JP2019044112A - Dynamic crosslinking type thermoplastic elastomer composition for composite molding and composite molded body - Google Patents

Abstract

To provide a dynamic crosslinking type thermoplastic elastomer composition for composite molding high in fusion strength and excellent in flowability and permanent compression set, and a composite molded body using the same.SOLUTION: There is provided a dynamic crosslinking type thermoplastic elastomer composition for composite molding containing following components (A), (B) and (C) and having Duro A hardness of 30 to 90. Component (A): an ethylene α-olefin non-conjugated diene copolymer rubber component. (B): modified polypropylene having melt flow rate (MFR, 230°C, load 21.2 N, according to JIS K7210) of 0.1 to 250 g/10 min. and melt tension of 1.0 to 20 cN, and melting point of 157°C or less and exhibiting strain hardening property.SELECTED DRAWING: None

Description

  The present invention relates to a dynamically cross-linked thermoplastic elastomer composition for composite molded bodies and a composite molded body using the dynamically cross-linked thermoplastic elastomer composition for composite molded bodies. Specifically, the present invention relates to a dynamically cross-linked thermoplastic elastomer composition for a composite molded body having high fluidity and compression set, and having excellent fusion properties for molding into a composite molded body, and the composite molding. The present invention relates to a composite molded body using a dynamically crosslinked thermoplastic elastomer composition for body.

  Conventionally, for automotive parts, electrical / electronic parts, building parts, etc., extrusion vulcanized molded products made of a rubber compound of ethylene / propylene / non-conjugated diene terpolymer (EPDM) require low hardness and rubber elasticity. It was commonly used in parts to be manufactured. However, in recent years, thermoplastic elastomer compositions that do not require a vulcanization step have begun to be used in these fields from the viewpoint of productivity, environmental friendliness, and weight reduction.

  For example, a mixture of a polyolefin resin such as polypropylene or polyethylene that imparts thermoplasticity, a mixture of ethylene / propylene / nonconjugated diene copolymer rubber that imparts rubber elasticity, and a softener that imparts flexibility and fluidity is crosslinked. The thermoplastic elastomer composition obtained by dynamic heat treatment in the presence of an agent exhibits the characteristics as a rubber-like soft material, without the need for a vulcanization step, and has the same moldability as that of a thermoplastic resin. It is known to have. Such a thermoplastic elastomer composition is called a dynamically cross-linked thermoplastic elastomer composition. From the viewpoint of rationalization of the manufacturing process, recyclability, etc., automobile parts, building materials, home appliances, medical equipment parts, electric wires, miscellaneous goods It is attracting attention in a wide range of fields. The internal structure of the dynamically crosslinked thermoplastic elastomer composition is known to be a sea-island structure in which the polyolefin resin is the sea and the ethylene / propylene / non-conjugated diene copolymer rubber is the island by dynamic crosslinking. .

For example, Patent Document 1 discloses an ethylene / α-olefin / non-conjugated polyene copolymer (A) as a thermoplastic elastomer composition excellent in adhesiveness to a vulcanized rubber molded body,
An α-olefin thermoplastic resin (B) having a melting point of 140 ° C. or higher and a heat of fusion measured in accordance with JIS K 7122 of 75 J / g or higher, and a heat of fusion measured in accordance with JIS K 7122 of 15 J / G or less of the α-olefin resin (C) and the raw material composition containing the crosslinking agent (D), and at least in the sea phase containing the α-olefin thermoplastic resin (B) Discloses a thermoplastic elastomer composition having a sea-island structure in which an island phase containing at least the ethylene / α-olefin / non-conjugated polyolefin copolymer (A) is dispersed.

  On the other hand, Patent Documents 2 and 3 include various properties at the time of injection foam molding, such as foaming characteristics, flexibility, heat resistance, and the like, by blending the thermoplastic elastomer composition with a modified polypropylene exhibiting strain-hardening properties. Techniques to improve are described.

JP 2014-193969 A JP 2011-102028 A Japanese Patent Laying-Open No. 2015-098542

The conventional thermoplastic elastomer composition is not sufficient in that it is inferior in rubber elasticity with compression set as an index compared to vulcanized rubber, and in severe applications where higher compression set is required. Substitution from vulcanized rubber is not progressing.
In addition, when molded into a multilayer molded body such as two-color molding or a composite molded body, it is important to have high fusion strength and good compression set characteristics, and high fluidity as a molding material. Desired.

  In response to such required characteristics, for example, in the dynamically crosslinked thermoplastic elastomer composition described in Patent Document 1, when high flow polypropylene having a low molecular weight is used in order to develop high fluidity, compression set is reduced. There was a tendency to get worse.

  On the other hand, Patent Document 2 and Patent Document 3 only disclose improvements in performance in injection foam molding by blending modified polypropylene exhibiting strain-hardening properties, and suggests improvements in fusion strength and compression set. Absent.

  The present invention has been made in view of such problems, and its purpose is to have high fusion strength with a counterpart material such as an olefin-based resin composition or an elastomer composition containing an olefin-based resin, fluidity and compression permanent. An object of the present invention is to provide a dynamically cross-linked thermoplastic elastomer composition for a composite molded article excellent in strain and a composite molded article using the same.

As a result of intensive studies to solve the above problems, the present inventor has heretofore been hard to feel and is a polypropylene resin that has been considered unsuitable for a high fluidity thermoplastic elastomer composition, A region in which a thermoplastic elastomer composition obtained by dynamically crosslinking a strain-curing modified polypropylene and ethylene / α-olefin / non-conjugated diene copolymer rubber in the presence of a crosslinking agent has high fluidity. However, it has been found that it exhibits high compression set and is excellent in fusion strength. And it discovered that this thermoplastic elastomer composition was a thermoplastic elastomer composition especially useful for a composite molding, and came to complete this invention.
That is, the gist of the present invention resides in the following [1] to [6].

[1] A dynamically cross-linked thermoplastic elastomer composition for composite molded bodies, comprising the following components (A), (B), and (C) and having a duro A hardness of 30 to 90.
Component (A): ethylene / α-olefin / non-conjugated diene copolymer rubber Component (B): Melt flow rate of 0.1 to 250 g / 10 minutes (MFR, 230 ° C., load 21.2 N, JIS K7210 compliant) And a modified polypropylene having a melt tension of 1.0 to 20 cN and exhibiting strain hardening with a melting point of not higher than ° C. Component (C): Crosslinker

[2] The dynamically cross-linked thermoplastic elastomer composition for composite molded bodies according to [1], wherein the component (B) is a modified polypropylene having strain-curing properties having a long-chain branched structure.

[3] 45 to 85 parts by mass of the component (A) and 15 to 55 parts by mass of the component (B) with respect to a total of 100 parts by mass of the components (A) and (B), [1] or [ 2] The dynamically crosslinked thermoplastic elastomer composition for composite molded bodies according to [2].

[4] The component (C) is at least one selected from the group consisting of organic peroxides, phenol resins, silicon hydride compounds, polyfunctional vinyl compounds, polyfunctional (meth) acrylate compounds, and tin chloride. And the composite molding in any one of [1]-[3] containing 0.05-20 mass parts of this component (C) with respect to a total of 100 mass parts of the said component (A) and the said component (B). Dynamic cross-linkable thermoplastic elastomer composition for body.

[5] The composite molded article according to any one of [1] to [4], comprising 5 to 200 parts by mass of the following component (D) with respect to a total of 100 parts by mass of the component (A) and the component (B). Dynamic crosslinkable thermoplastic elastomer composition.
Component (D): Hydrocarbon softener

[6] A composite molding comprising the dynamically crosslinked thermoplastic elastomer composition for composite moldings according to any one of [1] to [5] and an olefin resin composition or an elastomer composition containing an olefin resin. body.

  The dynamically cross-linked thermoplastic elastomer composition for a composite molded body of the present invention has good compression set characteristics while maintaining high fluidity, an olefin resin composition, an elastomer composition containing an olefin resin, and the like. Since a high fusion strength with respect to the mating material is developed, a composite molded product having a high commercial value suitable for a field requiring rubber elasticity and high interlayer adhesion can be provided.

  Embodiments of the present invention will be described in detail below, but the present invention is not limited to the following descriptions, and can be arbitrarily modified and implemented without departing from the gist of the present invention. In addition, in this specification, when expressing by putting a numerical value or a physical-property value before and behind using "-", it shall use as what includes the value before and behind.

[Dynamic cross-linked thermoplastic elastomer composition for composite molded article]
The dynamically cross-linked thermoplastic elastomer composition for composite molded bodies of the present invention (hereinafter sometimes referred to as “dynamic cross-linked thermoplastic elastomer composition of the present invention”) includes the following components (A) and (B ) And (C), and has a Duro A hardness of 30 to 90, and preferably further comprises the following component (D).
Component (A): ethylene / α-olefin / non-conjugated diene copolymer rubber Component (B): Melt flow rate of 0.1 to 250 g / 10 minutes (MFR, 230 ° C., load 21.2 N, JIS K7210 compliant) And a modified polypropylene having a melt tension of 1.0 to 20 cN and having a melting point of not more than 157 ° C. Component (C): Crosslinker Component (D): Hydrocarbon softener

<Mechanism>
The dynamic crosslinkable thermoplastic elastomer composition of the present invention is excellent in fluidity and compression set, and exhibits a high fusion strength when formed into a composite molded body. Due to the curability, the particle size of the component (A) can be reduced in the dynamic heat treatment stage, high fluidity and good rubber elasticity can be obtained, and the component (B) has a relatively low melting point as a polypropylene resin. Thus, it is presumed that high fusion strength can be obtained. Furthermore, it is presumed that the fluidity can be further improved by the component (D).

