Polypropylene resin composition, hydrogenated block copolymer, molded product, and automotive interior / exterior material

The polypropylene-based resin composition, incorporating a hydrogenated block copolymer with controlled vinyl bond content, addresses the issue of low-temperature impact resistance, improving the performance of molded articles and automotive materials.

JP7824877B2Active Publication Date: 2026-03-05KURARAY CO LTD
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Patent Information

Application Number
JP2022539559
Authority / Receiving Office
JP · JP
Patent Type
Patents
Current Assignee / Owner
Priority Date
2020-07-30
Filing Date
2021-07-29
Publication Date
2026-03-05
Estimated Expiration
2041-07-29

AI Technical Summary

Technical Problem

Conventional polypropylene-based resin compositions lack sufficient impact resistance, particularly at low temperatures, which is a challenge as products become thinner and demand for functionality and economy increases.

Method used

A polypropylene-based resin composition comprising a polypropylene polymer, an ethylene-α-olefin copolymer rubber, and a hydrogenated block copolymer with specific vinyl bond and aromatic vinyl compound unit content, where the hydrogenated block copolymer is a hydrogenated product of a block copolymer with butadiene and isoprene units, and the vinyl bond content is 20% or less.

Benefits of technology

The composition achieves excellent impact resistance, especially at low temperatures, enhancing the performance of molded articles and automotive interior/exterior materials.

✦ Generated by Eureka AI based on patent content.

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Abstract

Provided are: a polypropylene-based resin composition having excellent impact resistance, particularly impact resistance at a low temperature; a hydrogenated block copolymer contained in said polypropylene-based resin composition; a molded article including said polypropylene-based resin composition; and an interior-exterior decorative material which is for automobiles and which includes said molded article. A polypropylene-based resin composition comprising a polypropylene-based polymer (A), an ethylene-α-olefin copolymer rubber (B), a hydrogenated block copolymer (C), wherein the hydrogenated block copolymer (C) is a hydrogenated product of a block copolymer having at least one polymeric block (C-1) mainly formed of an aromatic vinyl compound unit and having at least one polymeric block (C-2) mainly formed of a butadiene (Bd) unit and an isoprene (Ip) unit, the contained amount of the aromatic vinyl compound unit in the hydrogenated block copolymer is less than 30 mass%, and the vinyl bound amount of the polymeric block (C-2) is 20% or less.
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Description

[Technical Field]

[0001] The present invention relates to a polypropylene-based resin composition, a hydrogenated block copolymer, a molded article, and an automotive interior / exterior material, and more particularly to a polypropylene-based resin composition, a hydrogenated block copolymer contained in the polypropylene-based resin composition, a molded article containing the polypropylene-based resin composition, and an automotive interior / exterior material containing the molded article. [Background technology]

[0002] Polypropylene resin compositions generally have excellent chemical resistance and mechanical properties and are therefore widely used as materials for various products such as machine parts and automobile parts.

[0003] Patent Document 1 discloses a propylene-based resin composition comprising a polypropylene-based resin, a rubber-like polymer, and a hydrogenated block copolymer. Patent Document 2 discloses a polypropylene resin composition containing a hydrogenated block copolymer consisting of two vinyl aromatic hydrocarbon compound polymer blocks A and one hydrogenated butadiene polymer block B, in which 90% or more of the olefinically unsaturated double bonds in the butadiene polymer block before hydrogenation have been hydrogenated. Patent Document 3 discloses a polypropylene resin composition containing 50 to 90 mass% of a polypropylene polymer (A), 5 to 50 mass% of an ethylene-α-olefin copolymer (B), and 0.1 to 5 mass% of a copolymer mainly composed of vinyl aromatic monomer units and alkylene monomer units, with the content of α-olefin monomer units in all alkylene monomers being 45 mol% or more. [Prior art documents] [Patent documents]

[0004] [Patent Document 1] Japanese Patent Application Laid-Open No. 2001-106844 [Patent Document 2] International Publication No. 99 / 64489 [Patent Document 3] International Publication No. 2010 / 104174 Summary of the Invention [Problem to be solved by the invention]

[0005] However, in recent years, in pursuit of functionality and economy in various products, products have become thinner, and there is a demand for polypropylene-based resin compositions having excellent impact resistance, particularly at low temperatures. However, conventional products have room for further improvement in impact resistance, particularly at low temperatures.

[0006] Therefore, an object of the present invention is to provide a polypropylene-based resin composition having excellent impact resistance, particularly excellent impact resistance at low temperatures, a hydrogenated block copolymer contained in the polypropylene-based resin composition, a molded article containing the polypropylene-based resin composition, and an automotive interior / exterior material containing the molded article. [Means for solving the problem]

[0007] As a result of intensive research into solving the above-mentioned problems, the present inventors have found that the above-mentioned problems can be solved by including a polypropylene polymer (A), an ethylene-α-olefin copolymer rubber (B), and a hydrogenated block copolymer (C) having an aromatic vinyl compound unit content of less than 30 mass% and having a vinyl bond content of 20% or less in the polymer block (C-2), and have completed the present invention. That is, the present invention is as follows.

[0008] [1] A polypropylene-based resin composition comprising a polypropylene-based polymer (A), an ethylene-α-olefin copolymer rubber (B), and a hydrogenated block copolymer (C), wherein the hydrogenated block copolymer (C) has at least one polymer block (C-1) mainly composed of aromatic vinyl compound units, and is a hydrogenated product of a block copolymer having at least one polymer block (C-2) mainly composed of butadiene (Bd) units and isoprene (Ip) units, and wherein the content of the aromatic vinyl compound units in the hydrogenated block copolymer (C) is less than 30% by mass, and the vinyl bond content of the polymer block (C-2) is 20% or less. [2] The polypropylene-based resin composition according to [1] above, wherein the content of the ethylene-α-olefin copolymer rubber (B) is 1 to 50 parts by mass relative to 100 parts by mass of the polypropylene-based polymer (A), and the content of the hydrogenated block copolymer (C) is 1 to 50 parts by mass relative to 100 parts by mass of the polypropylene-based polymer (A). [3] The polypropylene resin composition according to [1] or [2] above, which has a melt flow rate (MFR) of 3 to 200 g / 10 min, determined in accordance with JIS K7210 at a temperature of 230°C and a load of 2.16 kgf. [4] The polypropylene-based resin composition according to any one of [1] to [3] above, wherein the polypropylene-based polymer (A) has a melt flow rate (MFR) of 1 to 200 g / 10 min, determined in accordance with JIS K7210 at a temperature of 230°C and a load of 2.16 kgf. [5] The polypropylene resin composition according to any one of [1] to [4] above, wherein the ethylene-α-olefin copolymer rubber (B) has a melt flow rate (MFR) of 0.1 to 50 g / 10 min, determined in accordance with JIS K7210 under conditions of a temperature of 230°C and a load of 2.16 kgf. [6] The polypropylene resin composition according to any one of the above [1] to [5], wherein the ethylene-α-olefin copolymer rubber (B) is at least one selected from the group consisting of an ethylene-propylene copolymer, an ethylene-butene copolymer, and an ethylene-octene copolymer. [7] The polypropylene resin composition according to the above [6], wherein the ethylene-α-olefin copolymer rubber (B) is an ethylene-octene copolymer. [8] The above [1] to [1] further containing high-density polyethylene. 〔7〕 The polypropylene resin composition according to any one of the preceding claims. [9] The polypropylene resin composition according to any one of [1] to [8] above, wherein the hydrogenated block copolymer (C) has a melt flow rate (MFR) of 0.1 to 50 g / 10 min, determined in accordance with JIS K7210 at a temperature of 230°C and a load of 2.16 kgf.

[10] The polypropylene resin composition according to any one of the above [1] to [9], wherein the hydrogenated block copolymer (C) is a triblock copolymer of polystyrene-hydrogenated butadiene / isoprene copolymer-polystyrene, or a diblock copolymer of polystyrene-hydrogenated butadiene / isoprene copolymer.

[11] A hydrogenated block copolymer (C) which is a hydrogenated product of a block copolymer having a polymer block (C-1) mainly composed of aromatic vinyl compound units, a polymer block (C-2) mainly composed of butadiene (Bd) units and isoprene (Ip) units, and a polymer block (C-3) mainly composed of structural units derived from isoprene (Ip) units (excluding the polymer block (C-2)), wherein the hydrogenated block copolymer (C) is a tetrablock copolymer whose bonding structure is represented by ABAC when the polymer block (C-1) is represented by A, the polymer block (C-2) is represented by B, and the polymer block (C-3) is represented by C.

[12] The hydrogenated block copolymer (C) according to the above

[11] , wherein the vinyl bond content of the polymer block (C-2) is 20% or less.

[13] The hydrogenated block copolymer (C) according to

[11] or

[12] above, wherein the proportion of the polymer block (C-3) in the hydrogenated block copolymer (C) is 40 mass% or less of the total mass of the hydrogenated block copolymer (C).

[14] The hydrogenated block copolymer (C) according to any one of the above

[11] to

[13] , wherein the vinyl bond content of the polymer block (C-3) is 20% or less.

[15] The hydrogenated block copolymer (C) according to any one of

[11] to

[14] above, wherein the content of structural units derived from isoprene (Ip) in the polymer block (C-3) is 70 mass% or more based on the total mass of the polymer block (C-3).

[16] The hydrogenated block copolymer (C) according to any one of the above

[11] to

[15] , wherein the hydrogenation rate (hydrogenation rate) of the polymer block (C-3) in the hydrogenated block copolymer (C) is 80 mol % or more.

[17] A molded article comprising the polypropylene resin composition according to any one of [1] to

[10] above.

[18] An interior / exterior material for automobiles, comprising the molded article described in

[17] above. [Effects of the Invention]

[0009] According to the present invention, it is possible to provide a polypropylene-based resin composition having excellent impact resistance, particularly excellent impact resistance at low temperatures, a hydrogenated block copolymer contained in the polypropylene-based resin composition, a molded article containing the polypropylene-based resin composition, and an automotive interior / exterior material containing the molded article. DETAILED DESCRIPTION OF THE INVENTION

[0010] The present invention will be described in detail below. In this specification, the preferred definitions can be adopted arbitrarily, and it can be said that a combination of preferred definitions is more preferred. In addition, in this specification, the expression "XX to YY" means "XX or more and YY or less." Furthermore, in this specification, for preferred numerical ranges (e.g., ranges of content, etc.), the lower and upper limits described in stages can be independently combined. For example, the description "preferably 10 to 90, more preferably 30 to 60" can be combined with the "preferable lower limit (10)" and the "more preferable upper limit (60)" to form "10 to 60." Furthermore, in the numerical ranges described in this specification, the upper or lower limit of the numerical range may be replaced with a value shown in the examples. In addition, in this specification, the term "unit of ~" (where "~" indicates a monomer) means "a structural unit derived from ~", for example, "aromatic vinyl compound unit" means "a structural unit derived from an aromatic vinyl compound". In this specification, the weight average molecular weight is the weight average molecular weight calculated in terms of standard polystyrene obtained by gel permeation chromatography (GPC) measurement, as in the examples, and the number average molecular weight is the number average molecular weight calculated in terms of standard polystyrene obtained by gel permeation chromatography (GPC) measurement. Furthermore, in this specification, "high density polyethylene" means polyethylene having a density of 0.94 g / cm 3 The above polyethylene refers to polyethylene of the above type.

