JP2013209538A - Thermoplastic elastomer composition, and molded article and foamed article obtained from the same composition - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a thermoplastic elastomer composition capable of producing a foamed article having a low specific gravity and also excellent in outer appearance, and in addition excellent in the balance of the specific gravity, outer appearance and mechanical characteristics.SOLUTION: A thermoplastic elastomer includes: (A) an olefinic rubber comprising (Ax) an olefinic rubber having >50 mol% ethylene content or at least a part of which is crosslinked; (B) a non-crosslinked polyolefin resin; and (C) an olefinic rubber comprising (Cx) an olefinic rubber having ≤50 mol% content of each of constituting units originated from 2 to 20C α-olefins (except propylene) or at least a part of which is crosslinked. A molded article and a foamed article obtained from the composition are also provided.

Description

  The present invention relates to a thermoplastic elastomer composition, a molded product obtained from the composition, and a foamed product.

  Conventionally, a foam obtained by foaming a thermoplastic elastomer composition is known. For example, Patent Document 1 discloses a method of foaming a thermoplastic elastomer composition comprising a mixture of crystalline polyolefin plastic and rubber using water. However, this method uses a special foaming extruder and has a problem that foaming is possible only within an extremely narrow temperature range.

  Further, in Patent Document 2, in order to produce a foam, [I] a peroxide-crosslinked olefin copolymer which is an ethylene / α-olefin copolymer rubber or an ethylene / α-olefin / non-conjugated diene copolymer rubber. A mixture composed of a polymer rubber and a peroxide-decomposable olefin-based plastic, which is a homopolymer or copolymer of an α-olefin having 3 to 20 carbon atoms, is dynamically heat-treated in the presence of an organic peroxide. The resulting partially crosslinked thermoplastic elastomer composition is used. Specifically, this [I] thermoplastic elastomer composition is [II] a homopolymer or copolymer of an α-olefin having 2 to 20 carbon atoms, and has a specific melt flow rate. Olefin plastic and [III] foaming agent (C) are blended and foamed.

  Moreover, in patent document 3, in order to manufacture the foam which is excellent also in specific gravity, the balance of an external appearance, and a mechanical characteristic, the olefin type rubber (A) by which at least one part was bridge | crosslinked and non-crosslinked polyolefin resin (B And a kneaded product of the functionalized olefin resin (C1) and metal compound (E), the thermoplastic elastomer composition having a sea-island structure, The island phase containing the rubber (A) is dispersed in the sea phase containing the kneaded product of the functional group-containing olefin resin (C1) and metal compound (E) and the non-crosslinked polyolefin resin (B). A thermoplastic elastomer composition characterized in that it is used is used.

JP-A-6-73222 JP-A-9-143297 JP 2011-208052 A

  However, the foam disclosed in Patent Document 2 has room for improvement in terms of the balance between specific gravity and appearance and mechanical properties.

  Accordingly, an object of the present invention is to provide a thermoplastic elastomer composition that can produce a foam having a low specific gravity and excellent appearance, and also having a good balance between specific gravity and appearance and mechanical properties. Another object of the present invention is to provide a molded article and a foam having a low specific gravity and excellent appearance, and also excellent balance between specific gravity and appearance and mechanical properties.

  In the present invention, each structural unit derived from an olefin rubber (Ax) having an ethylene content of more than 50 mol%, a non-crosslinked polyolefin resin (B), and an α-olefin having 2 to 20 carbon atoms (excluding propylene). A thermoplastic elastomer composition comprising an olefin rubber (Cx) having a content of 50 mol% or less.

  The present invention also provides an olefin rubber (A) in which at least a part of an olefin rubber (Ax) having an ethylene content of more than 50 mol% is crosslinked, a non-crosslinked polyolefin resin (B), and a carbon number of 2 to 20. Olefin rubber (Cx) in which the content of each structural unit derived from α-olefin (excluding propylene) is 50 mol% or less, and olefin rubber in which at least a part of the olefin rubber (Cx) is crosslinked A thermoplastic elastomer composition comprising at least one selected from (C).

  The present invention also provides an olefin rubber (A) in which at least a part of an olefin rubber (Ax) having an ethylene content of more than 50 mol% is crosslinked, a non-crosslinked polyolefin resin (B), an olefin rubber (Cx). And a olefinic rubber (C) in which at least a part of the thermoplastic elastomer composition is crosslinked.