<Component (A)>
The component (A) ethylene / α-olefin / non-conjugated diene copolymer rubber is a copolymer containing ethylene, an α-olefin and a non-conjugated diene compound as a copolymer component. The ethylene / α-olefin / non-conjugated diene copolymer rubber includes a mixture of an ethylene / α-olefin / non-conjugated diene copolymer rubber and a hydrocarbon rubber softener (hereinafter referred to as “oil-extended ethylene / α- Olefin / non-conjugated diene copolymer rubber ”may be referred to as“ oil-extended type ”and non-oil-extended type that does not include a hydrocarbon-based rubber softener. Although an extended type copolymer rubber is intended, a low oil extended type or a non-oil extended type can also be suitably used. That is, in the present invention, the ethylene / α-olefin / non-conjugated diene copolymer rubber of the component (A) can be used in either an oil-extended type or a non-oil-extended type. Only one type of the exhibition type may be used alone, or two or more types may be used in any combination and ratio, one or more of the oil-extended type and one or two of the non-oil-extended type Species or more can also be used in any combination and ratio.
Here, when the component (A) is an oil-extended ethylene / α-olefin / non-conjugated diene copolymer rubber, a hydrocarbon contained in the oil-extended ethylene / α-olefin / non-conjugated diene copolymer rubber. The rubber-based softener is included in the hydrocarbon-based rubber softener as the component (D).

  As the α-olefin in the component (A), propylene, 1-butene, 3-methyl-1-butene, 1-pentene, 4-methyl-1-pentene, 4,4-dimethyl-1-pentene, 1- Examples thereof include α-olefins having 3 to 20 carbon atoms such as hexene, 4-methyl-1-hexene, 1-heptene, 1-octene, 1-decene and 1-octadecene, more preferably 3 to 8 carbon atoms. It is not specifically limited to these. Among these, propylene, 1-butene, 3-methyl-1-butene, and 1-pentene are preferable, and more preferably propylene, 1-pentene, from the viewpoints of crosslinkability with a crosslinking agent during dynamic crosslinking and bloomout suppression. Butene. In addition, only one type of α-olefin can be used alone, or two or more types can be used in any combination and ratio.

  Examples of the non-conjugated diene compound in component (A) include dicyclopentadiene, 1,4-hexadiene, cyclohexadiene, cyclooctadiene, dicyclooctadiene, 1,6-octadiene, 5-methyl-1,4- Hexadiene, 3,7-dimethyl-1,6-octadiene, 1,3-cyclopentadiene, 1,4-cyclohexadiene, 2-methyl-1,5-hexadiene, 6-methyl-1,5-heptadiene, 7- Ethylidene norbornene such as methyl-1,6-octadiene, tetrahydroindene, methyltetrahydroindene, 5-isopropylidene-2-norbornene, 5-vinyl-2-norbornene, vinylidene norbornene, 5-ethylidene-2-norbornene (ENB), Methyle such as 5-methylene-2-norbornene (MNB) Norbornene and the like, but not particularly limited thereto. Of these, dicyclopentadiene, ethylidene norbornene, and vinylidene norbornene are preferable from the viewpoint of crosslinkability by a crosslinking agent during dynamic crosslinking, and more preferably dicyclopentadiene, 5-ethylidene-2-norbornene, and vinylidene norbornene. . In addition, a nonconjugated diene can be used individually by 1 type, or can use 2 or more types by arbitrary combinations and a ratio.

  Specific examples of the ethylene / α-olefin / non-conjugated diene copolymer rubber include ethylene / propylene / 5-ethylidene-2-norbornene copolymer rubber, ethylene / propylene / dicyclopentadiene copolymer rubber, and ethylene / propylene. 1,4-hexadiene copolymer rubber, ethylene / propylene / non-conjugated diene copolymer rubber (EPDM) such as ethylene / propylene / 5-vinyl-2-norbornene copolymer rubber, Examples thereof include 5-ethylidene-2-norbornene copolymer rubber, but are not particularly limited thereto. Among these, ethylene / propylene / non-conjugated diene copolymer rubber (EPDM) is preferable from the viewpoints of crosslinkability by a crosslinking agent during dynamic crosslinking and suppression of bloom-out. In addition, only one type of ethylene / α-olefin / non-conjugated diene copolymer rubber can be used alone, or two or more types can be used in any combination and ratio.

  The ethylene unit content in the ethylene / α-olefin / non-conjugated diene copolymer rubber is not particularly limited, but is preferably 50 to 90% by mass, more preferably 55 to 85% by mass, and even more preferably 60%. -80 mass%. When the ethylene unit content is within the above preferred range, a dynamic cross-linked thermoplastic elastomer composition excellent in mechanical strength and rubber elasticity tends to be easily obtained.

  Further, the content of the α-olefin unit in the ethylene / α-olefin / non-conjugated diene copolymer rubber is not particularly limited, but is preferably 10 to 50% by mass, more preferably 15 to 45% by mass, and still more preferably. Is 20-40 mass%. When the content of the α-olefin unit is within the above preferred range, a dynamic cross-linked thermoplastic elastomer composition excellent in mechanical strength, moderate flexibility and rubber elasticity tends to be easily obtained.

  Further, the content of the non-conjugated diene unit in the ethylene / α-olefin / non-conjugated diene copolymer rubber is not particularly limited, but is preferably 0.5 to 30% by mass, more preferably 1 to 20% by mass. Yes, more preferably 2 to 10% by mass. When the content of the non-conjugated diene unit is within the above preferred range, it is easy to adjust the crosslinkability and moldability, and a dynamic crosslinkable thermoplastic elastomer composition excellent in mechanical strength and rubber elasticity tends to be obtained. is there.

  In addition, content of each structural unit of a component (A) can be calculated | required by infrared spectroscopy.

  In the present invention, the component (A) has an ethylene unit content of 55 to 75% by mass, a propylene unit content of 15 to 40% by mass, dicyclopentadiene, and 5-ethylidene-2. An ethylene / propylene / nonconjugated diene copolymer rubber copolymer having a content of at least one nonconjugated diene unit selected from the group consisting of norbornene and vinylidenenorbornene is preferably 1 to 10% by mass.

  In addition, as a manufacturing method of component (A), such as ethylene / propylene / non-conjugated diene copolymer rubber (EPDM), a known polymerization method using a known olefin polymerization catalyst can be applied. For example, EPDM can be produced by a slurry polymerization method, a solution polymerization method, a bulk polymerization method, a gas phase polymerization method, etc., using a Ziegler-Natta catalyst, a complex catalyst such as a metallocene complex or a nonmetallocene complex. . Here, the Ziegler-Natta catalyst is a polymerization catalyst comprising a titanium compound or a vanadium compound and an organoaluminum compound, and the metallocene complex catalyst is a cyclopentadienyl derivative of a transition metal such as titanium or zirconium and a promoter. Is a highly active polymerization catalyst. In general, a solution polymerization method using mainly aliphatic hydrocarbon as a solvent is employed, and a slurry polymerization method using a monomer as the main solvent is also employed in part. In addition, a gas phase polymerization method in which a polymerization reaction is performed using various inert materials (for example, carbon black) as a dispersant in a monomer gas has been industrialized. The synthesis by the solution polymerization method, unlike the gas phase polymerization method, is excellent in suppressing bloom-out because the polymer does not contain carbon black or the like. Furthermore, when a metallocene complex catalyst is used, the effect of suppressing bloom out is further improved. On the other hand, the synthesis by the gas phase polymerization method can synthesize a polymer having a higher molecular weight than the solution polymerization method or the slurry polymerization method, and as a result, the Mooney viscosity can be increased, which is effective in improving oil resistance and compression set. .

  The mass average molecular weight in terms of polypropylene by the gel permeation chromatography method (GPC method) of the ethylene / α-olefin / nonconjugated diene copolymer rubber of the component (A) is not particularly limited, but is 100,000 or more. Preferably, it is 200,000 or more, more preferably 300,000 or more, preferably 1,000,000 or less, more preferably 900,000 or less, and further preferably 800,000 or less. . When the mass average molecular weight of the component (A) ethylene / α-olefin / non-conjugated diene copolymer rubber is within the above preferred range, the moldability and processability are improved, and the component (D) hydrocarbon. There is a tendency that bleed-out of the softener for rubbers tends to be suppressed.

In the present specification, the measurement conditions of the weight average molecular weight in terms of polypropylene based on the GPC method of the ethylene / α-olefin / nonconjugated diene copolymer rubber of the component (A) are as follows.
Equipment: Waters 150C
Column: Shodex AD806MS × 3 (8.0 mm inner diameter × 300 mm length)
Detector: IR (dispersion type, 3.42 μm)
Solvent: ODCB (o-dichlorobenzene)
Temperature: 140 ° C
Flow rate: 1.0 mL / min Injection volume: 200 μL
Concentration: 10 mg / mL
Calibration sample: Polydisperse standard polyethylene Calibration method: Polypropylene conversion using Mark-Houwink equation

The density of the ethylene / α-olefin / non-conjugated diene copolymer rubber of the component (A) is not particularly limited, but is preferably 0.850 g / cm ³ or more, more preferably 0.860 g / cm ³ or more. On the other hand, it is preferably 0.900 g / cm ³ or less, more preferably 0.890 g / cm ³ or less. When the density of the ethylene / α-olefin / non-conjugated diene copolymer rubber of the component (A) is within the above preferred range, a thermoplastic elastomer composition excellent in processability, moldability, flexibility and the like is easily obtained. There is a tendency. Such density can be measured based on JIS K7112: 1999.

The Mooney viscosity (ML _{1 + 4} , 125 ° C.) of the component (A) non-oil-extended ethylene / α-olefin / non-conjugated diene copolymer rubber (pre-oil-extended ethylene / α-olefin / non-conjugated diene copolymer rubber) is Although not particularly limited, the Mooney viscosity (ML _{1 + 4} , 125 ° C.) of the oil-extended ethylene / α-olefin / conjugated diene copolymer rubber) is preferably 15 to 400, more preferably 30 to 300, although not particularly limited. , Preferably 15-100, more preferably 30-80. The Mooney viscosity of the component (A) is preferably from the viewpoint of improving the appearance of the molded article obtained when it is at least the above lower limit, and is preferably from the viewpoint of moldability and low-temperature impact resistance when it is at most the above upper limit. .