[0011] [Polypropylene Resin Composition] The present invention provides a polypropylene-based resin composition comprising a polypropylene-based polymer (A), an ethylene-α-olefin copolymer rubber (B), and a hydrogenated block copolymer (C), wherein the hydrogenated block copolymer (C) is a hydrogenated product of a block copolymer having at least one polymer block (C-1) mainly composed of aromatic vinyl compound units and at least one polymer block (C-2) mainly composed of butadiene (Bd) units and isoprene (Ip) units, and wherein the content of aromatic vinyl compound units in the hydrogenated block copolymer is less than 30% by mass, and the vinyl bond content of the polymer block (C-2) is 20% or less. In this specification, the term "polypropylene resin composition" refers to a composition containing 40% by mass or more of the polypropylene polymer (A). In this specification, the "content of aromatic vinyl compound units" refers to the same as in the examples described below. 1 The values ​​were measured by H-NMR.

[0012] The melt flow rate (MFR) of the polypropylene resin composition is not particularly limited, and a preferred value can be selected depending on the shape of the desired molded article and the molding method of the molded article. When the polypropylene resin composition of the present invention is molded by injection molding, the MFR of the polypropylene resin composition is preferably 3 to 200 g / 10 min, more preferably 3 to 150 g / 10 min, and particularly preferably 5 to 125 g / 10 min. When the melt flow rate (MFR) of the polypropylene resin composition is equal to or greater than the lower limit, the required flow distance during injection molding can be obtained, and even when thin-wall molding is performed, the molded article tends to have excellent appearance. On the other hand, when the MFR is equal to or less than the upper limit, the impact resistance tends to be good. When the polypropylene resin composition of the present invention is molded by extrusion into a pipe, the MFR of the polypropylene resin composition is preferably 0.05 to 10 g / 10 min, more preferably 0.1 to 5 g / 10 min, and particularly preferably 0.2 to 1.5 g / 10 min. An MFR within the above range is preferred from the viewpoint of parison stability during pipe extrusion molding. Furthermore, when the polypropylene resin composition of the present invention is molded by extrusion blow molding, the MFR of the polypropylene resin composition is preferably 0.05 to 10 g / 10 min, more preferably 0.1 to 5 g / 10 min, and particularly preferably 0.2 to 1.5 g / 10 min. It is preferable that the MFR is within the above-mentioned range. When the MFR of the polypropylene resin composition is equal to or greater than the lower limit, it becomes easier to mold large, complex-shaped blow-molded articles. On the other hand, when the MFR is equal to or less than the upper limit, the drawdown resistance of the parison and the impact resistance of the blow-molded article tend to be good. In this specification, the "melt flow rate (MFR)" is a value measured in accordance with JIS K7210 under conditions of a temperature of 230°C and a load of 2.16 kgf, as in the examples described later.

[0013] The polypropylene polymer (A), the ethylene-α-olefin copolymer rubber (B), the hydrogenated block copolymer (C), and other components that may be contained as needed, which are contained in the polypropylene resin composition, will be described in detail below.

[0014] (Polypropylene polymer (A)) The polypropylene polymer (A) may be a homopolypropylene (homoPP) or a copolymer of propylene and another monomer, but homopolypropylene is preferred for applications in which higher rigidity is required for the composition of the present invention.

[0015] The stereoregularity (tacticity) of the polypropylene polymer (A) is not particularly limited, and the polypropylene polymer (A) may be any of isotactic polypropylene resin, syndiotactic polypropylene resin, and atactic polypropylene resin. In applications where the polypropylene resin composition of the present invention is required to have higher rigidity and / or heat resistance, it is preferable to use an isotactic polypropylene resin as the polypropylene polymer (A).

[0016] The molecular structure of the polypropylene polymer (A) is not particularly limited, and examples thereof include a linear structure, a branched structure, and a graft structure of a modified product.

[0017] <Copolymer of propylene and other monomers> The copolymer of propylene and other monomers is not particularly limited, but from the viewpoint of a balance between high impact resistance and rigidity, random copolymers of propylene and an α-olefin comonomer (random PP) such as propylene-ethylene random copolymer, propylene-butene random copolymer, propylene-ethylene-butene random copolymer, propylene-pentene random copolymer, propylene-hexene random copolymer, propylene-octene random copolymer, propylene-ethylene-pentene random copolymer, and propylene-ethylene-hexene random copolymer are preferred. Among these, when the polypropylene resin composition of the present invention is used in an application requiring transparency, propylene-ethylene random copolymer is preferred from the viewpoint of transparency.

[0018] The content of propylene units in the polypropylene polymer (A) is not particularly limited, but is preferably 75 mol% or more, more preferably 80 mol% or more. When the content of propylene units in the polypropylene polymer (A) is equal to or more than the lower limit, the molded product obtained by molding the polypropylene resin composition of the present invention tends to have a good balance between rigidity and impact resistance.

[0019] The dispersion form of the polypropylene polymer (A) is not limited, and may be, for example, one type of polypropylene polymer present as a continuous phase and another type of polypropylene polymer forming a dispersed phase. When the polypropylene polymer (A) is a mixture of two or more types of polypropylene polymers, for example, isotactic polypropylene resin (homo PP) and propylene-ethylene random copolymer (random PP) may be polymerized in separate processes and formed into separate solid pellets, etc.

[0020] The method for preparing the polypropylene polymer (A) is not particularly limited, and examples thereof include slurry polymerization, gas phase polymerization, bulk polymerization, and solution polymerization. In the method for preparing the polypropylene polymer (A), various processes such as single-stage or multi-stage processes may be employed.

[0021] The catalyst used in the preparation of the polypropylene polymer (A) is not particularly limited, and examples thereof include metallocene catalysts and Ziegler-Natta catalysts.

[0022] The melt flow rate (MFR) of the polypropylene polymer (A) is not particularly limited, but is preferably 1 to 200 g / 10 min, more preferably 5 to 140 g / 10 min, and particularly preferably 10 to 80 g / 10 min. If the melt flow rate (MFR) of the polypropylene polymer (A) is not less than the lower limit, the processability tends to be good, and if it is not more than the upper limit, the rigidity tends to be good.

[0023] The content of the polypropylene polymer (A) in the polypropylene resin composition is not particularly limited, but is preferably 50 to 90 mass%, more preferably 53 to 85 mass%, even more preferably 55 to 80 mass%, and particularly preferably 57 to 75 mass%. When the content of the polypropylene polymer (A) is equal to or more than the lower limit, the rigidity tends to be good, and when it is equal to or less than the upper limit, the impact resistance and tensile elongation at break tend to be good.

[0024] (Ethylene-α-olefin copolymer rubber (B)) The ethylene-α-olefin copolymer rubber (B) is a copolymer of ethylene and an α-olefin.

[0025] <<α-olefin>> The α-olefin constituting the ethylene-α-olefin copolymer rubber (B) is not particularly limited, and examples thereof include C3 to C20 α-olefins. The C3 to C20 α-olefins may have either a linear structure or a branched structure, such as propylene, 1-butene, 1-pentene, 1-hexene, 1-heptene, 1-octene, 1-decene, 1-dodecene, 1-hexadodecene, 4-methyl-1-pentene, 2-methyl-1-butene, 3-methyl-1-butene, 3,3-dimethyl-1-butene, diethyl-1-butene, trimethyl-1-butene, 3-methyl-1-pentene, and ethyl-1-pentene. , propyl-1-pentene, dimethyl-1-pentene, methylethyl-1-pentene, diethyl-1-hexene, trimethyl-1-pentene, 3-methyl-1-hexene, dimethyl-1-hexene, 3,5,5-trimethyl-1-hexene, methylethyl-1-heptene, trimethyl-1-heptene, dimethyloctene, ethyl-1-octene, methyl-1-nonene, vinylcyclopentene, vinylcyclohexene, vinylnorbornene, etc. These may be used alone or in combination of two or more. Among these, from the viewpoints of impact resistance and tensile elongation at break, C4 to C8 α-olefin comonomers are preferred, and at least one selected from the group consisting of propylene, 1-butene, 1-hexene, 4-methyl-1-pentane, and 1-octene is more preferred. From the viewpoint of impact resistance, at least one selected from the group consisting of propylene, 1-butene, and 1-octene is even more preferred, with 1-octene being particularly preferred. On the other hand, from the viewpoint of moldability, at least one selected from the group consisting of propylene, 1-butene, and 1-octene is even more preferred, with propylene being particularly preferred. When the α-olefin constituting the ethylene-α-olefin copolymer rubber (B) is propylene, it is also a preferred embodiment to prepare the polypropylene-based polymer (A) using multistage polymerization. More specifically, one preferred embodiment of the present invention is to polymerize an isotactic polypropylene resin in the first stage of polymerization, polymerize an ethylene-propylene copolymer in the second stage, and then mix them.

[0026] The content of the α-olefin in the ethylene-α-olefin copolymer rubber (B) is not particularly limited, but is preferably 5 to 50 mass%, more preferably 20 to 45 mass%. When the content of the α-olefin in the ethylene-α-olefin copolymer rubber (B) is equal to or more than the lower limit, low-temperature hardening resistance and flexibility tend to be good, and when it is equal to or less than the upper limit, rigidity tends to be good.

[0027] Two or more kinds of ethylene-α-olefin copolymer rubbers may be used as the ethylene-α-olefin copolymer rubber (B). In this case, from the viewpoint of further improving impact resistance, tensile elongation at break, and rigidity, for example, two or more kinds of ethylene-α-olefin copolymer rubbers having different densities may be used in combination.