  Further, each of the above compositions comprises a step [I] of dynamically heat-treating the olefin rubber (Ax), the non-crosslinked polyolefin resin (B), the olefin rubber (Cx), and the crosslinking agent (D). The dynamic heat-treated product obtained by

  Further, in each of the above compositions, 10 to 200 parts by mass of the non-crosslinked polyolefin resin (B) and olefin rubber (Cx) with respect to 100 parts by mass of the olefin rubber (Ax) or the olefin rubber (A). Or it is preferable that the olefin rubber (C) is contained in an amount of 1 to 50 parts by mass.

  Further, in each of the above compositions, the olefin rubber (Ax) or the olefin rubber (A) is ethylene / α obtained from ethylene exceeding 50 mol%, an α-olefin having 3 to 20 carbon atoms, and a non-conjugated polyene. -Selected from olefin / non-conjugated polyene copolymer rubber (Ax) and ethylene / α-olefin copolymer rubber (A2) obtained from ethylene exceeding 50 mol% and α-olefin having 3 to 20 carbon atoms At least one kind of olefin rubber or at least part of the olefin rubber is crosslinked, and the non-crosslinked polyolefin resin (B) is a propylene homopolymer, propylene copolymer, and ethylene. An at least one non-crosslinked olefin resin selected from a copolymer, and an olefin rubber ( x) or olefin-based rubber (C) is a propylene / ethylene / nonconjugated polyene copolymer rubber (C1) obtained from propylene, 50 mol% or less of ethylene and nonconjugated polyene, and propylene and 50 mol% or less of ethylene. And at least one olefin rubber selected from the propylene / α-olefin copolymer rubber (C2) obtained from the above, or an olefin rubber in which at least a part of the olefin rubber is crosslinked.

  Further, in each of the above compositions, the olefin rubber (Cx) preferably has an intrinsic viscosity measured in decalin at 135 ° C. of 0.1 to 3.0 dl / g.

  Further, in each of the above compositions, the non-conjugated polyene contained in the copolymer rubber (Ax), the olefin rubber (Ax), the copolymer rubber (C1) and the olefin rubber (Cx) is 5-ethylidene- It is preferably at least one of 2-norbornene and 5-vinyl-2-norbornene.

Furthermore, in each said composition, it is preferable that the branch index represented by the following formula | equation (1) of olefin type rubber (C1) or olefin type rubber (Cx) is 2-20.
Branch index = [Log (η0.01) −Log (0.116 × η8) ^1.2367 ] × 10 (1)
[In the formula, η0.01 indicates a viscosity (Pa · sec) of 0.01 rad / sec at 190 ° C., and η8 indicates a viscosity (Pa · sec) of 8 rad / sec. ]
Furthermore, each said composition further contains a softener (E), and content of this softener (E) is 1-200 mass parts with respect to 100 mass parts of olefin rubber (Ax) or olefin rubber (A). It is preferable that

  Further, each of the above compositions further contains a fluorine resin (F), and the content of the fluorine resin (F) is 0.05 with respect to 100 parts by mass of the olefin rubber (Ax) or the olefin rubber (A). It is preferably ~ 20 parts by mass.

  Moreover, this invention is a molded object which consists of said each composition.

  Moreover, this invention is a thermoplastic elastomer composition for foaming formed by mix | blending each said composition and a foaming agent (G). The blending amount of the foaming agent (G) is preferably 0.1 to 30 parts by mass with respect to 100 parts by mass of the thermoplastic elastomer composition, and the foaming agent (G) is an inorganic or organic thermal decomposition. It is preferably a type chemical foaming agent or a physical foaming agent.

  Moreover, this invention is a foam obtained from said thermoplastic elastomer composition for foaming.

  Further, the present invention is an automobile part made of the above-mentioned foam, or a civil engineering / building material, an industrial part, an electric / electronic part, a sports / leisure article or a miscellaneous goods made of the above-mentioned foam.

  According to the thermoplastic elastomer composition of the present invention, since the melt tension in the composition is improved, foam breakage and outgassing during foam molding are suppressed, and a foam having a good extruded appearance is obtained. This improves the properties and is advantageous from the viewpoint of lowering the specific gravity, and also provides good rubber elasticity. As a result, it is possible to produce a foam having a low specific gravity and an excellent appearance, and also having an excellent balance between the specific gravity and the appearance and mechanical properties.

It is a figure for demonstrating the shape of the die | dye used in the Example.