In the present invention, the Mooney viscosity (ML _{1 + 4} , 125 ° C.) of the component (A) pre-oil-extended ethylene / α-olefin / conjugated diene copolymer rubber is as follows, as described in JP-A-1-103639: It is calculated by this method. That is, the following ML ₁ is actually measured, and ML ₂ (Mooney viscosity of component (A) (ML _{1 + 4} , 125 ° C.)) can be obtained as a calculated value.
Calculation formula: log (ML ₁ / ML ₂ ) = 0.0066 (ΔPHR)
ML ₁ : Mooney viscosity of oil-extended ethylene / α-olefin / non-conjugated diene copolymer rubber before oil expansion ML ₂ : Mooney viscosity of oil-extended ethylene / α-olefin / non-conjugated diene copolymer rubber ΔPHR: Ethylene / α -Oil extended amount per 100 parts by mass of olefin / non-conjugated diene copolymer rubber

  As described above, an oil-extended ethylene / α-olefin / conjugated diene copolymer can also be used as the component (A). In the oil-extended ethylene / α-olefin / conjugated diene copolymer, the hydrocarbon rubber softener softens the ethylene / α-olefin / non-conjugated diene copolymer rubber to increase flexibility and elasticity, It is used for the purpose of improving the processability and fluidity of the resulting thermoplastic elastomer composition.

  Examples of hydrocarbon rubber softeners used in oil-extended ethylene / α-olefin / conjugated diene copolymer rubber include mineral oil rubber softeners and synthetic resin rubber softeners. From the viewpoint of affinity with other components, mineral oil rubber softeners are preferred. The mineral oil rubber softener is generally a mixture of aromatic hydrocarbons, naphthene hydrocarbons, and paraffin hydrocarbons, and the ratio of paraffin hydrocarbon carbon to 50% by mass with respect to all carbon atoms. The above are paraffinic oil, naphthenic hydrocarbons with a carbon content of 30-45% by mass are naphthenic oils, and aromatic hydrocarbons with a carbon content of 35% by mass or more are aromatic oils. is called. Among these, as the softener for hydrocarbon rubber of the oil-extended ethylene / α-olefin / conjugated diene copolymer rubber of component (A), a softener for paraffinic rubber (paraffinic oil) is preferable. In addition, the hydrocarbon-type rubber softening agent can be used alone, or two or more kinds can be used in any combination and ratio.

  The paraffinic oil used for the oil-extended ethylene / α-olefin / nonconjugated diene copolymer rubber of component (A) is not particularly limited, but the kinematic viscosity at 40 ° C. is usually 20 cst (centistokes) or more, preferably 50 cst. These are usually 800 cst or less, preferably 600 cst or less. The pour point is usually −40 ° C. or higher, preferably −30 ° C. or higher and 0 ° C. or lower. The pour point is usually -40 ° C or higher, preferably -30 ° C or higher and 0 ° C or lower. Further, the flash point (COC) is usually 200 ° C. or higher, preferably 250 ° C. or higher, and usually 400 ° C. or lower, preferably 350 ° C. or lower is suitably used.

  Content ratio of ethylene / α-olefin / nonconjugated diene copolymer rubber and hydrocarbon rubber softener when oil-extended ethylene / α-olefin / nonconjugated diene copolymer rubber is used as component (A) The content of the softener for hydrocarbon rubber is usually 10 parts by mass or more, preferably 20 parts by mass with respect to 100 parts by mass of the ethylene / α-olefin / non-conjugated diene copolymer rubber. On the other hand, it is usually 200 parts by mass or less, preferably 160 parts by mass or less, and more preferably 120 parts by mass or less.

  The method (oil-extended method) for preparing the oil-extended ethylene / α-olefin / non-conjugated diene copolymer rubber is not particularly limited, and a known method can be used. As an oil expansion method, for example, a method of using a mixing roll or a Banbury mixer to mechanically knead an oil of ethylene / α-olefin / non-conjugated diene copolymer rubber and a hydrocarbon rubber softener, and extend the oil, ethylene -Addition of a predetermined amount of softening agent for hydrocarbon rubber to α-olefin / non-conjugated diene copolymer rubber, followed by desolvation by a method such as steam stripping, crumb-like ethylene, α-olefin, non- Examples thereof include a method in which a mixture of a conjugated diene copolymer rubber and a hydrocarbon rubber softener is impregnated by stirring with a Henschel mixer or the like. From the viewpoint of preparing a high molecular weight oil-extended ethylene / α-olefin / nonconjugated diene copolymer rubber, a polymerization reaction solution or suspension of the component (A) ethylene / α-olefin / nonconjugated diene copolymer rubber. A method of removing the solvent after adding a predetermined amount of the softener for hydrocarbon rubber to the liquid is preferable.

  In addition, as the component (A) ethylene / α-olefin / non-conjugated diene copolymer rubber, various grades are commercially available from domestic and foreign manufacturers, and commercially available products can be used. Examples of commercially available products include JSR EPR manufactured by JSR, Mitsui EPT manufactured by Mitsui Chemicals, Espren (registered trademark) manufactured by Sumitomo Chemical, Keltan (registered trademark) manufactured by ARLANXEO, and the like.

<Component (B)>
The component (B) modified polypropylene is a strain-hardening polypropylene resin (propylene homopolymer or propylene copolymer, hereinafter sometimes referred to as “propylene-based (co) polymer”). is there. Here, “strain hardening” means a phenomenon in which the viscosity increases as the stretch strain of the melt increases. In the present invention, the presence or absence of “strain hardening” is determined when the melt tension is measured under the conditions described later. It can be determined from the breaking behavior of the molten strand, and when the take-up speed is increased, the take-up load increases abruptly, and when it reaches cutting, it is determined to exhibit strain hardening.

  The modified polypropylene showing the strain-hardening property of the component (B) has a melting point of 157 ° C. or lower and a melt flow rate of 0.1 to 250 g / 10 minutes (MFR, 230 ° C., load 21.2 N, conforming to JIS K7210), and It has a melt tension of 1.0 to 20 cN.

Since the fusion between the adherend and the olefin resin composition or the elastomer composition containing the olefin resin depends on the melting point of the adherend, the melting point of the modified polypropylene exhibiting the strain hardening property of the component (B) is low. The lower one is preferable for the fusion property.
Here, the melting point of the modified polypropylene exhibiting strain hardening is a melting peak temperature measured by a differential scanning calorimeter.

  The MFR of the modified polypropylene showing the strain-hardening property of the component (B) is more preferably 0.3 g / 10 min or more and 100 g / 10 min or less, and further preferably 0.5 g / min from the viewpoint of moldability and the like. It is 10 minutes or more and 70 g / 10 minutes or less. In particular, from the viewpoint of compression set, the MFR of the modified polypropylene exhibiting the strain hardening property of the component (B) is preferably 50 g / 10 min or less, more preferably 30 g / 10 min or less, most preferably 10 g / 10 min. It is as follows. Here, the MFR of the modified polypropylene showing the strain hardening property of the component (B) is a value measured at 230 ° C. and a load of 2.12 N in accordance with JIS K7210.

  The melt tension of the modified polypropylene showing the strain-hardening property of the component (B) is more preferably 1.5 to 19 cN, further preferably 2.0 to 18 cN, from the viewpoints of moldability and compression set. Particularly preferred is 2.5 to 15 cN.

Here, the measurement method of melt tension is as follows.
That is, it is equipped with an attachment for melt tension measurement, using a capilograph (manufactured by Toyo Seiki Seisakusho) with a φ10 mm cylinder fitted with an orifice of φ1 mm and a length of 10 mm at the tip, 230 ° C., piston descending speed 10 mm / When the strand is lowered in minutes, the strand discharged from the die is applied to a pulley with a load cell 350 mm below and taken up at a speed of 1 m / min. After stabilization, the take-up speed is increased at a rate of reaching 200 m / min in 4 minutes. The load applied to the pulley with a load cell when the strand breaks is measured, and the measured load is taken as the melt tension.

  The type of the modified polypropylene showing the strain-hardening property of the component (B) is not particularly limited, and is a propylene-based polymer such as a propylene homopolymer, a block copolymer of propylene and another copolymer component, or a random copolymer. Any of the copolymers can be used. In addition, only one type of component (B) can be used alone, or two or more types can be used in any combination and ratio. Here, the propylene-based copolymer means one having a propylene unit content of more than 50% by mass. From the viewpoint of heat resistance, rigidity, crystallinity, chemical resistance, etc., the content of propylene units in the propylene-based copolymer is preferably 60% by mass or more, more preferably 75% by mass or more, and further preferably 90% by mass. % Or more. On the other hand, the upper limit is not particularly limited, but is usually less than 100% by mass. In addition, content of each structural unit of the propylene unit in a component (B) and the other copolymerization component described below can be calculated | required by infrared spectroscopy.

  When the modified polypropylene showing strain-hardening property of the component (B) is a propylene-based block copolymer or random copolymer, other copolymerization components copolymerized with propylene include ethylene, 1-butene, 1- Α-carbon having 2 or 4 to 12 carbon atoms such as butene, 2-methylpropylene, 1-pentene, 3-methyl-1-butene, 1-hexene, 4-methyl-1-pentene, 1-octene, 1-decene, etc. Olefin; Cyclopentene, norbornene, cyclic olefin such as tetracyclo [6,2,11,8,13,6] -4-dodecene; 5-methylene-2-norbornene, 5-ethylidene-2-norbornene, 1,4-hexadiene , Methyl-1,4-hexadiene, diene such as 7-methyl-1,6-octadiene; vinyl chloride, vinylidene chloride, acrylonitrile Examples include vinyl acetate, acrylic acid, methacrylic acid, maleic acid, ethyl acrylate, butyl acrylate, methyl methacrylate, maleic anhydride, vinyl monomers such as styrene, methylstyrene, vinyltoluene, and divinylbenzene. It is not specifically limited to these. These other copolymerization components can be used alone or in any combination and ratio of two or more. Among these, ethylene and 1-butene are preferable.