[0028] The melt flow rate (MFR) of the ethylene-α-olefin copolymer rubber (B) is not particularly limited, but is preferably 0.1 to 50 g / 10 min, more preferably 0.3 to 35 g / 10 min. When the melt flow rate (MFR) of the ethylene-α-olefin copolymer rubber (B) is equal to or higher than the lower limit, the processability tends to be good, and when it is equal to or lower than the upper limit, the mechanical properties tend to be good.

[0029] The molecular weight distribution (Mw / Mn; Mw is the weight average molecular weight, Mn is the number average molecular weight) of the ethylene-α-olefin copolymer rubber (B) is not particularly limited, but is preferably 1.3 to 5.0.

[0030] The density of the ethylene-α-olefin copolymer rubber (B) is not particularly limited, but is preferably 0.850 to 0.910 g / cm 3 , more preferably 0.855 to 0.885 g / cm 3 When the density of the ethylene-α-olefin copolymer rubber (B) is equal to or higher than the lower limit, the rigidity tends to be good, and when it is equal to or lower than the upper limit, the impact resistance and tensile elongation at break tend to be good.

[0031] The catalyst used in preparing the ethylene-α-olefin copolymer rubber (B) is not particularly limited, and examples thereof include catalysts that can easily produce a highly molecular weight α-olefin copolymer under processing conditions (e.g., titanium-, metallocene-, or vanadium-based catalysts). These may be used alone or in combination of two or more. Among these, metallocene catalysts and titanium chloride are preferred from the viewpoint of stability of structure control.

[0032] The polymerization form of the ethylene-α-olefin copolymer rubber (B) is not particularly limited, and may be a random copolymer of ethylene and an α-olefin, a block copolymer of ethylene and an α-olefin, etc. Specific examples include, but are not limited to, "TAFMER (registered trademark)" manufactured by Mitsui Chemicals as a random copolymer rubber of ethylene and 1-butene, "ENGAGE (registered trademark)" manufactured by Dow as a random copolymer rubber of ethylene and 1-octene, and "INFUSE (registered trademark)" manufactured by Dow as a block copolymer rubber of ethylene and 1-octene.

[0033] The content of the ethylene-α-olefin copolymer rubber (B) in the polypropylene resin composition is not particularly limited, but is preferably 1 to 50 parts by mass, more preferably 10 to 50 parts by mass, still more preferably 15 to 45 parts by mass, and particularly preferably 15 to 35 parts by mass, relative to 100 parts by mass of the polypropylene polymer (A). When the content of the ethylene-α-olefin copolymer rubber (B) is equal to or greater than the lower limit, the impact resistance and tensile elongation at break tend to be good, and when it is equal to or less than the upper limit, the rigidity tends to be good.

[0034] (Hydrogenated Block Copolymer (C)) The hydrogenated block copolymer (C) is a hydrogenated product of a block copolymer having at least one polymer block (C-1) mainly composed of aromatic vinyl compound units and at least one polymer block (C-2) mainly composed of butadiene (Bd) units and isoprene (Ip) units. The polymer block (C-1) and the polymer block (C-2) will be described below in order.

[0035] <Polymer block (C-1)> The polymer block (C-1) is mainly composed of structural units derived from an aromatic vinyl compound. Here, "mainly composed" means that the polymer block (C-1) contains 50% by mass or more of structural units derived from an aromatic vinyl compound, based on the total mass of the polymer block (C-1). From the viewpoint of the mechanical properties of the polypropylene resin composition, the content of structural units derived from an aromatic vinyl compound in the polymer block (C-1) is preferably 70% by mass or more, and even more preferably 90% by mass or more, based on the total mass of the polymer block (C-1). The aromatic vinyl compound is not particularly limited, and examples thereof include styrene, o-methylstyrene, m-methylstyrene, p-methylstyrene, α-methylstyrene, β-methylstyrene, 2,6-dimethylstyrene, 2,4-dimethylstyrene, α-methyl-o-methylstyrene, α-methyl-m-methylstyrene, α-methyl-p-methylstyrene, β-methyl-o-methylstyrene, β-methyl-m-methylstyrene, β-methyl-p-methylstyrene, 2,4,6-trimethylstyrene, α-methyl-2,6-dimethylstyrene, α-methyl-2,4-dimethylstyrene, β-methyl-2,6-dimethylstyrene, β-methyl-2,4-dimethylstyrene, o-chlorostyrene, m-chlorostyrene, p-chlorostyrene, 2,6-dichlorostyrene, 2,4-dichlorostyrene, Examples of the styrene-substituted styrene include α-chloro-o-chlorostyrene, α-chloro-m-chlorostyrene, α-chloro-p-chlorostyrene, β-chloro-o-chlorostyrene, β-chloro-m-chlorostyrene, β-chloro-p-chlorostyrene, 2,4,6-trichlorostyrene, α-chloro-2,6-dichlorostyrene, α-chloro-2,4-dichlorostyrene, β-chloro-2,6-dichlorostyrene, β-chloro-2,4-dichlorostyrene, ot-butylstyrene, mt-butylstyrene, pt-butylstyrene, o-methoxystyrene, m-methoxystyrene, p-methoxystyrene, o-chloromethylstyrene, m-chloromethylstyrene, p-chloromethylstyrene, o-, m-, or p-bromomethylstyrene, styrene derivatives substituted with a silyl group, indene, and vinylnaphthalene. Among these, from the viewpoint of the balance between production cost and physical properties, styrene, α-methylstyrene, and mixtures thereof are preferred, and styrene is more preferred.

[0036] However, the polymer block (C-1) may contain unsaturated monomers other than aromatic vinyl compounds, as long as the purpose and effects of the present invention are not hindered. The other unsaturated monomers are not particularly limited, and examples thereof include butadiene, isoprene, 2,3-dimethylbutadiene, 1,3-pentadiene, 1,3-hexadiene, isobutylene, methyl methacrylate, methyl vinyl ether, N-vinylcarbazole, β-pinene, 8,9-p-menthene, dipentene, methylenenorbornene, and 2-methylenetetrahydrofuran. When the polymer block (C-1) contains the other unsaturated monomer units, the bonding configuration is not particularly limited, and may be either random or tapered.

[0037] The content of aromatic vinyl compound units in the hydrogenated block copolymer (C) is not particularly limited as long as it is less than 30% by mass, but from the viewpoint of obtaining particularly excellent impact resistance, it is preferably 4 to 28% by mass, more preferably 8 to 25% by mass, and particularly preferably 12 to 22% by mass.

[0038] <Polymer block (C-2)> The polymer block (C-2) is mainly composed of structural units derived from butadiene (Bd) units and isoprene (Ip) units. Here, "mainly composed" means that the polymer block (C-2) contains 50% by mass or more of structural units derived from butadiene (Bd) and structural units derived from isoprene (Ip), based on the total mass of the polymer block (C-2). The content of the structural units derived from butadiene (Bd) and structural units derived from isoprene (Ip) in the polymer block (C-2) is more preferably 70% by mass or more, and even more preferably 90% by mass or more, based on the total mass of the polymer block (C-2). The conjugated diene compound constituting the polymer block (C-2) mainly comprises butadiene (Bd) units and isoprene (Ip) units, and may further contain at least one selected from, for example, 2,3-dimethylbutadiene, 1,3-pentadiene, 1,3-hexadiene, and the like. The content ratio of butadiene (Bd) units and isoprene (Ip) units (butadiene units / isoprene units) (molar ratio) is not particularly limited, but from the viewpoint of improving performance, it is preferably 10 / 90 to 90 / 10, more preferably 30 / 70 to 70 / 30, and particularly preferably 40 / 60 to 60 / 40. The bonding form of the polymer block (C-2) is not particularly limited, and may be random, tapered, completely alternate, partially block-like, block, or a combination of two or more thereof, but is preferably random.

[0039] The bond form of butadiene (Bd) and isoprene (Ip) constituting the polymer block (C-2) is not particularly limited. For example, butadiene may have a 1,2-bond or a 1,4-bond, and isoprene may have a 1,2-bond, a 3,4-bond, or a 1,4-bond. In this specification, the amount of 1,2-bonds in the butadiene units of a polymer block is referred to as the vinyl bond amount, and the total amount of 1,2-bonds and 3,4-bonds in the isoprene units of a polymer block is referred to as the vinyl bond amount. The vinyl bond content in the total bond form of a polymer block is referred to as the "vinyl bond amount (%) of the polymer block," and the vinyl bond content in the entire hydrogenated block copolymer is referred to as the "degree of vinylation (%) of the hydrogenated block copolymer (C)." As in the examples, the 1,2-bond amount and the 3,4-bond amount are 1 It can be calculated by H-NMR measurement.

[0040] The vinyl bond content of the polymer block (C-2) is not particularly limited as long as it is 20% or less, and is preferably 2 to 15%, more preferably 5 to 10%, and particularly preferably 6 to 8%. When the vinyl bond content of the polymer block (C-2) is within the above range, better impact resistance, particularly impact resistance at low temperatures, tends to be obtained.

[0041] Furthermore, from the viewpoint of affinity with the polypropylene-based polymer (A) and / or the ethylene-α-olefin copolymer rubber (B), the carbon-carbon double bonds of the polymer block (C-2) in the hydrogenated block copolymer (C) are preferably hydrogenated (hereinafter sometimes abbreviated as "hydrogenation"). The hydrogenation rate (hydrogenation rate) of the polymer block (C-2) in the hydrogenated block copolymer (C) is not particularly limited, but is preferably 80 mol% or more, more preferably 85 mol% or more, and particularly preferably 90 to 100 mol%. When the hydrogenation rate of the polymer block (C-2) in the hydrogenated block copolymer (C) is within the above-mentioned range, the hydrogenated block copolymer (C) exhibits good affinity with the polypropylene-based polymer (A) and the ethylene-α-olefin copolymer rubber (B), and as a result, the impact resistance of the polypropylene-based resin composition of the present invention tends to be better. In this specification, the "hydrogenation rate" is a value measured in the same manner as in the examples described below.

[0042] Furthermore, polymer block (C-2) may contain structural units derived from polymerizable monomers other than butadiene (Bd) units and isoprene (Ip) units, as long as the structural units do not interfere with the objectives and effects of the present invention. Examples of such other polymerizable monomers include styrene, α-methylstyrene, o-methylstyrene, m-methylstyrene, p-methylstyrene, pt-butylstyrene, 2,4-dimethylstyrene, vinylnaphthalene, vinylanthracene, methyl methacrylate, methyl vinyl ether, N-vinylcarbazole, β-pinene, 8,9-p-menthene, dipentene, methylenenorbornene, and 2-methylenetetrahydrofuran. When the polymer block (C-2) contains structural units derived from other polymer monomers than butadiene (Bd) units and isoprene (Ip) units, the content thereof is usually 30% by mass or less, preferably 10% by mass or less, more preferably 5% by mass or less, and particularly preferably 2% by mass or less, based on the total mass of the polymer block (C-2). When the polymer block (C-2) contains structural units derived from other polymer monomers than butadiene (Bd) units and isoprene (Ip) units, the bonding form is not particularly limited and may be either random or tapered.