<Thermoplastic elastomer composition>
The thermoplastic elastomer composition of the present invention includes an olefin rubber (Ax) having an ethylene content of more than 50 mol%, a non-crosslinked polyolefin resin (B), and an α-olefin having 2 to 20 carbon atoms (excluding propylene). It is a thermoplastic elastomer composition containing olefin rubber (Cx) whose content of each derived structural unit is 50 mol% or less.

  Further, by adding a cross-linking agent (D) to this composition, for example, by performing a heat treatment step [I], an olefin rubber (A) in which at least a part of the olefin rubber (Ax) is cross-linked, Heat of the present invention comprising a non-crosslinked polyolefin resin (B) and at least one selected from an olefin rubber (Cx) and an olefin rubber (C) in which at least a part of the olefin rubber (Cx) is crosslinked. A plastic elastomer composition is obtained.

  As the olefin rubber (Ax) and the olefin rubber (A), ethylene / α-olefin / nonconjugated polyene obtained from ethylene exceeding 50 mol%, an α-olefin having 3 to 20 carbon atoms, and a nonconjugated polyene can be used. Polymer rubber (A1) and at least one olefin rubber selected from ethylene / α-olefin copolymer rubber (A2) obtained from ethylene exceeding 50 mol% and α-olefin having 3 to 20 carbon atoms An olefin rubber in which at least a part of the olefin rubber is crosslinked is preferable.

  Among these, ethylene / α-olefin / non-conjugated polyene copolymer rubber is preferable and ethylene / propylene / non-conjugated polyene copolymer rubber is more preferable from the viewpoint of obtaining a foam having an appropriate cross-linked structure. Here, as the non-conjugated polyene, for example, 5-ethylidene-2-norbornene and 5-vinyl-2-norbornene are preferable. In particular, an ethylene / propylene / ethylidene norbornene copolymer rubber is preferable. The olefin rubber (Ax) will be described in more detail in the description of the production method described later.

  In general, it can be confirmed by measuring the gel content that the olefin rubber is crosslinked. Actually, when dissolved in para-xylene at 140 ° C. for 24 hours and measuring the gel fraction by fractionation using # 350 mesh, the olefin rubber (A) is in a proportion of 70 to 100%, depending on the degree of crosslinking. It turns out that it is bridge | crosslinked.

  The non-crosslinked polyolefin resin (B) is preferably at least one non-crosslinked olefin resin selected from propylene homopolymers, propylene copolymers, and ethylene copolymers.

  The blending amount of the non-crosslinked polyolefin resin (B) is preferably 10 to 200 parts by mass, more preferably 20 to 100 parts by mass with respect to 100 parts by mass of the olefin rubber (Ax) or the olefin rubber (A). It is.

  In the olefin rubber (Cx) and the olefin rubber (C) in which at least a part thereof is crosslinked, the content of each structural unit derived from an α-olefin having 2 to 20 carbon atoms (excluding propylene) is 50 mol% or less. These olefin rubbers and at least a part thereof are crosslinked olefin rubbers. The olefin rubbers (Cx) and (C) may be present in either the sea phase or the island phase in the composition, and have a function of improving the melt tension of the composition.

  As the olefin rubber (Cx) and the olefin rubber (C), propylene / ethylene / nonconjugated polyene copolymer rubber (C1) obtained from propylene, 50 mol% or less of ethylene and nonconjugated polyene, and propylene, Preference is given to at least one olefinic rubber selected from propylene / α-olefin copolymer rubber (C2) obtained from 50 mol% or less of ethylene and an olefinic rubber in which at least a part of the olefinic rubber is crosslinked.

  Among these, propylene / ethylene / non-conjugated polyene copolymer rubber is more preferable. Here, as the non-conjugated polyene, for example, 5-ethylidene-2-norbornene and 5-vinyl-2-norbornene are preferable. The olefin rubber (Cx) will be described in more detail in the description of the production method described later.

  The blending amount of the olefin rubber (Cx) and (C) is preferably 1 to 50 parts by mass, more preferably 3 to 30 parts by mass with respect to 100 parts by mass of the olefin rubber (Ax) or the olefin rubber (A). Part.

  The branching index represented by the following formula (1) of the olefin rubbers (Cx) and (C) is preferably 2 to 20, more preferably 3 to 15, and particularly preferably 4 to 10.