  Here, when component (B) is a propylene-based block copolymer, a propylene-based block copolymer obtained by polymerization in multiple stages is preferred. For example, a propylene-based block copolymer obtained by polymerizing polypropylene in the first stage and polymerizing propylene / ethylene copolymer in the second stage is preferably used.

  As the component (B), a propylene-based (co) polymer having a branched structure, a propylene-based (co) polymer having a high molecular weight component, and the like are also preferably used. Examples of such propylene-based (co) polymers include linear propylene homopolymers, propylene homopolymers, block copolymers, and random copolymers that are irradiated with radiation on linear polypropylene resins. Examples thereof include a crystalline propylene-based (co) polymer obtained by melt-mixing a polypropylene-based resin, a conjugated diene compound, and a radical polymerization initiator. Among these, those having a branched structure are preferable.

  The production method of the modified polypropylene showing the strain-hardening property of the component (B) is not particularly limited, and for example, a known polymerization method using a known olefin polymerization catalyst can be applied. As an example, A multistage polymerization method using a Ziegler-Natta catalyst can be mentioned. As this multistage polymerization method, a slurry polymerization method, a solution polymerization method, a bulk polymerization method, a gas phase polymerization method, and the like can be used, and these may be produced by combining two or more thereof.

  It is preferable that the modified polypropylene showing the strain hardening property of the component (B) used in the present invention has a long chain branched structure.

For long chain branched structures, see Macromol. Chem. Phys. 2003, vol. Detailed descriptions are given in 204 and 1738 as follows.
The propylene-based (co) polymer having a long chain branched structure has a specific branched structure as shown in the following structural formula (1). In the structural formula (1), Ca, Cb, and Cc represent methylene carbon adjacent to the branched carbon, Cbr represents the methine carbon at the root of the branched chain, and P1, P2, and P3 represent propylene-based (co) heavy Combined residues are indicated.
P1, P2, and P3 may contain a branched carbon (Cbr) different from Cbr described in the structural formula (1) in itself.

Such a branched structure is identified by ¹³ C-NMR analysis. The assignment of each peak is described in Macromolecules, Vol. 35, no. 10. The description of 2002, pages 3839-3842 can be referred to. That is, a total of three methylene carbons (Ca, Cb, Cc) were observed, each at 43.9-44.1 ppm, 44.5-44.7 ppm, and 44.7-44.9 ppm. Methine carbon (Cbr) is observed at ˜31.7 ppm. Hereinafter, the methine carbon observed at 31.5 to 31.7 ppm may be abbreviated as branched methine carbon (Cbr).
It is characterized in that three methylene carbons adjacent to the branched methine carbon Cbr are observed in three non-equivalent diastereotopics.

Such a branched chain assigned by ¹³ C-NMR represents a propylene-based (co) polymer residue having 5 or more carbon atoms branched from the main chain of the propylene-based (co) polymer, and it has 4 or less carbon atoms. This branching can be distinguished by the difference in the peak position of the branched carbon. Therefore, in the present invention, the presence or absence of the long chain branched structure can be determined by confirming the peak of the branched methine carbon.
In addition, about the measuring method of ¹³ C-NMR in this invention, it is as follows.

( ^13C -NMR measurement method)
A 200 mg sample is an NMR sample having an inner diameter of 10 mmφ together with 2.4 ml of o-dichlorobenzene / deuterated benzene bromide (C ₆ D ₅ Br) = 4/1 (volume ratio) and hexamethyldisiloxane which is a reference substance of chemical shift Dissolve in a tube and perform ¹³ C-NMR measurement.
^{The 13} C-NMR measurement is performed using an AV400M NMR apparatus manufactured by Bruker BioSpin Co., Ltd. equipped with a 10 mmφ cryoprobe.
The measurement is carried out by a proton complete decoupling method at a sample temperature of 120 ° C. Other conditions are as follows.
Pulse angle: 90 °
Pulse interval: 4 seconds Integration frequency: 20000 times The chemical shift was set at 1.98 ppm for the methyl carbon peak of hexamethyldisiloxane, and the chemical shifts for peaks due to other carbons were based on this.
The long chain branching amount can be calculated using a peak around 44 ppm.

The modified polypropylene having a long-chain branched structure according to the present invention has a long-chain branch amount determined from a peak around 44 ppm of ¹³ C-NMR spectrum of 0.01 / 1000 total propylene (1000 total skeleton-forming carbons). Or more), more preferably 0.03 / 1000 total propylene or more, more preferably 0.05 / 1000 total propylene or more, preferably 1.00 / 1000 total propylene or more, more preferably Is 0.50 pieces / 1000 total propylene or less, more preferably 0.30 pieces / 1000 total propylene or less. Within this range, a polypropylene-based resin having no or little gel and a high degree of strain hardening can be obtained.

  The modified polypropylene having a long-chain branch structure according to the present invention has a branching index g ′ known as a direct index for long-chain branching of an absolute molecular weight Mabs of 1,000,000. It is 0.55 or more, 0.75 or more, and 0.78 or more, and an upper limit is less than 1.0, 0.98 or less, 0.96 or less, and 0.95 or less in a preferable order. The above lower limit and upper limit can be arbitrarily combined. When the branching index g ′ is in a range between any of the above preferred lower limits and any of the above preferred upper limits, a highly crosslinked component is not formed, which is preferable in terms of molding appearance. The most preferable range of the branching index g ′ in the present invention is 0.78 or more and 0.95 or less.

The branching index g ′ is known as a direct index for long chain branching. The branching index g ′ is described in detail in “Developments in Polymer Characterization-4” (JV Dawkins ed. Applied Science Publishers, 1983), and the definition thereof is as follows.
Branch index g ′: [η] br / [η] lin
[Η] br: Intrinsic viscosity of polymer (br) having a long chain branched structure [η] lin: Intrinsic viscosity of linear polymer having the same molecular weight as polymer (br)

  As is clear from the above definition, when the branching index g ′ takes a value smaller than 1, it is determined that a long chain branching structure exists, and the value of the branching index g ′ decreases as the long chain branching structure increases. .

  The branching index g ′ can be obtained as a function of the absolute molecular weight Mabs by using GPC with a light scatterometer and viscometer in the detector. The method for measuring the branching index g ′ in the present invention is described in detail in JP-A-2015-40213, but is as follows.

<Measurement method>
GPC: Alliance GPCV2000 (Waters)
Detector: Described in the order of connection Multi-angle laser light scattering detector (MALLS): DAWN-E (Wyatt Technology)
Differential refractometer (RI): attached to GPC Viscometer (Viscometer): attached to GPC Mobile phase solvent: 1,2,4-trichlorobenzene (Irganox 1076 added at a concentration of 0.5 mg / mL)
Mobile phase flow rate: 1 mL / min Column: Tosoh Corporation GMHHR-H (S) Two HT connections Sample injection part temperature: 140 ° C.
Column temperature: 140 ° C
Detector temperature: 140 ° C for all
Sample concentration: 1 mg / mL
Injection volume (sample loop volume): 0.2175 mL

<Analysis method>
When calculating the absolute molecular weight (Mabs) obtained from the multi-angle laser light scattering detector (MALLS), the root mean square radius of inertia (Rg), and the intrinsic viscosity ([η]) obtained from the Viscometer, data processing attached to MALLS Calculation is performed using the software ASTRA (version 4.73.04) with reference to the following document.
References:
1. “Developments in Polymer Characterization-4” (JV Dawkins ed. Applied Science Publishers, 1983. Chapter 1.)
2. Polymer, 45, 6495-6505 (2004).
3. Macromolecules, 33, 2424-2436 (2000)
4). Macromolecules, 33, 6945-6952 (2000)

  Such a modified polypropylene having strain-curing properties having a long-chain branched structure is produced by a method using a macromer copolymerization method in which a long-chain branched structure is formed during polymerization. Examples of this method include, for example, JP-T-2001-525460, JP-A-10-338717, JP-A-2002-523575, JP-A-2009-57542, JP-A-05027353, JP-A-10 The method etc. which are indicated by -338717 gazette are mentioned. In particular, the macromer copolymerization method disclosed in JP2009-57542A is suitable for the present invention.

  In addition, as a modified polypropylene which shows the strain hardening property of a component (B), the thing of various grades is marketed many from domestic and foreign manufacturers, and the commercial item can be used. Examples of commercially available products include Prime Polypro (registered trademark) manufactured by Prime Polymer Co., Ltd., Sumitomo Noblen (registered trademark) manufactured by Sumitomo Chemical Co., Ltd., Polypropylene block copolymer manufactured by Sun Allomer Co., and Novatec (registered trademark) PP manufactured by Nippon Polypro Co., Ltd. , Waymax (WAYMAX (registered trademark)), Moplen (registered trademark) manufactured by LyondellBasel, ExxonMobil PP manufactured by ExxonMobil, Formolene (registered trademark) manufactured by Formosa Plastics, Borealis PP manufactured by Borealis, and Galelice PP manufactured by Borealis SEETEC PP, A. ASI POLYPROPYLENE manufactured by Schulman, INEOS PP manufactured by INEOS Olefins & Polymers, Braschem PP manufactured by Braschem, PIC from SEMUN TAL PET YUPLENE (registered trademark) manufactured by SK. Among them, as a polypropylene having a long chain branching structure and exhibiting strain hardening, Waymax is preferably used.

