2) was synthesized by a conventional method. The characteristics of the block copolymer resin (d-4) are shown below.
Bonded styrene content: 42%
Total vinyl bond content in polybutadiene unit (total ratio of 1,2-vinyl bond and 3,4-vinyl bond to all bonds): 9%
Hydrogenation ratio of block copolymer to ethylenic double bond (double bond in polybutadiene unit): 10%
Number average molecular weight (Mnd): 110,000
Number average molecular weight (MndA) of polystyrene block (1): 22,000
Number average molecular weight (MndA) of polystyrene block (2): 24,000

[Examples 1-8 and Comparative Examples 1-5]
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 of d) was supplied to the first to third raw material supply ports of the extruder with 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 Of tan δ measured at −45 ° C. and 0 ° C. (−45 ° C. tan δ / 0) ° C tan δ) was calculated. Similarly, the ratio of tan δ at −50 ° C. and 0 ° C. (−50 ° C. tan δ / 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 plate was obtained. A virtual plane is set for this flat plate from the 15 points shown in FIG. 1 by a least square method using a three-dimensional measuring instrument manufactured by Mitutoyo Corporation, and the value obtained by subtracting the minimum value from the maximum value of the deviation from the plane is The flatness of the flat plate was used. 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 first hydrogenated block copolymer resin, and (d) a second hydrogenated block copolymer resin,
The block copolymer comprising the components (c) and (d) 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,
In the total bond of the conjugated diene compound unit in the component (d), 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%,
The resin composition whose hydrogenation rate with respect to the ethylenic double bond (double bond in a conjugated diene compound unit) of the block copolymer is 10 to 60 % in the component (d).     The resin composition according to claim 1, wherein the total proportion of 1,2-vinyl bonds and 3,4-vinyl bonds is 45 to 90% in all bonds of the conjugated diene compound unit in component (c).     The resin composition of Claim 1 or 2 in which the said (c) component contains 30-50 mass% of vinyl aromatic compound units.     The resin composition of any one of Claims 1-3 in which the said (d) component contains 20-70 mass% of vinyl aromatic compound units. 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.     The resin composition of any one of Claims 1-5 in which the said (d) component contains 20-60 mass% of vinyl aromatic compound units. Number average molecular weight of the polymer block A to form the component (d) (MNDA) is a 5,000 to 25,000, the resin composition according to any one of claims 1-6. Number average molecular weight of component (c) (Mnc) is 100,000 or less, the resin composition according to any one of claims 1-7. The number average molecular weight (Mnd) of the said (d) component is 100,000 or less, The resin composition of any one of Claims 1-8 . Wherein (d) the total binding of the conjugated diene compound unit in the component, the total proportion of 1,2-vinyl bond and 3,4-vinyl bond is 30-50%, any one of claims 1-9 The resin composition described in 1. The component (a) is homopolypropylene and / or block polypropylene,
Wherein component (a) a melt flow rate (MFR: compliant with JIS K7210, 230 ° C., measured under a load of 2.16 kg) is 0.1 to 100 g / 10 min, any one of claims 1-10 The resin composition according to item. 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). The ratio (−45 ° C. tan δ / 0 ° C. tan δ) of the loss tangent at −45 ° C. (−45 ° C. tan δ) obtained by the following measurement method to the loss tangent of 0 ° C. (0 ° C. tan δ) is 0.41 or more. The resin composition according to any one of claims 1 to 12 ;
<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 −45 ° C. and 0 ° C. when measured in a temperature sweep mode of 0.5 N, temperature rising rate: 3 ° C./min, temperature range: −100 ° C. to 160 ° C. Molded article comprising a resin composition according to any one of claims 1 to 13.

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