Branch index = [Log (η0.01) −Log (0.116 × η8) ^1.2367 ] × 10 (1)
[In the formula, η0.01 indicates a viscosity (Pa · sec) of 0.01 rad / sec at 190 ° C., and η8 indicates a viscosity (Pa · sec) of 8 rad / sec. ]
The branching index is a measure of the amount of long-term branching that the copolymer rubber has, and the larger the branching index, the greater the amount of long chain branching. When the branching index is within the above range, the rubber composition is excellent in extrudability, press moldability, injection moldability and other moldability, and roll processability, and the strength and flexibility of the molded product obtained from the rubber composition. It is preferable because of its excellent properties.

  The branching index used as an indicator of the amount of the long-chain branched structure is based on the polymer structure of the binary copolymer that does not contain a non-conjugated diene, and the ternary copolymer containing a non-conjugated diene that is the third component. It shows the degree of branching produced by the polymer.

  In order to obtain the branching index, the complex viscosity on the low frequency side (0.01 rad / sec) that most affects the polymer structure due to the long-chain branching structure, and rubber (ethylene / alpha-olefin having 3 to 20 carbon atoms) The melt viscosity corresponding to the Mooney viscosity measurement frequency (8 rad / sec), which is an index of the conjugated polyene copolymer, is taken, and the ratio is calculated.

  The larger the ratio of the calculated values, the greater the change in melt viscosity at low and high frequencies, and this change represents the molecular structure of the polymer. A large change in melt viscosity means that the molecular structure has few main chains and many branches, and reacts sensitively to external stress, and the behavior appears greatly (the influence of branching is large). On the other hand, when there are many main chains and there are few branches, the molecular chains are relatively uniform, the entanglement of the molecular chains is strong, insensitive to external stress, and the behavior appears small (the influence of the main chain is large) ).

  Therefore, in a polymer having a long chain branching structure, there are many branches with respect to the main chain, and the value calculated from the branching index formula becomes large, and many branches are introduced into the polymer. However, when a large number of branched structures are introduced into the polymer, the overall processability is improved, but the strength of the polymer is reduced due to the decrease in the main chain structure. Therefore, the more long-chain branched structures, the better. A polymer having a good balance between processability and strength is optimal.

  Ethylene / C3-C20 α-olefin / non-conjugated polyene copolymer having a specific branching index, that is, ethylene / C3-C20 α-olefin / non-conjugated having a controlled long-chain branch structure By using a polyene copolymer, the rubber composition is excellent in workability and strength balance.

  It should be noted that ethylene / α-olefin / non-conjugated polyene copolymer having 3 to 20 carbon atoms using a metallocene catalyst (preferably a catalyst having a structure represented by formula (iii) of JP2011-16907A). Can produce an olefin-based rubber having the above branching index. Generally, by increasing the polymerization temperature when producing an ethylene / C3-C20 α-olefin / non-conjugated polyene copolymer, the branching index tends to increase, and by lowering the polymerization pressure, The branching index tends to be high.

  The branching index was determined by measuring with a viscoelasticity tester while changing the frequency, with a viscosity of 0.01 rad / sec at 190 ° C. (Pa · sec) and a viscosity of 8 rad / sec at 190 ° C. ( Pa · sec).

  The amount of the olefin rubber (A), the non-crosslinked polyolefin resin (B), the olefin rubber (C) and the kneaded product can be determined from the amount charged when the thermoplastic elastomer composition is produced. For example, when using the manufacturing method of the thermoplastic elastomer composition mentioned later, the quantity of the olefin type rubber (A) and (C) by which at least one part in the composition was bridge | crosslinked is the olefin type rubber ( It can be considered to correspond to the total charge of Ax) and (Cx), the crosslinking agent (D) and the crosslinking aid. The amount of the kneaded product in the composition can be considered to correspond to the total charge amount of each component used in the production of the thermoplastic elastomer composition.

  The thermoplastic elastomer composition of the present invention may further contain a softener (E), and the softener (E) comprises an olefin rubber (A), a non-crosslinked polyolefin resin (B), It is preferable that it is contained in an amount of 1 to 200 parts by mass with respect to 100 parts by mass in total with the olefin rubber (C). The softening agent (E) facilitates processing and aids dispersion of carbon black and the like when preparing the thermoplastic elastomer composition. The softening agent (E) may be present in either the island phase or the sea phase.

  The thermoplastic elastomer composition of the present invention may further contain a fluorine resin (F), and the fluorine resin (F) comprises an olefin rubber (A) and a non-crosslinked polyolefin resin (B). In addition, it is preferably contained in an amount of 0.05 to 20 parts by mass with respect to 100 parts by mass in total of the olefin rubber (C). The fluororesin (F) is used to increase the melt tension of the composition when producing a foam from the thermoplastic elastomer composition. The fluororesin (F) is usually present in the sea phase.