<Ingredient (C)>
The cross-linking agent of component (C) partially cross-links the above-described component (A) in the resin composition containing each component in the dynamic heat treatment. Things are realized. Such a crosslinking agent can be appropriately selected from known ones and is not particularly limited, but organic peroxides and phenol resins are preferably used. In addition, a crosslinking agent can be used individually by 1 type, or can use 2 or more types by arbitrary combinations and a ratio.

  Examples of the organic peroxide of component (C) include aromatic organic peroxides and aliphatic organic peroxides. Specifically, di-t-butyl peroxide, t-butylcumyl peroxide, dicumyl peroxide, 2,5-dimethyl-2,5-di (t-butylperoxy) hexane, 2,5-dimethyl -2,5-di (t-butylperoxy) hexyne-3, 1,3-bis (t-butylperoxyisopropyl) benzene, 1,1-di (t-butylperoxy) -3,3,5 -Dialkyl peroxides such as trimethylcyclohexane; t-butylperoxybenzoate, t-butylperoxyisopropyl carbonate, 2,5-dimethyl-2,5-di (benzoylperoxy) hexane, 2,5-dimethyl-2 Peroxyesters such as, 5-di (benzoylperoxy) hexyne-3; acetyl peroxide, lauroyl peroxide, benzoy Peroxide, p- chlorobenzoyl peroxide, 2,4-dichlorobenzoyl but hydroperoxides such peroxide such like, not particularly limited thereto. Among these, 2,5-dimethyl-2,5-di (t-butylperoxy) hexane is preferable.

  Examples of the component (C) phenol resin include alkylphenol formaldehyde and alkylbromide phenol formaldehyde. These phenol resins may be used alone or in combination of two or more.

  The phenol resin of component (C) is particularly preferably a non-halogen phenol resin, and specifically, one represented by the following formula (I) is preferable.

(In the formula, Q is selected from -divalent linking group -CH _2- , or -CH ₂ -O-CH _2- , n is an integer of 0 to 20, and R is less than 20 carbon atoms, preferably Is an organic group having 1 to 12 carbon atoms.)

  Examples of the non-halogen phenolic resin products include Taquilol 201, 202 (trade name) manufactured by Taoka Chemical Industry Co., Ltd., PR-4507 (trade name) manufactured by Gunei Chemical Industry Co., Ltd., and manufactured by Hoechst. Vulkaresat 510E, 532E, Vulcaresen E, 105E, 130E, Vulcaresol 315E (trade name), Amberol ST 137X (trade name) manufactured by Rohm & Haas, Sumitomo Durez Co., Ltd. Sumitrite Resin PR-22193ch (or trade name), A Chem. Symform-C-100, C-1001 (trade name) manufactured by the company, Tamanol 531 (trade name) manufactured by Arakawa Chemical Industries, Ltd., and Chemichemistry Chem. Specifieddy SP1045, SP1055, SP1056, SP1059 (trade name), U.S.A. C. Examples include CRR-0803 (trade name) manufactured by C, CRM-0803 (trade name) manufactured by Showa Union Synthesis Co., Ltd., Vulkadur A (trade name) manufactured by Bayer, and the like.

  As the non-halogen phenol resin of component (C), a p-octylphenol formaldehyde resin represented by the following formula (II) is particularly preferably used, and among them, those having a mass average molecular weight of 2,500 to 4,000 are the most. Preferably used. As such a non-halogen type phenol resin, what is marketed as said Tackirol 201,202 (brand name) can be utilized.

In addition to the organic peroxides and phenol resins described above, other crosslinking agents may be used. For example, silicon hydride compounds such as metrohydrogen silicon, sulfur, p-quinone dioxime, p-di Auxiliaries for peroxides such as nitrosobenzene and 1,3-diphenylguanidine; polyfunctional vinyl compounds such as divinylbenzene, triallyl cyanurate, triallyl isocyanurate, diallyl phthalate; ethylene glycol di (meth) acrylate, diethylene glycol di Polyfunctional (meth) acrylate compounds such as (meth) acrylate, polyethylene glycol di (meth) acrylate, trimethylolpropane tri (meth) acrylate, allyl (meth) acrylate; N, N′-m-phenylenebismaleimide, N, N'-m-toluylene bis Compounds having a bismaleimide structure such Reimido; trimethylolpropane, trimethylolpropane trimethacrylate, tin chloride (SnCl _2), and the like. Of these, divinylbenzene is preferred.

In addition, a crosslinking agent can be used individually by 1 type, or can use 2 or more types by arbitrary combinations and a ratio.
For example, the organic peroxide is preferably used in combination with the polyfunctional vinyl compound or the polyfunctional (meth) acrylate compound, and the phenol resin is preferably used in combination with tin chloride.

  In addition, what is marketed as a crosslinking agent includes hydrocarbon rubber softeners and fillers corresponding to the component (D) described later, and the crosslinking agent used is for hydrocarbon rubber. When a softening agent is contained, the said hydrocarbon rubber softener shall be contained in the hydrocarbon rubber softener as a component (D). The same applies to the filler.

<Component (D)>
The dynamically cross-linked thermoplastic elastomer composition of the present invention contains a hydrocarbon rubber softener as component (D) from the viewpoint of increasing flexibility and elasticity and improving processability and fluidity. Is preferred. The component (D) includes a hydrocarbon rubber softener contained therein when the oil-extended ethylene / α-olefin / non-conjugated diene copolymer rubber is used as the component (A). In the case of using an oil-extended ethylene / α-olefin / non-conjugated diene copolymer rubber as the component (A), a component (in addition to the oil-extended ethylene / α-olefin / non-conjugated diene copolymer rubber) It is preferable to separately add a hydrocarbon rubber softener as D). In this case, the separately added hydrocarbon rubber softener is the same, the same, or different from the hydrocarbon rubber softener in the oil-extended ethylene / α-olefin / non-conjugated diene copolymer rubber of component (A). Any of these hydrocarbon rubber softeners can be used. The same applies to the case where the crosslinking agent of component (C) contains a hydrocarbon rubber softener.

  Examples of the hydrocarbon rubber softener to be added separately from the component (A) include mineral oil rubber softener and synthetic resin rubber softener. Among these, affinity with other components From the viewpoint of properties and the like, a mineral oil rubber softener is preferred. As described above, the softener for mineral oil rubber is generally a mixture of aromatic hydrocarbon, naphthene hydrocarbon and paraffin hydrocarbon, and the ratio of paraffin hydrocarbon carbon to total carbon atoms. Are those with paraffinic oil and naphthenic hydrocarbon carbon content of 30-45 mass% are those with naphthenic oil and aromatic hydrocarbon carbon content of 35 mass% or more. It is called aromatic oil. Among these, the hydrocarbon rubber softener is preferably a liquid hydrocarbon rubber softener that is liquid at normal temperature (23 ± 2 ° C.), and more preferably liquid paraffin oil that is liquid at normal temperature. By using a liquid hydrocarbon rubber softener as the hydrocarbon rubber softener, the flexibility and elasticity of the dynamically crosslinked thermoplastic elastomer composition of the present invention can be increased. Tend to improve dramatically. Only one type of the softener for hydrocarbon rubber can be used alone, or two or more types can be used in any combination and ratio.

  The paraffinic oil is not particularly limited, but the kinematic viscosity at 40 ° C. is usually 20 cst (centistokes) or more, preferably 50 cSt or more, and usually 800 cSt or less, preferably 600 cSt or less. The pour point is usually −40 ° C. or higher, preferably −30 ° C. or higher and 0 ° C. or lower. The pour point is usually -40 ° C or higher, preferably -30 ° C or higher and 0 ° C or lower. Further, the flash point (COC) is usually 200 ° C. or higher, preferably 250 ° C. or higher, and usually 400 ° C. or lower, preferably 350 ° C. or lower is suitably used.

  In addition, when using an oil-extended ethylene / α-olefin / non-conjugated diene copolymer rubber as the component (A), a component (D) is added by adding a hydrocarbon rubber softener as the component (D). D) The content of the hydrocarbon rubber softener in D) is arbitrarily adjusted without depending on the content of the hydrocarbon rubber softener in the oil-extended ethylene / α-olefin / non-conjugated diene copolymer rubber. Is possible.

<Combination ratio>
In the dynamically crosslinked thermoplastic elastomer composition of the present invention, the content of the component (A) and the component (B) is 45 to 85 parts by mass of the component (A) and 15 to 55 parts by mass of the component (B). Is preferable (however, the total of the component (A) and the component (B) is 100 parts by mass). When the content of the component (A) is more than the above upper limit and the content of the component (B) is less than the lower limit, the molding appearance is deteriorated. Conversely, the content of the component (A) is less than the lower limit, and the component (B ) Exceeds the above upper limit, the hardness tends to be high and rubber elasticity tends to be lost. From this viewpoint, the content of the component (A) in the total 100 parts by mass of the component (A) and the component (B) is 50 to 80 parts by mass and the content of the component (B) is 20 to 50 parts by mass. The content of component (A) is 45 to 75 parts by mass, and the content of component (B) is more preferably 25 to 45 parts by mass.
Here, the content of component (A) does not include hydrocarbon rubber softener when oil-extended ethylene / α-olefin / non-conjugated diene copolymer rubber is used as component (A). The content of ethylene / α-olefin / non-conjugated diene copolymer rubber.

In addition, the content of the crosslinking agent (including the crosslinking assistant) of component (C) with respect to 100 parts by mass of component (A) and component (B) is 0.05 mass from the viewpoint of sufficiently proceeding with the crosslinking reaction. Part or more, preferably 0.1 part by weight or more, more preferably 0.2 part by weight or more. On the other hand, the content of the component (C) is 20 parts by mass or less, preferably 10 parts by mass or less, more preferably from the viewpoint of controlling the crosslinking reaction with respect to 100 parts by mass in total of the component (A) and the component (B). Is 8 parts by mass or less, more preferably 6 parts by mass or less, and particularly preferably 4 parts by mass or less.
As described above, when the component (C) contains a hydrocarbon-based rubber softener or filler, these are not included in the content as the component (C).