[0043] <Bonding Form Between Polymer Block (C-1) and Polymer Block (C-2)> The bonding form of the hydrogenated block copolymer (C) is not particularly limited as long as the polymer block (C-1) and the polymer block (C-2) are bonded, and examples thereof include linear, branched, radial, etc. These may be used alone or in combination of two or more. Among these, linear is preferred. Specific examples of the linear bonding form include a diblock copolymer represented by AB, a triblock copolymer represented by ABA, a tetrablock copolymer represented by ABAB, a pentablock copolymer represented by ABABA, and an (AB)nX type copolymer (X represents a coupling agent residue, and n represents an integer of 3 or more), where A represents polymer block (C-1) and B represents polymer block (C-2). Among these, from the viewpoint of the impact resistance of the polypropylene resin composition of the present invention, at least one selected from the group consisting of a triblock copolymer (ABA), a tetrablock copolymer (ABAB), and a diblock copolymer (AB) is preferred, and a triblock copolymer (ABA) and / or a tetrablock copolymer (ABAB) is more preferred. Here, in this specification, when polymer blocks of the same type are linearly bonded via a bifunctional coupling agent or the like, the entire bonded polymer blocks are treated as a single polymer block. Accordingly, polymer blocks that should strictly be expressed as YXY (X represents a coupling residue), including the above examples, are expressed as Y as a whole, unless there is a particular need to distinguish them from a single polymer block Y. In this specification, since this type of polymer block containing a coupling agent residue is treated as above, for example, a block copolymer containing a coupling agent residue and that should strictly be expressed as ABXBA (X represents a coupling agent residue) is expressed as ABA and is treated as an example of a triblock copolymer.

[0044] Furthermore, the hydrogenated block copolymer (C) may contain a polymer block (C-3) composed of a polymerizable monomer other than the polymer block (C-1) and the polymer block (C-2), provided that the object of the present invention is not impaired. The polymer block (C-3) is not particularly limited, but in a preferred embodiment, the polymer block (C-3) is mainly composed of structural units derived from isoprene (Ip) units. Here, "mainly composed" means that the polymer block (C-3) contains 50% by mass or more of structural units derived from isoprene (Ip) based on the total mass of the polymer block (C-3). The content of structural units derived from isoprene (Ip) in the polymer block (C-3) is more preferably 70% by mass or more, and even more preferably 90% by mass or more, based on the total mass of the polymer block (C-3). The conjugated diene compound constituting the polymer block (C-3) mainly contains isoprene (Ip) units and may further contain at least one selected from, for example, 2,3-dimethylbutadiene, 1,3-pentadiene, 1,3-hexadiene, and the like. When the polymer block (C-3) contains more than 90% by mass of structural units derived from isoprene (Ip) units, the vinyl bond content is not particularly limited, but is preferably 20% or less, more preferably 2 to 15%, and particularly preferably 5 to 10%. Having the vinyl bond content of the polymer block (C-3) within the above range tends to result in better impact resistance, particularly impact resistance at low temperatures. On the other hand, when the polymer block (C-3) contains both butadiene (Bd) units and isoprene (Ip) units, the content ratio of the butadiene (Bd) units and the isoprene (Ip) units (butadiene units / isoprene units) (molar ratio) is not particularly limited, but from the viewpoint of improving performance, it is preferably 10 / 90 to 90 / 10, more preferably 30 / 70 to 70 / 30, and particularly preferably 40 / 60 to 60 / 40. Furthermore, when the polymer block (C-3) contains both butadiene (Bd) units and isoprene (Ip) units in a molar ratio of 10 / 90 to 90 / 10, the vinyl bond content is not particularly limited, but is preferably 25% or more, more preferably 40 to 80%, even more preferably 45 to 75%, and particularly preferably 50 to 70%. Having the vinyl bond content within the above range tends to provide better impact resistance, particularly impact resistance at low temperatures.

[0045] In addition, the carbon-carbon double bonds of the polymer block (C-3), like those of the polymer block (C-2), are preferably hydrogenated from the viewpoint of affinity with the polypropylene-based polymer (A) and / or the ethylene-α-olefin copolymer rubber (B). The hydrogenation rate (hydrogenation ratio) of the polymer block (C-3) in the hydrogenated block copolymer (C) is not particularly limited, but is preferably 80 mol% or more, more preferably 85 mol% or more, and particularly preferably 90 to 100 mol%. When the hydrogenation rate of the polymer block (C-3) in the hydrogenated block copolymer (C) is within the above-mentioned range, the hydrogenated block copolymer (C) exhibits good affinity with the polypropylene-based polymer (A) and the ethylene-α-olefin copolymer rubber (B), and as a result, the impact resistance of the composition tends to be improved.

[0046] When polymer block (C-1) is represented by A, polymer block (C-2) by B, and polymer block (C-3) by C, examples of the block copolymer structure include a triblock copolymer represented by ABC, a tetrablock copolymer represented by ABCA, and a tetrablock copolymer represented by ABAC. Among these, a tetrablock copolymer represented by ABAC is preferred from the viewpoint of the impact resistance of the composition of the present invention. When the balance between rigidity and low-temperature impact resistance is particularly important in the composition of the present invention, the bonding structure of the hydrogenated block copolymer (C) is preferably a tetrablock copolymer represented by ABAB or a tetrablock copolymer represented by ABAC, i.e., a tetrablock copolymer having polymer blocks represented by B or C at the terminal blocks. When the hydrogenated block copolymer (C) has the structure of a tetrablock copolymer represented by ABAB or a tetrablock copolymer represented by ABAC, the ratio of the terminal blocks B or C in the hydrogenated block copolymer (C) is not particularly limited. From the viewpoint of obtaining a better balance between rigidity and impact resistance at low temperatures, the proportion of the terminal block B or C is preferably 40 mass% or less, more preferably 1 to 35 mass%, even more preferably 4 to 30 mass%, and particularly preferably 12 to 30 mass%, of the entire hydrogenated block copolymer (C).

[0047] A specific example of the hydrogenated block copolymer (C) is preferably a polystyrene-hydrogenated butadiene / isoprene copolymer-polystyrene triblock copolymer (hereinafter sometimes referred to as "SEEPS"), which is presumed to have a structure represented by the following general formula (1) from the viewpoint of impact resistance. [ka] In the above formula (1), i, k, l, m, and n each represent an integer of 1 or greater. In the above formula (1), the order of the isoprene unit and the butadiene unit is random.

[0048] The melt flow rate (MFR) of the hydrogenated block copolymer (C) is not particularly limited, but is preferably 0.1 to 50 g / 10 min, more preferably 0.2 to 40 g / 10 min, and particularly preferably 0.3 to 30 g / 10 min. If the melt flow rate (MFR) of the hydrogenated block copolymer (C) is equal to or higher than the lower limit, the processability tends to be good, and if it is equal to or lower than the upper limit, the mechanical properties tend to be good.

[0049] The weight average molecular weight (Mw) of the hydrogenated block copolymer (C) is not particularly limited, but is preferably 10,000 to 200,000, more preferably 20,000 to 180,000, even more preferably 30,000 to 160,000, still more preferably 50,000 to 160,000, and particularly preferably 70,000 to 150,000. When the weight average molecular weight (Mw) of the hydrogenated block copolymer (C) is at least the lower limit, the impact resistance tends to be good, and when it is at most the upper limit, the compatibility with the polypropylene polymer (A) tends to be good.

[0050] The content of the hydrogenated block copolymer (C) is not particularly limited, but is preferably 1 to 50 parts by mass, more preferably 5 to 45 parts by mass, even more preferably 7 to 40 parts by mass, still more preferably 10 to 40 parts by mass, and particularly preferably 10 to 35 parts by mass, relative to 100 parts by mass of the polypropylene polymer (A). When the content of the hydrogenated block copolymer (C) is at least the lower limit, impact resistance tends to be good, while when it is at most the upper limit, costs tend to be reduced while rigidity is maintained.

[0051] <Method for producing hydrogenated block copolymer (C)> Examples of methods for producing the hydrogenated block copolymer (C) include solution polymerization, emulsion polymerization, and solid-phase polymerization. Among these, solution polymerization is preferred, and known methods such as ionic polymerization methods such as anionic polymerization and cationic polymerization; and radical polymerization can be applied. Among these, anionic polymerization is preferred. In the anionic polymerization method, a mixture of an aromatic vinyl compound, butadiene (Bd), and isoprene (Ip) is sequentially added in the presence of a solvent, an anionic polymerization initiator, and, if necessary, a Lewis base to obtain a block copolymer, which is then hydrogenated to obtain the hydrogenated block copolymer (C).

[0052] Examples of organolithium compounds used as polymerization initiators in the above method include monolithium compounds such as methyllithium, ethyllithium, pentyllithium, n-butyllithium, sec-butyllithium, and tert-butyllithium; and dilithium compounds such as tetraethylenedilithium. The solvent is not particularly limited as long as it does not adversely affect the polymerization reaction, and examples thereof include aliphatic hydrocarbons such as cyclohexane, methylcyclohexane, n-hexane, and n-pentane; aromatic hydrocarbons such as benzene, toluene, and xylene; etc. The polymerization reaction is usually carried out at 0 to 100°C for 0.5 to 50 hours.

[0053] After polymerization by the above method, the polymerization reaction can be terminated by adding an active hydrogen compound such as an alcohol, a carboxylic acid, or water, and the resulting product can be hydrogenated in an inert organic solvent in the presence of a hydrogenation catalyst according to a known method to obtain a hydrogenated product. The hydrogenation reaction can be carried out in the presence of a hydrogenation catalyst under conditions of a reaction temperature of 20 to 100°C and a hydrogen pressure of 0.1 to 10 MPa. Examples of hydrogenation catalysts include Raney nickel; heterogeneous catalysts in which a metal such as Pt, Pd, Ru, Rh, or Ni is supported on a substrate such as carbon, alumina, or diatomaceous earth; Ziegler catalysts formed by combining a transition metal compound with an alkylaluminum compound, an alkyllithium compound, or the like; and metallocene catalysts.