  Moreover, the thermoplastic elastomer composition of the present invention may contain a rubber other than the olefinic rubbers (A) and (C) as long as the object of the present invention is not impaired. That is, when the thermoplastic elastomer composition of the present invention contains the rubber (A), the proportion is usually more than 0 parts by mass and 50 parts by mass or less with respect to 100 parts by mass of the olefinic rubbers (A) and (C). Is included. This rubber may be present in either the island phase or the sea phase.

  Furthermore, the thermoplastic elastomer composition of the present invention comprises known fillers, heat stabilizers, anti-aging agents, weathering stabilizers, antistatic agents, metal soaps, lubricants such as wax, pigments, dyes, crystal nucleating agents, Additives such as a flame retardant, an anti-blocking agent and an antioxidant may be included within a range not impairing the object of the present invention. That is, the thermoplastic elastomer composition of the present invention may not contain the above-mentioned additives, but may contain them. When the filler is included, the filler is usually 0 mass with respect to a total of 100 parts by mass of the olefin rubber (A), the non-crosslinked polyolefin resin (B), and the olefin rubber (C). More than 120 parts by mass, preferably 2 to 100 parts by mass. When the antioxidant is included, the antioxidant is usually used for 100 parts by mass in total of the olefin rubber (A), the non-crosslinked polyolefin resin (B), and the olefin rubber (C). It is included at a ratio of 0.01 to 10. The additive may be present in either the island phase or the sea phase.

  In the thermoplastic elastomer composition, the softener (E), fluorine-based agent relative to the total amount of the olefin rubber (A), the non-crosslinked polyolefin resin (B), the olefin rubber (C), and the kneaded product. The amount of the resin (F) and other additives can be determined from the amount charged when the thermoplastic elastomer composition is produced. Here, for example, when the method for producing a thermoplastic elastomer composition described later is used, at least a partially crosslinked olefin rubber (A), non-crosslinked polyolefin resin (B), olefin rubber ( The total amount of C) and the kneaded product is the olefinic rubber (Ax), crosslinking agent (D), crosslinking aid, olefinic resin (C1) and metal compound (used in the production of the thermoplastic elastomer composition ( It can be considered that it corresponds to the total preparation amount of E). Further, the amount of the rubber (A ′) with respect to the olefin rubber (A) that is at least partially crosslinked can also be determined from the amount charged when the thermoplastic elastomer composition is produced. Here, for example, when the method for producing a thermoplastic elastomer composition described later is used, the amount of the olefin rubber (A) that is at least partially crosslinked is determined by the amount of the olefin rubber used in the production of the thermoplastic elastomer composition. It can be regarded as corresponding to the total charge of (Ax), the crosslinking agent (D) and the crosslinking aid.

<Method for producing thermoplastic elastomer composition>
The method for producing the thermoplastic elastomer composition of the present invention preferably includes the step [I] described below. In other words, the thermoplastic elastomer composition of the present invention comprises an olefin rubber (Ax) having an ethylene content of more than 50 mol%, a non-crosslinked polyolefin resin (B), and a carbon number in the presence of a crosslinking agent (D). A dynamically heat-treated product having a sea-island structure is obtained by dynamically heat-treating an olefin-based rubber (Cx) having a content of each structural unit derived from 2 to 20 α-olefin (excluding propylene) of 50 mol% or less. Obtained by the manufacturing process.

[Step [I]]
In the step [I], the olefin rubber (Ax), the non-crosslinked polyolefin resin (B), and the olefin rubber (Cx) are dynamically heat-treated in the presence of the crosslinking agent (D) to obtain the olefin rubber. The composition contains an olefin rubber (A) in which at least a part of (Ax) is crosslinked and an olefin rubber (C) in which at least a part of olefin rubber (Cx) is crosslinked. Here, a sea-island structure is formed in which the olefin rubber (A) becomes an island phase and the non-crosslinked polyolefin resin (B) becomes a sea phase, and the olefin rubber (C) exists in either the sea phase or the island phase. Some of them may be co-crosslinked with the olefinic rubber (A) and contribute to the interaction between the sea phase and the island phase.

  In addition, the manufacturing method of the thermoplastic elastomer composition of this invention is not necessarily limited to said process [I]. For example, the olefinic rubber (Ax), the non-crosslinked polyolefin resin (B), and the dynamically heat-treated product obtained by the step [I ′] of dynamically heat-treating the crosslinking agent (D) ( Cx) may be blended.