When the dynamically crosslinked thermoplastic elastomer composition of the present invention further contains a component (D), the content of the component (D) is 5 to 200 masses relative to 100 parts by mass in total of the components (A) and (B). Part. If the content of the component (D) is less than the above lower limit, the effect of improving the flexibility, elasticity, fluidity, and workability due to the component (D) cannot be sufficiently obtained, and if the content exceeds the above upper limit, the surface bleeds out. There is a fear. In this respect, the content of the component (D) with respect to the total of 100 parts by mass of the component (A) and the component (B) is preferably 20 to 170 parts by mass, and more preferably 30 to 150 parts by mass. .
Here, the content of component (D) is the hydrocarbon rubber in component (A) when oil-extended ethylene / α-olefin / non-conjugated diene copolymer rubber is used as component (A). Is a total content of the softener for hydrocarbons and the softener for hydrocarbon rubber as component (D) to be added to component (A), and the softener for hydrocarbon rubber in component (C) Is included, it is the total content including the hydrocarbon rubber softener.

<Other ingredients>
In the dynamically crosslinked thermoplastic elastomer composition of the present invention, as long as the object of the present invention is not impaired, other components other than the components (A) to (D) (in this specification, simply It may be referred to as “other components”). Examples of other components include resins and elastomers other than components (A) and (B) (in the present specification, these may be collectively referred to as “other resins”) and various additives.

  Other resins that can be contained in the dynamically crosslinked thermoplastic elastomer composition of the present invention include polyolefin resins (excluding those corresponding to the component (B)), polyester resins, polyamide resins, styrene resins, Resins such as acrylic resin, polycarbonate resin, polyvinyl chloride resin, olefinic elastomers such as ethylene / propylene copolymer rubber (EPM), ethylene / butene copolymer rubber (EBM), ethylene / propylene / butene copolymer rubber; polyamide -Polyamide elastomers such as polyol copolymers; polyvinyl chloride elastomers and polybutadiene elastomers, hydrogenated products thereof, modified with acid anhydrides, etc. to introduce polar functional groups, and other single quantities The body is grafted, random and / or block copolymerized Etc. The. Other resins mentioned above may contain only one type or two or more types.

  Among these, as the polyolefin resin, a C2-C4 α-olefin such as ethylene, propylene, and 1-butene may be used alone or a copolymer containing these as a main component. Specifically, these polyolefin resins are not limited to homopolymers such as polyethylene, polypropylene, poly-1-butene, and the like, as long as the main component is an α-olefin having 2 to 4 carbon atoms. It also includes a copolymer with ~ 20 α-olefin or a vinyl compound such as vinyl acetate, vinyl chloride, acrylic acid, methacrylic acid or styrene. Further, it may be a graft copolymer graft-modified with an unsaturated carboxylic acid such as maleic anhydride, maleic acid, acrylic acid or a derivative thereof. Furthermore, these polyolefin resins may be a mixture.

When the dynamically cross-linked thermoplastic elastomer composition of the present invention contains a polyolefin resin such as polypropylene (excluding those corresponding to the component (B)), the content thereof is determined by the components (A) and ( Preferably it is 0.1-40 mass parts per 100 mass parts of the sum total of B).
The dynamically cross-linked thermoplastic elastomer composition of the present invention has a polyolefin resin, particularly a melt flow rate (230 ° C., 21.18 N, conforming to JIS K7210) of 0.1 to 2,000 g / 10 min. By including polypropylene not shown, the desired fluidity and mechanical properties can be controlled.

  When the dynamically crosslinkable thermoplastic elastomer composition of the present invention contains other resins such as polyolefin resin, the content of other resins in the dynamically crosslinkable thermoplastic elastomer composition of the present invention is the sum thereof, It is preferably 40 parts by mass or less, more preferably 30 parts by mass or less, per 100 parts by mass in total of the component (A) and the component (B).

  Examples of additives that can be contained in the dynamically crosslinked thermoplastic elastomer composition of the present invention include molding stabilizers such as antioxidants, crystal nucleating agents, and lubricants, light stabilizers such as ultraviolet absorbers and hindered amine compounds. Agents, anti-hydrolysis improvers, colorants such as pigments and dyes, antistatic agents, conductive agents, flame retardants, reinforcing agents, fillers, plasticizers, mold release agents, foaming agents and the like.

  For example, in the dynamically crosslinked thermoplastic elastomer composition of the present invention, as an antioxidant, a dithiocarbamate-based antioxidant, a hindered phenol-based antioxidant, a sulfur-based antioxidant, a phosphorus-based antioxidant, etc. Can be blended.

  As the dithiocarbamate antioxidant, a metal salt of dialkyldithiocarbamate is preferable, among which nickel dialkyldithiocarbamate is preferable, and nickel dibutyldithiocarbamate is particularly preferable because it has a large effect of improving heat aging resistance.

Specific examples of hindered phenol antioxidants include 2,4-dimethyl-6-t-butylphenol, 2,6-di-t-butylphenol, 2,6-di-t-butyl-p-cresol, hydroxy Methyl-2,6-di-t-butylphenol, 2,6-di-t-α-dimethylamino-p-cresol, 2,5-di-t-butyl-4-ethylphenol, 4,4′-bis (2,6-di-t-butylphenol), 2,2'-methylene-bis-4-methyl-6-t-butylphenol, 2,2'-methylene-bis (4-ethyl-6-t-butylphenol) 4,4′-methylene-bis (6-t-butyl-o-cresol), 4,4′-methylene-bis (2,6-di-t-butylphenol), 2,2′-methylene-bis ( 4-methyl-6-cyclohex Ruphenol), 4,4′-butylidene-bis (3-methyl-6-tert-butylphenol), 4,4′-thiobis (6-tert-butyl-3-methylphenol), bis (3-methyl-4) -Hydroxy-5-t-butylbenzyl) sulfide, 4,4'-thiobis (6-t-butyl-o-cresol), 2,2'-thiobis (4-methyl-6-t-butylphenol), 2, 6-bis (2′-hydroxy-3′-tert-butyl-5′-methylbenzyl) -4-methylphenol, 3,5-di-tert-butyl-4-hydroxybenzenesulfonic acid diethyl ester, 2,2 '-Dihydroxy-3,3'-di (α-methylcyclohexyl) -5,5'-dimethyl-diphenylmethane, α-octadecyl-3 (3', 5'-di-t-butyl-4'-hydroxyphenyl) Propi 6- (hydroxy-3,5-di-t-butylanilino) -2,4-bis-octyl-thio-1,3,5-triazine, hexamethylene glycol-bis [β- (3,5-di -T-butyl-4-hydroxyphenol) propionate], N, N'-hexamethylene-bis (3,5-di-t-butyl-4-hydroxyhydrocinnamide), 2,2-thio [diethyl- Bis-3 (3,5-di-tert-butyl-4-hydroxyphenyl) propionate], 3,5-di-tert-butyl-4-hydroxybenzenephosphonic acid dioctadecyl ester, tetrakis [methylene-3 (3 5-Di-tert-butyl-4-hydroxyphenyl) propionate] methane, 1,3,5-trimethyl-2,4,6-tris (3,5-di-tert-butyl-4-hydride Xylbenzyl) benzene, 1,1,3-tris (2-methyl-4-hydroxy-5-di-t-butylphenyl) butane, tris (3,5-di-t-butyl-4-hydroxyphenyl) isocyanurate , Tris [β- (3,5-di-t-butyl-4hydroxyphenyl) propionyl-oxyethyl] isocyanurate and the like.
Among these, the use of those having a molecular weight of 500 or more such as tetrakis [methylene-3 (3,5-di-t-butyl-4-hydroxyphenyl) propionate] methane is preferable.

  The sulfur-based antioxidant is a compound containing sulfur such as thioether, dithioate, mercaptobenzimidazole, thiocarbanilide, and thiodipropion ester. However, those corresponding to the above dithiocarbamate antioxidants are not included. Among these, thiodipropion ester compounds are particularly preferable.

  Examples of the phosphorus antioxidant include phosphorus-containing compounds such as phosphoric acid, phosphorous acid, hypophosphorous acid derivatives, phenylphosphonic acid, polyphosphonate, dialkylpentaerythritol diphosphite, and dialkylbisphenol A diphosphite.

  These antioxidants may be used alone or in combination of two or more.

  When the dynamically crosslinked thermoplastic elastomer composition of the present invention contains an antioxidant, the content of the antioxidant is preferably 0.01 per 100 parts by mass in total of the component (A) and the component (B). -5 parts by mass. When the content of the antioxidant is 0.01 parts by mass or more, it is preferable from the viewpoint of the effect of improving heat deterioration resistance. On the other hand, when the content is 5 parts by mass or less, problems such as bleeding are unlikely to occur. It is preferable from the viewpoint of mechanical strength.

  In addition, the dynamically crosslinked thermoplastic elastomer composition of the present invention preferably contains a colorant such as carbon black in order to improve designability and weather resistance. In this case, the colorant contains a component (A ) And 100 parts by mass of the component (B), preferably 0.1 to 5 parts by mass, particularly 0.3 to 3 parts by mass. In addition, it is preferable in terms of uniform dispersibility in the thermoplastic elastomer composition that a trace amount component such as a colorant such as carbon black is blended as a master batch of a resin such as a polyolefin resin.