[0054] The hydrogenated block copolymer (C) thus obtained can be obtained by pouring the polymerization reaction liquid into methanol or the like to coagulate it, followed by drying under heat or reduced pressure, or by pouring the polymerization reaction liquid into hot water together with steam to remove the solvent by azeotropy (so-called steam stripping), followed by drying under heat or reduced pressure. The hydrogenated block copolymer (C) can be produced, for example, according to the method described in JP-A-10-67894 and WO 2009 / 031625.

[0055] (Other ingredients) Examples of other optional components include other polymers (D), inorganic fillers (E), and other additives (F).

[0056] <Other polymers (D)> The other polymer (D) is a polymer other than the polypropylene-based polymer (A), the ethylene-α-olefin copolymer rubber (B), and the hydrogenated block copolymer (C). The other polymer (D) is not particularly limited, and examples thereof include polyethylenes such as low-density polyethylene (LDPE), linear low-density polyethylene (LLDPE), medium-density polyethylene (MDPE), and high-density polyethylene (HDPE); polystyrenes such as syndiotactic polystyrene; polycyclohexylethane; polyesters such as polyethylene terephthalate; and ethylene / styrene interpolymers. These may be used alone or in combination of two or more. Among these, polyethylenes such as medium-density polyethylene (MDPE) and high-density polyethylene (HDPE) are preferred, with high-density polyethylene (HDPE) being particularly preferred, from the viewpoint of achieving higher rigidity while maintaining the impact resistance of the polypropylene-based resin composition of the present invention.

[0057] In one preferred embodiment, the polypropylene resin composition of the present invention is a resin composition consisting essentially of resin components, i.e., the polypropylene polymer (A), the ethylene-α-olefin copolymer rubber (B), the hydrogenated block copolymer (C), and another polymer (D). In the case of such a composition, since no inorganic components are contained in the resin composition, even when a molded article obtained by molding the resin composition is incinerated, no residue derived from the inorganic components is generated in the incinerator. Generally, polypropylene resin compositions are often used with the addition of inorganic fillers to achieve a balance between rigidity and impact resistance. However, the resin composition of the present invention is excellent in that it maintains an excellent balance between rigidity and impact resistance even without the addition of inorganic fillers. In another preferred embodiment, the polypropylene resin composition of the present invention consists solely of the polypropylene polymer (A), the ethylene-α-olefin copolymer rubber (B), and the hydrogenated block copolymer (C). In another preferred embodiment, the polypropylene resin composition of the present invention further contains another polymer (D). When the other polymer (D) is further contained, the content of the other polymer (D) in the resin components of the polypropylene resin composition of the present invention is not particularly limited, but from the viewpoints of impact resistance, tensile elongation at break, and rigidity, it is preferably 30% by mass or less, more preferably 25% by mass or less, even more preferably 20% by mass or less, particularly preferably 15% by mass or less, preferably 1% by mass or more, more preferably 3% by mass or more, even more preferably 5% by mass or more, and particularly preferably 7% by mass or more.

[0058] <Inorganic filler (E)> The inorganic filler (E) is not particularly limited, and examples thereof include silica, calcium carbonate, magnesium carbonate, magnesium hydroxide, aluminum hydroxide, calcium sulfate, barium sulfate, carbon black, glass fiber, glass beads, glass balloons, glass flakes, graphite, titanium oxide, potassium titanate whiskers, carbon fiber, alumina, kaolin clay, silicic acid, calcium silicate, quartz, mica, talc, clay, zirconia, potassium titanate, alumina, and metal particles. These may be used alone or in combination of two or more. Among these, talc and calcium carbonate are preferred, and talc is more preferred, from the viewpoints of rigidity and impact resistance. The shape of the inorganic filler (E) is not particularly limited, and examples thereof include scale-like, spherical, granular, powdery, irregularly shaped, etc. These may be used alone or in combination of two or more.

[0059] The polypropylene resin composition of the present invention may further contain an inorganic filler (E) when used in applications requiring particularly high rigidity. When the inorganic filler (E) is contained, the content of the inorganic filler (E) in the polypropylene resin composition is not particularly limited, but is preferably 5 to 30 parts by mass, more preferably 10 to 25 parts by mass, and particularly preferably 15 to 23 parts by mass, per 100 parts by mass of the total resin components in the polypropylene resin composition (the total of the polypropylene polymer (A), the ethylene-α-olefin copolymer rubber (B), the hydrogenated block copolymer (C), and the other polymer (D)). When the content of the inorganic filler (E) is equal to or greater than the lower limit, the rigidity and impact resistance tend to be good, while when the content is equal to or less than the upper limit, the impact resistance and tensile elongation at break tend to be good.

[0060] <Other Additives (F)> The other additives (F) are not particularly limited and include, for example, flame retardants, stabilizers, colorants, pigments, antioxidants, antistatic agents, dispersants, flow enhancers, mold release agents such as metal stearates, silicone oils, mineral oil-based softeners, synthetic resin-based softeners, copper inhibitors, crosslinking agents, nucleating agents, etc. These may be used alone or in combination of two or more. When other additives (F) are contained, the content of the other additives (F) in the polypropylene resin composition is not particularly limited, but is preferably less than 20 parts by mass, more preferably less than 10 parts by mass, and particularly preferably less than 5 parts by mass per 100 parts by mass of the total resin components in the polypropylene resin composition (the total of the polypropylene polymer (A), the ethylene-α-olefin copolymer rubber (B), the hydrogenated block copolymer (C), and the other polymer (D)).

[0061] The polypropylene-based resin composition of the present invention can be prepared by known blending or mixing means, and a suitable method can be selected as appropriate. The components to be mixed are preferably blended together in a single-stage process or a multi-stage process. Furthermore, the polypropylene-based resin composition may be prepared by dry blending the individual components followed by melt mixing, either directly in an extruder for producing molded articles (e.g., finished products such as automobile parts) or by premixing in a separate extruder (e.g., a Banbury mixer). The dry blend of the polypropylene-based resin composition of the present invention may also be directly injection molded without premelt mixing.

[0062] The mixing device is not particularly limited, and examples thereof include a Banbury mixer, a Labo Plastomill, and extruders such as a single-screw extruder and a twin-screw extruder. These may be used alone or in combination of two or more. Among these, extruders are preferred from the viewpoints of productivity and good kneading properties. To obtain better performance, some of the components to be mixed may be blended in different steps.

[0063] [Hydrogenated Block Copolymer (C)] The present invention also provides a hydrogenated block copolymer (C). The hydrogenated block copolymer (C) of the present invention is a hydrogenated product of a block copolymer having a polymer block (C-1) mainly composed of aromatic vinyl compound units, a polymer block (C-2) mainly composed of butadiene (Bd) units and isoprene (Ip) units, and a polymer block (C-3) mainly composed of structural units derived from isoprene (Ip) units (excluding the polymer block (C-2)), and is a tetrablock copolymer whose bonding structure is represented by ABAC when the polymer block (C-1) is represented by A, the polymer block (C-2) is represented by B, and the polymer block (C-3) is represented by C.

[0064] The vinyl bond content of the polymer block (C-2) in the hydrogenated block copolymer (C) of the present invention is not particularly limited, but is preferably 20% or less, more preferably 2 to 15%, even more preferably 5 to 10%, and particularly preferably 6 to 8%. When the vinyl bond content of the polymer block (C-2) is within the above range, better impact resistance, particularly impact resistance at low temperatures, tends to be obtained.

[0065] The proportion of the polymer block (C-3) in the hydrogenated block copolymer (C) of the present invention is not particularly limited, but is preferably 40 mass% or less of the entire hydrogenated block copolymer (C), more preferably 1 to 35 mass%, even more preferably 4 to 30 mass%, and particularly preferably 12 to 30 mass%.

[0066] The content of structural units derived from isoprene (Ip) in the polymer block (C-3) in the hydrogenated block copolymer (C) of the present invention is not particularly limited, but is preferably 70% by mass or more, even more preferably 90% by mass or more, and particularly preferably 100% by mass, based on the total mass of the polymer block (C-3). On the other hand, when the polymer block (C-3) contains both butadiene (Bd) units and isoprene (Ip) units, the content ratio of the butadiene (Bd) units and the isoprene (Ip) units (butadiene units / isoprene units) (molar ratio) is not particularly limited, but from the viewpoint of improving performance, it is preferably 10 / 90 to 90 / 10, more preferably 30 / 70 to 70 / 30, and particularly preferably 40 / 60 to 60 / 40.

[0067] The vinyl bond content of the polymer block (C-3) in the hydrogenated block copolymer (C) of the present invention is not particularly limited, but when the content of structural units derived from isoprene (Ip) in the polymer block (C-3) exceeds 90% by mass, it is preferably 20% or less, more preferably 2 to 15%, even more preferably 5 to 10%, and particularly preferably 6 to 8%. Furthermore, when the polymer block (C-3) contains both butadiene (Bd) units and isoprene (Ip) units in a molar ratio of 10 / 90 to 90 / 10, the vinyl bond content is not particularly limited, but is preferably 25% or more, more preferably 40 to 80%, even more preferably 45 to 75%, and particularly preferably 50 to 70%. Having a vinyl bond content within the above range tends to provide better impact resistance, particularly at low temperatures.

[0068] The hydrogenation rate (hydrogenation rate) of the polymer block (C-3) in the hydrogenated block copolymer (C) of the present invention is not particularly limited, but is preferably 80 mol % or more, more preferably 85 mol % or more, and particularly preferably 90 to 100 mol %.

[0069] The weight average molecular weight (Mw) of the hydrogenated block copolymer (C) of the present invention is not particularly limited, but is preferably 10,000 to 200,000, more preferably 20,000 to 180,000, even more preferably 30,000 to 160,000, still more preferably 50,000 to 160,000, and particularly preferably 70,000 to 150,000.

[0070] The molecular weight distribution (Mw / Mn) of the hydrogenated block copolymer (C) of the present invention is not particularly limited, but is preferably 1.50 or less, more preferably 1.30 or less, and particularly preferably 1.10 or less.

[0071] The content of aromatic vinyl compound units in the hydrogenated block copolymer (C) of the present invention is not particularly limited as long as it is less than 30% by mass, but from the viewpoint of obtaining particularly excellent impact resistance, it is preferably 4 to 28% by mass, more preferably 8 to 25% by mass, and particularly preferably 12 to 22% by mass.

[0072] The weight average molecular weight (Mw) of the polymer block (C-1) in the hydrogenated block copolymer (C) of the present invention is not particularly limited, but is preferably 1,000 to 20,000, more preferably 2,000 to 10,000, even more preferably 3,000 to 9,000, and particularly preferably 4,000 to 8,000.