  The olefin rubber (Ax) is an olefin rubber having an ethylene content of more than 50 mol%, and the olefin rubber (Cx) is a component of each structural unit derived from an α-olefin having 2 to 20 carbon atoms (excluding propylene). It is an olefin rubber having a content of 50 mol% or less.

  The ethylene content of the olefin rubber (Ax) is more than 50 mol%, preferably 55 mol% or more, more preferably 60 mol% or more. The ethylene content of the olefin rubber (Cx) is preferably 45 mol% or less, more preferably 40 mol% or less.

  The olefin rubbers (Ax) and (Cx) are olefin copolymer rubbers that are mixed with an organic peroxide and kneaded under heating, for example, to crosslink, resulting in reduced fluidity or non-flowability. It is also called a peroxide-crosslinked olefin copolymer. In addition, when the olefin rubbers (Ax) and (Cx) are thermally reacted with the organic peroxide, a decomposition reaction and a cross-linking reaction occur. The apparent molecular weight of (Ax) and (Cx) is thought to increase.

  As the olefin rubbers (Ax) and (Cx), an ethylene / α-olefin / nonconjugated polyene copolymer rubber obtained by polymerizing ethylene, an α-olefin having 3 to 20 carbon atoms and a nonconjugated polyene ( Amorphous random elastic copolymer), and ethylene / α-olefin copolymer rubber (amorphous random elastic copolymer) obtained by polymerizing ethylene and an α-olefin having 3 to 20 carbon atoms. It is done. The olefin rubber (Ax) may be used alone or in combination of two or more.

  In the ethylene / α-olefin / non-conjugated polyene copolymer rubber and the ethylene / α-olefin copolymer rubber, the α-olefin preferably has 3 to 20 carbon atoms, more preferably 3 to 10 carbon atoms. Specific examples of the α-olefin include propylene, 1-butene, 4-methyl-1-pentene, 1-hexene and 1-octene. The α-olefins may be used alone or in combination of two or more. Of these, propylene, 1-butene and 1-octene are preferred.

  As the non-conjugated polyene for producing the ethylene / α-olefin / non-conjugated polyene copolymer rubber, a cyclic or chain non-conjugated polyene is used. Examples of the cyclic non-conjugated polyene include 5-ethylidene-2-norbornene, dicyclopentadiene, 5-vinyl-2-norbornene, norbornadiene, methyltetrahydroindene and the like. Examples of the chain non-conjugated polyene include 1,4-hexadiene, 7-methyl-1,6-octadiene, 8-methyl-4-ethylidene-1,7-nonadiene, 4-ethylidene-1,7- Examples include undecadiene. A nonconjugated polyene may be used independently or may use 2 or more types together. Of these, 5-ethylidene-2-norbornene, dicyclopentadiene, and 5-vinyl-2-norbornene are preferable, and 5-ethylidene-2-norbornene is more preferable.

  Among these, since a foam having an appropriate cross-linked structure can be obtained, preferably an ethylene / α-olefin / non-conjugated polyene copolymer rubber, more preferably an ethylene / propylene / non-conjugated polyene copolymer rubber, Preferably, an ethylene / propylene / ethylidene norbornene copolymer is used.

  In the ethylene / α-olefin / nonconjugated polyene copolymer rubber, the copolymerization amount of the nonconjugated polyene is preferably 3 to 50, more preferably 5 to 45, and particularly preferably 8 to 40 in terms of iodine value. In order to optimize the value of the effective network chain concentration ν and improve the compression set, a value higher than the iodine value of 10 is desirable.

  In the olefin rubber (Ax), the intrinsic viscosity [η] measured in decalin (decahydronaphthalene) at 135 ° C. is usually 0.8 to 6.0 dl / g, preferably 1.0 to 5.0 dl / g, More preferably, it is 1.1-4.0 dl / g. In the olefin rubber (Cx), the intrinsic viscosity [η] is preferably 0.1 to 3.0 dl / g, more preferably 0.5 to 2.0 dl / g.

  The olefin rubber (Ax) comprising the ethylene / α-olefin copolymer rubber and the ethylene / α-olefin / non-conjugated polyene copolymer rubber having the characteristics as described above is a polymer production process (Industry Research Co., Ltd.). Issued by the association), pages 309 to 330, and the like.