  In addition, the dynamically crosslinked thermoplastic elastomer composition of the present invention may contain a filler for the purpose of improving production stability, dimensional stability, and flame retardancy. Fiber, hollow glass sphere, carbon fiber, talc, calcium carbonate, mica, potassium titanate fiber, silica, metal soap, titanium dioxide, carbon black, etc. (carbon black is used as a colorant and filler) It is possible.) When mix | blending a filler, a filler is normally used at 0.1-200 mass parts with respect to a total of 100 mass parts of a component (A) and a component (B).

[Method for producing dynamically cross-linked thermoplastic elastomer composition]
The dynamically cross-linked thermoplastic elastomer composition of the present invention comprises the above components (A), (B) and (C), component (D) used as necessary, and other resin components and various additives. Can be produced by mixing, kneading, or melt-kneading in a conventional manner using an ordinary extruder, Banbury mixer, mixing roll, roll, Brabender plastograph, kneader Brabender or the like. Among these, it is preferable to use an extruder, particularly a twin screw extruder. When knead | mixing and manufacturing the dynamic crosslinking type thermoplastic elastomer composition of this invention with an extruder etc., it is preferable to melt-knead normally in the state heated at 80-300 degreeC, Preferably it is 100-250 degreeC. In addition, although the processing time at the time of performing dynamic heat processing is not specifically limited, Considering productivity etc., it is 0.1 to 30 minutes normally.

  Here, “dynamic heat treatment” means kneading in the molten state or semi-molten state in the presence of the component (C). This dynamic heat treatment is preferably performed by melt kneading. When a twin screw extruder is used, each component is supplied to a raw material supply port (hopper) of a twin screw extruder having a plurality of raw material supply ports. It is more preferable to perform a thermal treatment. Thus, the dynamic cross-linking thermoplastic elastomer composition can be obtained by performing the dynamic heat treatment by melt-kneading in the presence of the component (C).

[Various physical properties]
The value of the hardness duro A (conforming to JIS K6253, hardness after 15 seconds) of the dynamically crosslinked thermoplastic elastomer composition of the present invention is not particularly limited, but is preferably 90 or less, more preferably 85 or less, and still more preferably. 80 or less. In addition, the measuring method of hardness duro A is shown in the Example mentioned later.

  The value of compression set (70 ° C. × 22 hours) of the dynamically crosslinked thermoplastic elastomer composition of the present invention is preferably 45% or less. In addition, the measuring method of compression set is shown in the Example mentioned later.

  The melt flow rate (MFR, conforming to JIS K7210, temperature 230 ° C., load 49 N) of the dynamically crosslinked thermoplastic elastomer composition of the present invention is not particularly limited, but is 5 to 200 g / 10 from the viewpoint of moldability and the like. Preferably, it is 5 g / 10 min or more and 150 g / 10 min or less, more preferably 5 g / 10 min or more and 100 g / 10 min or less.

[Composite molded body]
The dynamically cross-linked thermoplastic elastomer composition of the present invention is useful as a constituent material of a composite molded article because it is excellent in fusibility with a counterpart material such as an olefin resin composition or an elastomer composition containing an olefin resin. It is. There is no restriction | limiting in particular as a manufacturing method of the composite molded object using the thermoplastic elastomer composition of this invention, A well-known method can be used normally, for example, the composite molded object of this invention is injection molding (insert molding method). , Two-color molding method, sandwich molding method, core back molding method), coextrusion molding method (inflation molding, T-die film molding, laminate molding, blow molding), and compression molding method. Moreover, it can also be set as a composite molded object by heat-pressing the several shaping | molding sheet (or shaping | molding film) previously shape | molded, and melt | fusing it.

  As the counterpart material of the dynamically cross-linked thermoplastic elastomer composition of the present invention used in the composite molded body of the present invention, because it is excellent in fusion with the dynamic cross-linked thermoplastic elastomer composition of the present invention, An olefin resin composition or an elastomer composition containing an olefin resin is preferably used.

The olefin resin composition is a composition containing an olefin resin as a main component.
The olefin resin is a homopolymer of α-olefin such as ethylene, propylene, 1-butene, 1-pentene, 1-hexene, 4-methyl-1-pentene, 1-octene, 1-decene or the like. Two or more types of copolymers, and the olefin resin composition used in the present invention is preferably composed mainly of polypropylene.

Polypropylene is a known polymer mainly composed of propylene, such as a propylene homopolymer, a random copolymer of propylene and an α-olefin, a block copolymer, and the like.
Polypropylene is polymerized by a known polymerization method. When polymerizing propylene, you may copolymerize alpha olefins, such as ethylene, butene-1, pentene-1, 4-methylpentene-1. As the three-dimensional structure, an isotactic structure is preferable, but a syndiotactic structure, a mixture of these structures, or a structure partially including an atactic structure can also be used.

  The melt flow rate of the polypropylene used in the present invention (according to JIS K6758, measured at a temperature of 230 ° C. and a load of 21.18 N) is preferably 0.05 to 1000 g / 10 minutes, more preferably 0.1 to 1000 g. / 10 minutes.

  The olefin resin composition as the counterpart material includes thermoplastic resins other than olefin resins such as polyamide and polyester, elastomers such as conjugated diene copolymer rubber and styrene / conjugated diene copolymer rubber as inorganic components, and inorganic filling. Agent, antioxidant, ultraviolet absorber, light stabilizer, lubricant, lubricant, plasticizer, thickener, antistatic agent, flame retardant, processability improver, colorant, nucleating agent, molecular weight modifier, coating Various additives such as a property improving agent may be contained.

  Examples of the inorganic filler include talc, mica, calcium carbonate, magnesium carbonate, calcium sulfate, magnesium sulfate, barium sulfate, molybdenum sulfide, carbon black, glass fiber, carbon fiber, potassium titanate fiber, titanium oxide, clay, and kaolin. Examples thereof include plates such as alumina, silica and hollow glass spheres, needles, granules and fibers. Two or more of these may be used in combination. These inorganic fillers can be used after being surface-treated with various organic silanes, titanates and the like in order to improve the affinity with the resin component.

  The elastomer containing the olefin resin is an elastomer containing a rubber component and a plasticizer in an arbitrary ratio to the olefin resin.

  The rubber component may be the ethylene / α-olefin / non-conjugated diene copolymer rubber of the above-mentioned component (A), and other than that, ethylene / α-olefin copolymer, propylene / α-olefin. Examples thereof include olefin elastomers such as copolymers, styrene / butadiene rubber (SBR), acrylonitrile / butadiene rubber (NBR), diene rubbers such as natural rubber (NR) and butyl rubber (IIR), SEBS, and polyisobutylene. Two or more of these may be used in combination.

  Plasticizers include process oil, lubricating oil, paraffin, liquid paraffin, polyethylene wax, polypropylene wax, petroleum asphalt, petroleum jelly and other softeners; coal tar, coal tar pitch and other coal tar softeners; castor oil, Fat oil softeners such as linseed oil, rapeseed oil, soybean oil, coconut oil; tall oil; sub (factis); waxes such as beeswax, carnauba wax, lanolin; ricinoleic acid, palmitic acid, stearic acid, barium stearate Fatty acids and fatty acid salts such as calcium stearate and zinc laurate; naphthenic acid; pine oil, rosin or derivatives thereof; synthetic polymer substances such as terpene resin, petroleum resin, coumarone indene resin, atactic polypropylene; dioctyl phthalate, dioctyl Adipate, di Ester softeners such Kuchirusebaketo; microcrystalline wax, liquid polybutadiene, modified liquid polybutadiene, liquid polyisoprene, end modified polyisoprene, water 添末 end modified polyisoprene, liquid Thiokol, and a hydrocarbon-based synthetic lubricating oils. Among these, petroleum softeners, particularly process oils are preferably used. The blending amount of these softeners is appropriately selected depending on the application.

  In addition, an elastomer containing an olefin resin is also provided with an inorganic filler, an antioxidant, an ultraviolet absorber, a light stabilizer, a lubricant, a lubricant, a thickener, an antistatic agent, as in the case of the olefin resin composition. Various additives such as a flame retardant, a processability improver, a colorant, a nucleating agent, a cross-linking agent, a cross-linking aid, a molecular weight modifier, and a paintability improving agent may be included.

  The composite molded article of the present invention is excellent in compression set and has various uses such as exterior moldings; wind seal gaskets; door seal gaskets; trunk seal gaskets; roof side rails, side moldings, weather strips, and glass run channels. Interior and exterior skin materials such as instrument panels, door trims, console boxes, rack and pinion boots, suspension boots, constant velocity joint boots, bumpers, leather seats, armrests, airbag covers, etc .; automobiles, vehicles Liner materials used in parts that require watertightness and airtightness in materials, building materials, electrical / electronic products, food containers, daily necessities, and other fields; civil engineering / architectural sealing materials, pressure hoses, fire hoses Painting hose, washing machine hose Fuel tubes, oil / pneumatic tubes, dialysis tubes and other hoses and tubes; grip materials for various products (for example, electric drills, scissors, drivers, toothbrushes, pens, cameras, toothpaste, and other infant products); refrigerators Home appliance parts such as gaskets, vacuum cleaner bumpers, waterproof bodies; office machine parts such as copier feeding rollers and take-up rollers; furniture such as sofas and chairs and seats; parts such as switch covers, casters, stoppers, and rubber feet; conveyors Industrial materials such as belts, electric belts, pelletizer rolls, etc .; Elastic members for sanitary materials such as paper diapers, haptics, bandages; Band applications such as hair bands, wristbands, watch bands, and eyeglass bands; flooring materials, snow chains, wire coverings Materials, trays, films, sheets, stationery, toys, household goods, sports equipment, etc. It can be widely applied to the general processed products.

  Hereinafter, although the specific aspect of this invention is demonstrated in detail using an Example, this invention is not limited by a following example, unless the summary is exceeded. In addition, the values of various production conditions and evaluation results in the following examples have meanings as preferable values of the upper limit or the lower limit in the embodiment of the present invention, and the preferable range is the above-described upper limit or lower limit value. A range defined by a combination of values of the following examples or values of the examples may be used.