[0073] A specific example of the hydrogenated block copolymer (C) of the present invention is preferably a polystyrene-hydrogenated butadiene / isoprene copolymer-polystyrene-hydrogenated polyisoprene tetrablock copolymer, which is presumed to have a structure represented by the following general formula (2) from the viewpoint of impact resistance. Another preferred embodiment is a tetrablock copolymer of polystyrene-hydrogenated butadiene / isoprene copolymer 1-polystyrene-hydrogenated butadiene / isoprene copolymer 2. In this case, the vinyl bond amounts of the hydrogenated butadiene / isoprene copolymer 1 block and the hydrogenated butadiene / isoprene copolymer 2 blocks may be the same or different. [ka] In the above formula (2), o, p, q, r, s, and t each represent an integer of 1 or greater. In the above formula (2), the order of the isoprene unit and the butadiene unit is random.

[0074] [Molded products, interior and exterior materials for automobiles] The present invention also provides a molded article containing at least the polypropylene resin composition of the present invention. The molded article of the present invention can be obtained, for example, by molding the polypropylene resin composition of the present invention by softening or melting it with heat. The molding technique is not particularly limited, and examples thereof include compression molding, injection molding, gas-assisted injection molding, hollow molding, sheet molding, rotational molding, lamination molding, calendaring, vacuum molding, thermoforming, heat molding, and extrusion. These may be used alone or in combination of two or more. Among these, injection molding is preferred from the viewpoint of productivity. The uses of the molded article of the present invention are not particularly limited, and examples thereof include automotive interior and exterior materials such as bumper beams, bumper plates, pillars, and instrument panels; housings and covers for electrical equipment; freezer containers; garden furniture; and building and construction sheets. These may be used alone or in combination of two or more. Among these, automotive interior and exterior materials are preferred from the viewpoint of impact resistance. [Example]

[0075] EXAMPLES The present invention will be specifically explained below with reference to examples and comparative examples, but the present invention is not limited to these examples at all. The composition components (polypropylene polymer (A), ethylene-α-olefin copolymer rubber (B), hydrogenated block copolymer (C)) used in the preparation of each example and the melt flow rate (MFR) of the polypropylene resin composition obtained in each example, the content of aromatic vinyl compound units (styrene content) in hydrogenated block copolymers 1 to 7 (SEEPS, SEBS, SEP, SEEPSEP, SEEPSEEP) produced in each production example, and the hydrogenation time for hydrogenated block copolymers 1 to 7 (SEEPS, SEBS, SEP, SEEPSEP, SEEPSEEP) produced in each production example are also shown. The "vinyl bond amount of polymer block (C-2)" in block copolymer (C), the "vinyl bond amount of polymer block (C-3)" in hydrogenated block copolymers 6 and 7 produced in Production Examples 6 and 7, the hydrogenation rate in polymer blocks (C-2) (and (C-3)) of hydrogenated block copolymer (C) for hydrogenated block copolymers 1 to 7 (SEEPS, SEBS, SEP, SEEPSEP, SEEPSEEP) produced in each Production Example, and the impact resistance (Charpy impact strength), flexural strength, and flexural modulus of elasticity of the molded products obtained in each Example were evaluated according to the evaluation methods described below.

[0076] (1. Melt flow rate (MFR) evaluation method) The composition components (polypropylene polymer (A), ethylene-α-olefin copolymer rubber (B), hydrogenated block copolymer (C)) used in the preparation of each example and the polypropylene resin composition obtained in each example were evaluated for melt flow rate (MFR) in accordance with ISO1133:1997 (unit: g / 10 min, 230°C, 2.16 kgf).

[0077] (2. Method for evaluating the content of aromatic vinyl compound units (styrene content) in hydrogenated block copolymer (C)) The hydrogenated block copolymers 1 to 7 (SEEPS, SEBS, SEP, SEEPSEP, SEEPSEEP) produced in each Production Example were each dissolved in CDCl3, 1H-NMR measurement [apparatus: "ADVANCE 400 Nano bay" (manufactured by Bruker), measurement temperature: 30°C] was performed, and the content of aromatic vinyl compound units (styrene content) in the hydrogenated block copolymer was calculated from the obtained spectrum.

[0078] (3. Method for evaluating "amount of vinyl bond in polymer block (C-2) or (C-3)" and "degree of vinylization of hydrogenated block copolymer (C)" in hydrogenated block copolymer (C) Dissolve the block copolymer (C) before hydrogenation in CDCl3. 1H-NMR measurements were performed using an "ADVANCE 400 Nano bay" (Bruker) at a measurement temperature of 30°C. The vinyl bond content (the total content of 3,4-bond units and 1,2-bond units) was calculated from the ratio of the peak areas corresponding to the 3,4-bond units and 1,2-bond units in the isoprene structural units and the 1,2-bond units in the butadiene structural units to the total peak area of ​​the structural units derived from isoprene and / or butadiene. When the hydrogenated block copolymer (C) was a triblock copolymer consisting of polymer block (C-1), polymer block (C-2), and polymer block (C-1), the vinyl bond content of polymer block (C-2) was taken as the degree of vinylation of the hydrogenated block copolymer (C). On the other hand, when the hydrogenated block copolymer (C) was a tetrablock copolymer consisting of polymer block (C-1)-polymer block (C-2)-polymer block (C-1)-polymer block (C-3), a portion of the polymerization solution was sampled at the stage where a triblock copolymer consisting of polymer block (C-1)-polymer block (C-2)-polymer block (C-1) was polymerized, and the vinyl bond content of polymer block (C-2) was measured using the method described above. Then, after polymerizing a tetrablock copolymer consisting of polymer block (C-1)-polymer block (C-2)-polymer block (C-1)-polymer block (C-3), the vinyl content of the entire polymer was measured using the method described above. The vinyl bond content of polymer block (C-3) was calculated from the resulting vinyl bond content of polymer block (C-2), the vinyl content of the entire polymer, and the respective contents of polymer block (C-2) and polymer block (C-3).

[0079] (4. Method for Evaluating the Hydrogenation Ratio of Polymer Blocks (C-2) (and (C-3)) of Hydrogenated Block Copolymer (C)) Hydrogenated block copolymer was dissolved in CDCl3 1 H-NMR measurement [apparatus: "ADVANCE 400 Nano bay" (manufactured by Bruker), measurement temperature: 30°C] was performed, and the hydrogenation rate was calculated from the ratio of the peak area derived from the residual olefin of isoprene or butadiene to the peak area derived from ethylene, propylene, and butylene.

[0080] (5. Method for Evaluating Weight-Average Molecular Weight of Hydrogenated Block Copolymer (C)) It was determined by measuring through GPC measurement under the following conditions. <GPC Measuring Apparatus and Measuring Conditions> · Apparatus: GPC apparatus "HLC-8020" (manufactured by Tosoh Corporation) · Separation column: Two "TSKgel G4000HX" manufactured by Tosoh Corporation were connected in series. · Eluent: Tetrahydrofuran · Eluent flow rate: 0.7 mL / min · Sample concentration: 5 mg / 10 mL · Column temperature: 40 °C · Detector: Differential refractive index (RI) detector · Calibration curve: Prepared using standard polystyrene

[0081] (6. Method for Evaluating Impact Resistance (Charpy Impact Strength)) For the molded products of the polypropylene-based resin compositions obtained in each example, in accordance with ISO179, the impact resistance (Charpy impact strength) was evaluated (with notch: Type A Charpy (Test Methods E23) specimens, Hammer capacity: 7.5 J, number of samples: n = 5, measurement temperatures: +21 °C, 0 °C, -20 °C, -40 °C).

[0082] (7. Method for Evaluating Specified Flexural Strength (Strain 3.5%) and Flexural Modulus (Strain 0.05 - 0.25%)) Using the polypropylene-based resin compositions obtained in each example, injection molding was performed with an injection molding machine ("EC75SX", manufactured by Toshiba Machine Co., Ltd.) to produce JIS multi-purpose test piece A1. Using the central part thereof (length 80 mm × width 10 mm × thickness 4 mm), based on JIS K 7171 (ISO 178), a flexural strength test was performed using a universal testing machine (manufactured by Instron, model 5566) to measure the specified flexural strength [MPa] (strain 3.5%) and flexural modulus [MPa] (strain 0.05 - 0.25%).

[0083] [Production Example 1] A nitrogen-purged, dried pressure vessel equipped with a stirrer was charged with 50 kg of cyclohexane dried over molecular sieves A4 and 190 g of a 10% by mass sec-butyllithium cyclohexane solution (effective amount of sec-butyllithium added: 19 g) as an anionic polymerization initiator. After heating the pressure vessel to 50 ° C, 2000 g of fully dehydrated styrene (1) was added and polymerized at 50 ° C for 60 minutes. After that, a previously prepared mixture of 8400 g of isoprene and 5600 g of butadiene was added and polymerized at 50 ° C for 60 minutes. 2000 g of styrene (2) was then added and polymerized at 50 ° C for 60 minutes. Methanol was added to terminate the reaction, and a styrene-isoprene / butadiene-styrene type block copolymer (hereinafter referred to as block copolymer 1) was prepared as a cyclohexane solution. The reaction solution was heated to 50°C and pressurized to a hydrogen pressure of 1 MPa, and then a Ziegler catalyst (hydrogenation catalyst) formed from nickel octylate and trimethylaluminum was added under a hydrogen atmosphere. The temperature was raised to 80°C by the heat of reaction, and the reaction was continued until hydrogen absorption ceased, thereby carrying out the hydrogenation reaction of polymer block (C-2). The reaction solution was allowed to cool and the pressure was released, and then the Ziegler catalyst was removed by washing with water, and the resulting mixture was dried in vacuo to obtain a hydrogenated product of a polystyrene-poly(isoprene / butadiene)-polystyrene triblock copolymer (hereinafter abbreviated as hydrogenated block copolymer 1). The obtained hydrogenated block copolymer 1 was a polystyrene-hydrogenated butadiene / isoprene copolymer-polystyrene triblock copolymer (SEEPS), had a styrene content of 20 mass%, a "vinyl bond content of polymer block (C-2)" (i.e., the vinylization degree of hydrogenated block copolymer 1) of 6.3%, a weight-average molecular weight of 98,000, a hydrogenation rate in polymer block (C-2) of 98.7%, and a melt flow rate (MFR) of 1.0 g / 10 min (230°C, 2.16 kgf).