  The non-crosslinked polyolefin resin (B) is an olefin resin that decomposes and increases its fluidity when mixed with, for example, an organic peroxide and kneaded under heating, and is also an organic peroxide non-crosslinked olefin polymer. Say. In addition, when the non-crosslinked polyolefin resin (B) is thermally reacted with the organic peroxide, a decomposition reaction and a cross-linking reaction occur. As a result of many decomposition reactions, the non-crosslinked polyolefin is present in the dynamic heat-treated product. The apparent molecular weight of the resin (B) is considered to decrease.

  Examples of the non-crosslinked polyolefin resin (B) include a propylene homopolymer, a propylene copolymer, and an ethylene copolymer. The non-crosslinked polyolefin resin (B) may be used alone or in combination of two or more. Of these, propylene homopolymers and propylene copolymers are preferably used.

  The propylene-based copolymer preferably contains 50 to 99% by mass of propylene-derived structural units and 50 to 1% by mass of ethylene and α-olefins having 4 to 20 carbon atoms. This copolymer may be a random copolymer or a block copolymer.

  The number of carbon atoms of the α-olefin used in the propylene-based copolymer is preferably 4-20, more preferably 4-10. Specific examples of the α-olefin include 1-butene, 4-methyl-1-pentene, 1-hexene, 1-octene and the like. The α-olefins may be used alone or in combination of two or more. Among these, as a monomer copolymerized with propylene, ethylene, 1-butene, and 1-octene are preferable.

  The ethylene-based copolymer may contain a structural unit derived from ethylene exceeding 50 mass% and 99 mass% or less, and a structural unit derived from an α-olefin having 3 to 20 carbon atoms, less than 50 mass% and 1 mass% or more. preferable. This copolymer may be a random copolymer or a block copolymer.

  The number of carbon atoms of the α-olefin used in the ethylene copolymer is preferably 3 to 20, more preferably 3 to 10. Specific examples of the α-olefin include propylene, 1-butene, 4-methyl-1-pentene, 1-hexene and 1-octene. The α-olefins may be used alone or in combination of two or more. Of these, propylene, 1-butene and 1-octene are preferred.

  The melt flow rate (ASTM D-1238-65T, 230 ° C., 2.16 kg load) of the non-crosslinked polyolefin resin (B) is preferably 0.05 to 80 g / 10 minutes, more preferably 0.1 to 20 g. It is desirable to be in the range of / 10 minutes.

  The propylene homopolymer, propylene copolymer and ethylene copolymer as described above are prepared by a conventionally known method.

  The amount of the non-crosslinked polyolefin resin (B) used in step [I] will be described together in step [II] described later.

  Specifically, an organic peroxide is used as the crosslinking agent (D). Examples of the organic peroxide include dicumyl organic peroxide, di-tert-butyl organic peroxide, 2,5-dimethyl-2,5-di- (tert-butylperoxy) hexane, and 2,5-dimethyl-2,5-di- (Tert-Butylperoxy) hexyne-3,1,3-bis (tert-butylperoxyisopropyl) benzene, 1,1-bis (tert-butylperoxy) -3,3,5-trimethylcyclohexane, n-butyl-4 , 4-bis (tert-butylperoxy) valerate, benzoyl organic peroxide, p-chlorobenzoyl peroxide, 2,4-dichlorobenzoyl organic peroxide, tert-butylperoxybenzoate, tert-butylperbenzoate, tert-butylperoxyisopropyl carbonate And diacetyl organic peroxide, lauroyl organic peroxide, tert-butyl cumyl organic peroxide, and the like. An organic peroxide may be used independently or may use 2 or more types together.

  Among these, in terms of odor and scorch stability, 2,5-dimethyl-2,5-di- (tert-butylperoxy) hexane and 2,5-dimethyl in terms of odor and scorch stability. -2,5-di- (tert-butylperoxy) hexyne-3,1,3-bis (tert-butylperoxyisopropyl) benzene, 1,1-bis (tert-butylperoxy) -3,3,5-trimethyl Cyclohexane and n-butyl-4,4-bis (tert-butylperoxy) valerate are more preferably used, and 1,3-bis (tert-butylperoxyisopropyl) benzene is more preferably used.

  In the present invention, the organic peroxide contains the olefin rubber (A), the non-crosslinked polyolefin resin (B) and the kneaded product in the above-mentioned amounts in the finally obtained thermoplastic elastomer composition. What is necessary is just to use it. For example, the organic peroxide is preferably used at a ratio of 0.05 to 10 parts by mass with respect to 100 parts by mass of the olefin rubber (Ax).