  In the following examples and comparative examples, the raw materials used for the preparation of the thermoplastic elastomer composition and the evaluation methods of the obtained thermoplastic elastomer composition are as follows.

<Raw materials>
The raw materials used in the following examples and comparative examples are as follows.

[Component (A)]
(A): The following ethylene / propylene / 5-ethylidene-2-norbornene copolymer (A-1) 100 parts by mass and paraffinic oil (D-1) 100 parts by mass (A-1): ethylene Propylene / 5-ethylidene-2-norbornene copolymer Ethylene unit content: 67% by mass
5-ethylidene-2-norbornene unit content: 4.5% by mass
Mooney viscosity ML _{1 + 4} (125 ° C.) of the mixture of (A-1) and (D-1): 64
(D-1): Paraffinic rubber softener (paraffinic oil trade name manufactured by Idemitsu Kosan Co., Ltd. Trade name: Diana (registered trademark) Process Oil PW90)
Kinematic viscosity at 40 ° C .: 95.54 cSt (centistokes)
Pour point: -15 ° C
Flash point: 272 ° C

[Component (B)]
(B-1): Modified polypropylene exhibiting strain hardening (trade name: WAYMAX MFX8, manufactured by Nippon Polypro Co., Ltd.)
Melting point: 155 ° C
MFR (230 ° C., 21.2 N): 1 g / 10 min Melt tension: 24 cN (230 ° C.)
Methylene carbon (Ca, Cb, Cc) and methine carbon (Cbr): Observed long chain branching amount: 0.1 / 1000 total propylene (per 1000 total skeleton-forming carbons)
The branching index g ′ when the absolute molecular weight Mabs is 1 million: 0.89
(B-2): Modified polypropylene exhibiting strain-hardening properties (trade name: WAYMAX MFX3, manufactured by Nippon Polypro Co., Ltd.)
Melting point: 154 ° C
MFR (230 ° C., 21.2 N): 8 g / 10 minutes Melt tension: 5 cN (230 ° C.)
Methylene carbon (Ca, Cb, Cc) and methine carbon (Cbr): Observed long chain branching amount: 0.2 / 1000 total propylene (per 1000 total skeleton-forming carbons)
The branching index g 'when the absolute molecular weight Mabs is 1 million: 0.87

[Component (C)]
(C-1): 2,5-dimethyl-2,5-di (t-butylperoxy) hexane (trade name: Kayahexa AD40C 2,5-dimethyl-2,5-di (t -Butylperoxy) Mixture of 40% by weight of hexane and 60% by weight of calcium carbonate)
(C-2): Divinylbenzene (mixture of 55% by mass of divinylbenzene and 45% by mass of ethylvinylbenzene manufactured by Wako Pure Chemical Industries, Ltd.)
(C-3): Trimethylolpropane trimethacrylate (trade name: Acryester TMP manufactured by Mitsubishi Chemical Corporation)

[Component (D)]
(D-2): Paraffinic rubber softener (paraffinic oil trade name, manufactured by Idemitsu Kosan Co., Ltd. Trade name: Diana (registered trademark) Process Oil PW90)
Kinematic viscosity at 40 ° C .: 95.54 cSt (centistokes)
Pour point: -15 ° C
Flash point: 272 ° C

[Component (E)]
(E-1): Polypropylene resin (polypropylene homopolymer manufactured by Nippon Polypro Co., Ltd. Trade name: Novatec (registered trademark) PP FY6)
Melting point: 161 ° C
MFR (230 ° C., load 21.2 N): 2.5 g / 10 min Density (JIS K7112: 1999): 0.90 g / cm ³
(E-2): Polypropylene resin (Nippon Polypro Co., Ltd. ethylene / propylene copolymer, trade name: Novatec (registered trademark) PP EG8B)
Melting point: 143 ° C
MFR (230 ° C., load 21.2 N): 0.8 g / 10 min Density (JIS K7112: 1999): 0.90 g / cm ³

[Component (F)]
Filler (Talc brand name PHSH manufactured by Takehara Chemical Co., Ltd.)

[Component (G)]
Antioxidant (trade name: Irganox (registered trademark) 1010, manufactured by BASF Japan Ltd.)
[Ingredient (H)]
Antioxidant (trade name: Irganox (registered trademark) FS301FF, manufactured by BASF Japan Ltd.)
[Component (I)]
Black pigment (trade name: PC40C, carbon concentration 40% by mass, low-density polyethylene 60% by mass, manufactured by Dainichi Seikagaku Corporation)

<Evaluation method>
Various evaluation methods of the dynamically crosslinked thermoplastic elastomer composition in Examples and Comparative Examples are shown below. In the following measurements (2) to (4), an inline screw type injection molding machine (manufactured by Toshiba Machine Co., Ltd., product number: IS130) was used, injection pressure 50 MPa, cylinder temperature 220 ° C., mold temperature 40 ° C. Under these conditions, each thermoplastic elastomer composition was injection-molded to form a sheet having a thickness of 2 mm, a width of 120 mm, and a length of 80 mm. In the compression set of (3) below, in accordance with JIS K6262, Type A disk obtained by punching the obtained sheet (thickness 2 mm × width 120 mm × length 80 mm): stacking 6 pieces of 29 mmφ It produced and measured using this test piece. In the measurement of the fusion strength in the following (4), the same injection molded sheet was molded and used for the olefin elastomer as the counterpart material.

(1) Melt flow rate (MFR)
Based on JIS K7210, it measured by 230 degreeC and the load 49N.

(2) Hardness duro A
The hardness (after 15 seconds) was measured according to JIS K6253 (Duro-A).

(3) Compression set Based on the standard of JIS K6262, it measured on 70 degreeC, 22 hours, and 25% compression conditions.

(4) Fusion strength Each injection molded sheet of each thermoplastic elastomer composition and olefinic elastomer (Mitsubishi Chemical Co., Ltd. Zelas (registered trademark) 5013) is placed side by side in a metal frame, and the press temperature is set to 155 ° C. A press sheet is obtained, and a dumbbell-shaped test piece is punched out using a test piece punching blade (JIS No. 3 type dumbbell shape) around the boundary between both materials, and this test piece is used to pull in accordance with JIS K6251. The test was conducted.

[Example 1]
As shown in Table 1, raw materials other than components (C) and (D-2) were blended and mixed for 1 minute using a Henschel mixer. Subsequently, the obtained mixture is charged into the supply port upstream of the same-direction twin screw extruder (manufactured by Nippon Steel Works, product number: TEX25, L / D = 53, number of cylinder blocks: 14) with a mass feeder. did. Then, the components (C) and (D-2) are supplied from the supply port in the middle of the extruder with a liquid pump, and the downstream portion is 120 to 200 ° C. from the upstream portion at a discharge rate of 20 kg / h in total. The temperature was raised in a range, melt kneading was performed, and pelletization was performed to produce the dynamically crosslinked thermoplastic elastomer composition of Example 1. Table 1 shows various physical properties of the obtained dynamically crosslinked thermoplastic elastomer composition of Example 1.

[Examples 2-3 and Comparative Examples 1-2]
Except changing to the compounding composition shown in Table 1, it processed similarly to Example 1 and obtained the pellet of the dynamic crosslinking type thermoplastic elastomer composition of Examples 2-3 and Comparative Examples 1-2, respectively. Various physical properties of each are shown in Table 1.

[Evaluation results]
As shown in Table 1, Examples 1 to 3 corresponding to the dynamically crosslinked thermoplastic elastomer composition of the present invention all have excellent fluidity, good fusion properties, and compression set characteristics. I understand that. On the other hand, the dynamically crosslinked thermoplastic elastomer compositions of Comparative Examples 1 and 2 that do not contain the component (B) have low fluidity, and either fusibility or compression set characteristics are insufficient. . From these results, it was found that the dynamically crosslinked thermoplastic elastomer composition having the component (B) is excellent in both compression set and fusion property.

Claims (6)

A dynamically cross-linked thermoplastic elastomer composition for composite molded bodies, comprising the following components (A), (B), and (C) and having a duro A hardness of 30 to 90.
Component (A): ethylene / α-olefin / non-conjugated diene copolymer rubber Component (B): Melt flow rate of 0.1 to 250 g / 10 minutes (MFR, 230 ° C., load 21.2 N, JIS K7210 compliant) And a modified polypropylene having a melt tension of 1.0 to 20 cN and exhibiting strain hardening with a melting point of 157 ° C. or lower. Component (C): Crosslinking agent   The dynamically cross-linked thermoplastic elastomer composition for a composite molded article according to claim 1, wherein the component (B) is a modified polypropylene having strain-curing properties having a long-chain branched structure.   The component (A) is 45 to 85 parts by mass, and the component (B) is 15 to 55 parts by mass with respect to a total of 100 parts by mass of the components (A) and (B). A dynamically crosslinked thermoplastic elastomer composition for a composite molded article.   The component (C) is at least one selected from the group consisting of organic peroxides, phenol resins, silicon hydride compounds, polyfunctional vinyl compounds, polyfunctional (meth) acrylate compounds, and tin chloride, and The dynamics for a composite molded article according to any one of claims 1 to 3, comprising 0.05 to 20 parts by mass of the component (C) with respect to 100 parts by mass in total of the component (A) and the component (B). Cross-linked thermoplastic elastomer composition. The composite component dynamic according to any one of claims 1 to 4, comprising 5 to 200 parts by mass of the following component (D) with respect to 100 parts by mass in total of the component (A) and the component (B). Cross-linked thermoplastic elastomer composition.
Component (D): Hydrocarbon softener   A composite molded body comprising the dynamically crosslinked thermoplastic elastomer composition for a composite molded body according to any one of claims 1 to 5 and an olefin resin composition or an elastomer composition containing an olefin resin.