[0084] [Production Example 2] A nitrogen-purged, dried pressure vessel equipped with a stirrer was charged with 50 kg of cyclohexane dried over molecular sieves A4 and 70 g of a 10% by mass sec-butyllithium cyclohexane solution (7 g of sec-butyllithium) as an anionic polymerization initiator. After heating the pressure vessel to 50 ° C, 3,000 g of thoroughly dehydrated styrene (1) was added and polymerized at 50 ° C for 60 minutes. A previously prepared mixture of 8,400 g of isoprene and 5,600 g of butadiene was added and polymerized at 50 ° C for 60 minutes. 3,000 g of styrene (2) was then added and polymerized at 50 ° C for 60 minutes. Methanol was added to terminate the reaction, and a styrene-isoprene / butadiene-styrene block copolymer (hereinafter referred to as block copolymer 2) was prepared as a cyclohexane solution. A cyclohexane solution of the obtained block copolymer 2 was subjected to a hydrogenation reaction under the same conditions as those described in Production Example 1 to obtain a hydrogenated product of a polystyrene-poly(isoprene / butadiene)-polystyrene triblock copolymer (hereinafter abbreviated as hydrogenated block copolymer 2). The obtained hydrogenated block copolymer 2 was a polystyrene-hydrogenated butadiene / isoprene copolymer-polystyrene triblock copolymer (SEEPS), had a styrene content of 30% by mass, a "vinyl bond content of polymer block (C-2)" (i.e., "degree of vinylization of hydrogenated block copolymer 2") of 6.3%, a weight-average molecular weight of 270,000, and a hydrogenation rate of polymer block (C-2) of 98.7%. Furthermore, the melt flow rate (MFR) was measured, and it did not flow under the conditions of "230°C, 2.16 kgf."

[0085] [Production Example 3] A nitrogen-purged, dried pressure vessel equipped with a stirrer was charged with 50 kg of cyclohexane dried over molecular sieves A4 and 70 g of a 10% by mass sec-butyllithium cyclohexane solution (7 g of sec-butyllithium) as an anionic polymerization initiator. After heating the pressure vessel to 50 ° C, 3,400 g of fully dehydrated styrene (1) was added and polymerized at 50 ° C for 60 minutes. 90 g of tetrahydrofuran was then added, followed by 14,000 g of butadiene, and polymerization was continued at 60 ° C for 60 minutes. 3,400 g of styrene (2) was then added and polymerized at 50 ° C for 60 minutes. Methanol was then added to terminate the reaction, yielding a styrene-butadiene-styrene block copolymer (hereinafter referred to as block copolymer 3) as a cyclohexane solution. A cyclohexane solution of the obtained block copolymer 3 was subjected to a hydrogenation reaction under the same conditions as those described in Production Example 1 to obtain a hydrogenated product of a polystyrene-polybutadiene-polystyrene triblock copolymer (hereinafter abbreviated as hydrogenated block copolymer 3). The obtained hydrogenated block copolymer 3 was a polystyrene-hydrogenated polybutadiene-polystyrene triblock copolymer (SEBS), had a styrene content of 33% by mass, a "vinyl bond content of polymer block (C-2)" (i.e., "degree of vinylization of hydrogenated block copolymer 3") of 38.3%, a weight-average molecular weight of 290,000, and a hydrogenation rate of polymer block (C-2) of 99.5%. Furthermore, the melt flow rate (MFR) was measured, and it did not flow under the conditions of "230°C, 2.16 kgf."

[0086] [Production Example 4] A hydrogenated polystyrene-poly(isoprene / butadiene)-polystyrene triblock copolymer (hereinafter referred to as hydrogenated block copolymer 4) was obtained in accordance with the method described in Production Example 2, except that 220 g of a 10% by mass sec-butyllithium cyclohexane solution (effective amount of sec-butyllithium added: 22 g) was used instead of 70 g of a 10% by mass sec-butyllithium cyclohexane solution (effective amount of sec-butyllithium added: 7 g) as the anionic polymerization initiator. The obtained hydrogenated block copolymer 4 was a polystyrene-hydrogenated butadiene / isoprene copolymer-polystyrene triblock copolymer (SEEPS), had a styrene content of 30% by mass, a weight-average molecular weight of 90,000, a hydrogenation rate of 98.2% in the polymer block (C-2), and a melt flow rate (MFR) of less than 0.1 g / 10 min (230 °C, 2.16 kgf).

[0087] [Production Example 5] A nitrogen-purged, dried pressure vessel equipped with a stirrer was charged with 50 kg of cyclohexane dried over molecular sieves A4 and 160 g of a 10% by mass cyclohexane solution of sec-butyllithium as an anionic polymerization initiator (effective amount of sec-butyllithium added: 16 g). After heating the pressure vessel to 50 °C, 8,000 g of fully dehydrated styrene was added and polymerized at 50 °C for 60 minutes. Then, 14,000 g of isoprene was added and polymerized at 60 °C for 60 minutes. Methanol was added to terminate the reaction, and a styrene-isoprene block copolymer (hereinafter referred to as block copolymer 5) was prepared as a cyclohexane solution. The resulting cyclohexane solution of block copolymer 5 was subjected to a hydrogenation reaction under the same conditions as those described in Production Example 1, yielding a hydrogenated polystyrene-polyisoprene diblock copolymer (hereinafter referred to as hydrogenated block copolymer 5). The obtained hydrogenated block copolymer 5 was a polystyrene-hydrogenated polyisoprene diblock copolymer (SEP), had a styrene content of 36% by mass, a weight-average molecular weight of 90,000, and a hydrogenation rate of 98.2% in the polymer block (C-2). The melt flow rate (MFR) was measured, and it did not flow under the conditions of "230°C, 2.16 kgf".

[0088] [Production Example 6] A nitrogen-purged, dried pressure vessel equipped with a stirrer was charged with 50 kg of cyclohexane dried over molecular sieves A4 and 130 g of a 10% by mass sec-butyllithium cyclohexane solution (effective amount of sec-butyllithium added: 13 g) as an anionic polymerization initiator. After heating the pressure vessel to 50 ° C, 1100 g of fully dehydrated styrene (1) was added and polymerized at 50 ° C for 60 minutes. After that, a previously prepared mixture of 5000 g of isoprene and 3950 g of butadiene was added and polymerized at 50 ° C for 60 minutes. 1100 g of styrene (2) was added and polymerized at 50 ° C for 60 minutes. 1250 g of isoprene was added and polymerized at 50 ° C for 60 minutes. Methanol was added to terminate the reaction, and a styrene-isoprene / butadiene-styrene-isoprene type block copolymer (hereinafter referred to as block copolymer 6) was prepared as a cyclohexane solution. The reaction solution was heated to 50°C and pressurized to a hydrogen pressure of 1 MPa, and then a Ziegler catalyst (hydrogenation catalyst) formed from nickel octylate and trimethylaluminum was added under a hydrogen atmosphere. The temperature was raised to 80°C by the heat of reaction, and the reaction was continued until hydrogen absorption ceased, thereby carrying out the hydrogenation reaction of polymer blocks (C-2) and (C-3). The reaction solution was allowed to cool and the pressure was released, and then the Ziegler catalyst was removed by washing with water, and the resulting mixture was dried in vacuo to obtain a hydrogenated product of a polystyrene-poly(isoprene / butadiene)-polystyrene-polyisoprene tetrablock copolymer (hereinafter abbreviated as hydrogenated block copolymer 6). The obtained hydrogenated block copolymer 6 was a polystyrene-hydrogenated butadiene / isoprene copolymer-polystyrene-hydrogenated isoprene tetrablock copolymer (SEEPSEP), with a styrene content of 18% by mass, a "vinyl bond content of polymer block (C-2)" of 6.1%, and a "degree of vinylization of hydrogenated block copolymer 6" of 6.3%. The proportion of polymer block (C-3) in hydrogenated block copolymer 6 was 10% by mass, and the calculated "vinyl bond content of polymer block (C-3)" was 6.6%. In addition, the content of structural units derived from isoprene (Ip) in polymer block (C-3) was 100% by mass.Furthermore, the weight average molecular weight of the hydrogenated block copolymer 6 was 132,000, the hydrogenation rate in the polymer blocks (C-2) and (C-3) was 99.2%, and the melt flow rate (MFR) was 0.7 g / 10 min (230°C, 2.16 kgf).

[0089] [Production Example 7] In a pressure vessel equipped with a stirrer that had been purged with nitrogen and dried, 50 kg of cyclohexane dried over molecular sieves A4 and 135 g of a cyclohexane solution of sec-butyllithium with a concentration of 10% by mass as an anionic polymerization initiator (actual amount of sec-butyllithium added: 13.5 g) were placed. After the temperature inside the pressure vessel was raised to 50°C, 1100 g of sufficiently dehydrated styrene (1) was added and polymerization was carried out at 50°C for 60 minutes. After that, a previously prepared mixture of 4150 g of isoprene and 3400 g of butadiene was added and polymerization was carried out at 50°C for 60 minutes. Further, 1100 g of styrene (2) was added and polymerization was carried out at 50°C for 60 minutes. Further, a previously prepared mixture of 1350 g of isoprene and 1100 g of butadiene and 300 g of tetrahydrofuran were added and polymerization was carried out at 50°C for 60 minutes. Methanol was added to terminate the reaction, and a styrene-isoprene / butadiene-styrene-isoprene type block copolymer (hereinafter abbreviated as block copolymer 6) was prepared as a cyclohexane solution. The reaction solution was heated to 50°C and pressurized to a hydrogen pressure of 1 MPa, and then a Ziegler catalyst (hydrogenation catalyst) formed from nickel octylate and trimethylaluminum was added under a hydrogen atmosphere. The temperature was raised to 80°C by the heat of reaction, and the reaction was continued until hydrogen absorption ceased, thereby carrying out the hydrogenation reaction of polymer blocks (C-2) and (C-3). The reaction solution was allowed to cool and the pressure was released, and then the Ziegler catalyst was removed by washing with water. The reaction solution was then vacuum dried to obtain a hydrogenated product of a polystyrene-poly(isoprene / butadiene)-polystyrene-poly(isoprene / butadiene) tetrablock copolymer (hereinafter abbreviated as hydrogenated block copolymer 7). The obtained hydrogenated block copolymer 7 was a polystyrene-hydrogenated butadiene / isoprene copolymer-polystyrene-hydrogenated poly(isoprene / butadiene) tetrablock copolymer (SEEPSEEP), with a styrene content of 18% by mass, a "vinyl bond content of polymer block (C-2)" of 6.5%, and a "degree of vinylization of hydrogenated block copolymer 7" of 20.7%. The proportion of polymer block (C-3) in hydrogenated block copolymer 7 was 20% by mass, and the calculated "vinyl bond content of polymer block (C-3)" was 60.2%.The content of structural units derived from butadiene (Bd) in polymer block (C-3) was 44% by mass, and the content of structural units derived from isoprene (Ip) was 56% by mass. The weight-average molecular weight of the hydrogenated block copolymer 7 was 120,000, the hydrogenation rate in polymer blocks (C-2) and (C-3) was 98.2%, and the melt flow rate (MFR) was 2.5 g / 10 min (230°C, 2.16 kgf).

[0090] [Example 1 and Comparative Examples 1 to 6] The components shown in Table 1 below were mixed in a twin-screw extruder (L / D = 56, 26 mmΦ) at 180°C, 350 rpm, and an extrusion rate of 5 kg / hour to prepare a polypropylene resin composition. The polypropylene resin composition was then molded at an injection molding temperature of 220°C and a mold temperature of 40°C to produce a molded product of the polypropylene resin composition. The melt flow rate (MFR) of the resulting polypropylene resin composition was evaluated, and the impact resistance (Charpy impact strength) of the molded product of the resulting polypropylene resin composition was evaluated. The flexural modulus (strain 0.05-0.25%) of the molded product of the polypropylene resin composition was also evaluated. The results are shown in Table 1.

[0091] [Table 1]

[0092] (Explanation of each component in Table 1) Polypropylene polymer (A): PP: homopolypropylene: trade name "P4C5Z-27", manufactured by Flint Hills Resources, Inc.: melt flow rate (MFR) 20 g / 10 min (230°C, 2.16 kgf) Ethylene-α-olefin copolymer rubber (B): EOR: ethylene / 1-octene random copolymer: trade name "ENGAGE® 8200", manufactured by Dow: melt flow rate (MFR) 5 g / 10 min (230°C, 2.16 kgf), density 0.87 g / cm 3 Hydrogenated block copolymer (C): Triblock copolymer of polystyrene-hydrogenated butadiene / isoprene copolymer-polystyrene (SEEPS): Hydrogenated block copolymer 1 (styrene content 20% by mass) obtained in Production Example 1 Hydrogenated block copolymer (C): Triblock copolymer of polystyrene-hydrogenated butadiene / isoprene copolymer-polystyrene (SEEPS): Hydrogenated block copolymer 2 (styrene content 30% by mass) obtained in Production Example 2 Hydrogenated block copolymer (C): Polystyrene-hydrogenated polybutadiene-polystyrene triblock copolymer (SEBS): Hydrogenated block copolymer 3 (styrene content 33% by mass) obtained in Production Example 3 Hydrogenated block copolymer (C): Triblock copolymer of polystyrene-hydrogenated butadiene / isoprene copolymer-polystyrene (SEEPS): Hydrogenated block copolymer 4 (styrene content 30% by mass) obtained in Production Example 4 Hydrogenated block copolymer (C): Polystyrene-hydrogenated polyisoprene diblock copolymer (SEP): Hydrogenated block copolymer 5 (styrene content 36% by mass) obtained in Production Example 5

[0093] As can be seen from Table 1, the molded product produced in Example 1 was excellent in impact resistance, particularly in impact resistance at low temperatures (-20°C and -40°C). On the other hand, the molded articles produced in Comparative Examples 1 to 6 did not have good impact resistance, particularly at low temperatures (-20°C and -40°C).

[0094] Hydrogenated block copolymers (C) having styrene contents of 4 mass%, 15 mass%, and 25 mass% were produced in the same manner as in Production Example 1, and polypropylene-based resin compositions were prepared in the same manner as in Example 1. Molded articles produced from these compositions are expected to exhibit the effects of the present invention. A hydrogenated block copolymer (C) was produced in the same manner as in Production Example 1, and a polypropylene-based resin composition was prepared in the same manner as in Example 1. Among these molded articles produced by these methods, the effects of the present invention can be expected for molded articles containing 5 parts by mass, 10 parts by mass, or 45 parts by mass of the hydrogenated block copolymer (C) per 100 parts by mass of the polypropylene-based polymer (A).

[0095] [Examples 2 to 10 and Comparative Example 7] The components shown in Table 2 below were mixed in a twin-screw extruder (L / D = 56, 26 mmΦ) at 180°C, 350 rpm, and an extrusion rate of 5 kg / hour to prepare a polypropylene resin composition. The polypropylene resin composition was then molded at an injection molding temperature of 220°C and a mold temperature of 40°C to produce a molded product of the polypropylene resin composition. The melt flow rate (MFR) of the resulting polypropylene resin composition was evaluated, and the impact resistance (Charpy impact strength) of the molded product of the resulting polypropylene resin composition was evaluated. The flexural modulus (strain 0.05-0.25%) and specified flexural strength (strain 3.5%) of the molded product of the polypropylene resin composition were also evaluated. The results are shown in Table 2.

[0096] [Table 2]

[0097] (Explanation of each component in Table 2) Polypropylene polymer (A): hPP: homopolypropylene; Prime Polypro J106G, manufactured by Prime Polymer; melt flow rate (MFR) 15 g / 10 min (230°C, 2.16 kgf) Polypropylene polymer (A) + ethylene-α-olefin copolymer rubber (B): block-PP: a mixture of homopolypropylene and ethylene-propylene rubber (EPR) (mass ratio 70.6:29.4): Prime Polypro J750HP, manufactured by Prime Polymer: melt flow rate (MFR) 14g / 10min (230℃, 2.16kgf), ethylene content 14.7% by mass Hydrogenated block copolymer (C): Polystyrene-hydrogenated butadiene / isoprene copolymer-polystyrene triblock copolymer (SEEPS): Hydrogenated block copolymer 1 obtained in Production Example 1 (styrene content 20% by mass, Mw 98,000, "vinyl bond amount in polymer block (C-2)" (i.e., "degree of vinylization of hydrogenated block copolymer (C)") 6.3%, hydrogenation rate in polymer block (C-2) 98.7%) Hydrogenated block copolymer (C): Polystyrene-hydrogenated butadiene / isoprene copolymer-polystyrene-polyisoprene tetrablock copolymer: Hydrogenated block copolymer 6 obtained in Production Example 6 Hydrogenated block copolymer (C): Polystyrene-hydrogenated butadiene / isoprene copolymer-polystyrene-hydrogenated butadiene / isoprene copolymer tetrablock copolymer: Hydrogenated block copolymer 7 obtained in Production Example 7 Ethylene-α-olefin copolymer rubber (B): EOR: ethylene / 1-octene random copolymer: trade name "ENGAGE® 8200", manufactured by Dow: melt flow rate (MFR) 5 g / 10 min (230°C, 2.16 kgf), density 0.87 g / cm 3 High-density polyethylene (HDPE): Bio-based polyethylene (bio-based PE): Product name "SHE150", manufactured by Braskem; melt flow rate (MFR) 1g / 10 min (190°C, 2.16 kgf) Antioxidant: Product name "ADEKA STAB AO-60" manufactured by ADEKA Corporation

[0098] As can be seen from Table 2, the molded articles produced in Examples 2 to 10 were excellent in impact resistance, particularly in impact resistance at low temperatures (-20°C and -40°C). On the other hand, the molded product produced in Comparative Example 7 did not have good impact resistance, particularly at low temperatures (-20°C and -40°C). [Industrial Applicability]

[0099] The polypropylene resin composition of the present invention is a polypropylene resin composition having good impact resistance, particularly good impact resistance at low temperatures, and further, the polypropylene resin composition containing the hydrogenated block copolymer of the present invention has the above-mentioned good properties, and is therefore useful as a material for various products such as machine parts and automobile parts.

Claims

1. A polypropylene polymer (A), an ethylene-α-olefin copolymer rubber (B), and A polypropylene-based resin composition comprising a hydrogenated block copolymer (C), the hydrogenated block copolymer (C) is a hydrogenated product of a block copolymer having at least one polymer block (C-1) mainly composed of aromatic vinyl compound units and at least one polymer block (C-2) mainly composed of butadiene (Bd) units and isoprene (Ip) units; the content of the aromatic vinyl compound unit in the hydrogenated block copolymer (C) is less than 30% by mass, the polymer block (C-2) has a vinyl bond content of 20% or less, the polypropylene-based resin composition contains 1 to 50 parts by mass of the ethylene-α-olefin copolymer rubber (B) per 100 parts by mass of the polypropylene-based polymer (A), and contains 7 to 40 parts by mass of a hydrogenated block copolymer (C) per 100 parts by mass of the polypropylene-based polymer (A); Polypropylene resin composition Injection molded products including:

2. 10. The injection molded article of claim 1, further comprising high density polyethylene.

3. 3. The injection-molded product according to claim 1, wherein the melt flow rate (MFR) measured in accordance with JIS K7210 at a temperature of 230°C and a load of 2.16 kgf is 3 to 200 g / 10 min.

4. The polypropylene polymer (A) is cured at a temperature of 230°C in accordance with JIS K7210.

4. The injection-molded product according to claim 1, wherein the melt flow rate (MFR) measured under a load of 2.16 kgf is 1 to 200 g / 10 min.

5. The injection-molded product according to any one of claims 1 to 4, wherein the ethylene-α-olefin copolymer rubber (B) has a melt flow rate (MFR) of 0.1 to 50 g / 10 min, as determined in accordance with JIS K7210 under conditions of a temperature of 230°C and a load of 2.16 kgf.

6. The injection-molded product according to any one of claims 1 to 5, wherein the ethylene-α-olefin copolymer rubber (B) is at least one selected from the group consisting of an ethylene-propylene copolymer, an ethylene-butene copolymer, and an ethylene-octene copolymer.

7. 7. The injection-molded product according to claim 6, wherein the ethylene-α-olefin copolymer rubber (B) is an ethylene-octene copolymer.

8. The injection-molded article according to any one of claims 1 to 6, wherein the hydrogenated block copolymer (C) has a melt flow rate (MFR) of 0.1 to 50 g / 10 min, as determined in accordance with JIS K7210 under conditions of a temperature of 230°C and a load of 2.16 kgf.

9. The injection-molded product according to any one of claims 1 to 8, wherein the hydrogenated block copolymer (C) is a triblock copolymer of polystyrene-hydrogenated butadiene / isoprene copolymer-polystyrene, or a diblock copolymer of polystyrene-hydrogenated butadiene / isoprene copolymer.

10. An interior / exterior material for an automobile, comprising an injection-molded product according to any one of claims 1 to 9.

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