  In the present invention, in the crosslinking treatment with the organic peroxide, sulfur, p-quinonedioxime, p, p′-dibenzoylquinonedioxime, N-methyl-N-4-dinitrosoaniline, nitroso are used as crosslinking aids. Peroxy crosslinking aids such as benzene, diphenylguanidine, trimethylolpropane-N, N′-m-phenylenedimaleimide, or divinylbenzene, triallyl cyanurate, ethylene glycol dimethacrylate, diethylene glycol dimethacrylate, polyethylene glycol dimethacrylate, Polyfunctional methacrylate monomers such as trimethylolpropane trimethacrylate and allyl methacrylate, and polyfunctional vinyl monomers such as vinyl butyrate and vinyl stearate can be blended. The crosslinking aids may be used alone or in combination of two or more.

  By using such a compound, a uniform and mild crosslinking reaction can be expected. In particular, divinylbenzene is preferably used in the present invention. Divinylbenzene is easy to handle, has good compatibility with the olefin rubber (Ax) and the non-crosslinked polyolefin resin (B), and has an action of solubilizing the organic peroxide. Work as. For this reason, a homogeneous cross-linking effect is obtained, and a dynamic heat-treated product having a balance between fluidity and physical properties is obtained.

  The cross-linking aid is such that the olefin rubber (A), the non-cross-linked polyolefin resin (B), and the kneaded product are included in the amounts described above in the finally obtained thermoplastic elastomer composition. Use it. For example, the crosslinking aid is preferably used at a ratio of 0.05 to 10 parts by mass with respect to 100 parts by mass of the olefin rubber (Ax). When the blending ratio of the crosslinking aid is in the above range, a foam having a small compression set and good moldability can be obtained.

  In step [I], the olefin rubber (Ax) and the non-crosslinked polyolefin resin (B) are dynamically heat-treated in the presence of a crosslinking agent (D) and, if necessary, a crosslinking aid.

  Said dynamic heat treatment means kneading said component in a molten state. The dynamic heat treatment is performed using a kneading apparatus such as an open-type mixing roll, a non-release-type Banbury mixer, a kneader, a single or twin-screw extruder, and a continuous mixer, but is performed in a non-open type kneading apparatus. It is preferable. The dynamic heat treatment is preferably performed in an atmosphere of an inert gas such as nitrogen or carbon dioxide.

  The kneading is desirably performed at a temperature at which the half-life of the organic peroxide used is less than 1 minute. The kneading temperature is usually 150 to 280 ° C., preferably 170 to 240 ° C., and the kneading time is usually 1 to 20 minutes, preferably 1 to 5 minutes.

  The dynamic heat treatment may be performed by further blending the softening agent (E). The softening agent (E) can generally be used as an additive for softening the material, and the effect of softening is increased by blending with the olefin copolymer rubber in advance. In addition, the shear applied to the material in the extruder can be reduced, facilitating kneading and sometimes assisting the dispersion state of other additives. On the other hand, when the olefin copolymer rubber is rolled, the intermolecular force of the rubber is weakened to facilitate the processing and help to disperse carbon black and the like.

  As the softener (E), process oil, lubricating oil, paraffin, liquid paraffin, petroleum asphalt, mineral oil softener such as petroleum jelly, coal tar softener such as coal tar and coal tar pitch, castor oil, rapeseed oil , Fatty oil softeners such as soybean oil and coconut oil, waxes such as tall oil, beeswax, carnauba wax, lanolin, fatty acids such as ricinoleic acid, palmitic acid, stearic acid, barium stearate, calcium stearate or metal salts thereof , Naphthenic acid or metal soap thereof, pine oil, rosin or derivatives thereof, terpene resin, petroleum resin, coumarone indene resin, synthetic polymer materials such as atactic polypropylene, ester systems such as dioctyl phthalate, dioctyl adipate, dioctyl sebacate Plasticizer, diisododecyl carbonate, etc. Ester plasticizers, other microcrystalline wax, sub (factice), liquid polybutadiene, modified liquid polybutadiene, liquid Thiokol, and a hydrocarbon-based synthetic lubricating oils. A softener (E) may be used independently or may use 2 or more types together. Of these, petroleum softeners and hydrocarbon synthetic lubricants are preferred.

  Moreover, the softening agent (E) may be contained in the olefin rubbers (Ax) and (Cx) that have been oil-extended in advance.

  The amount of the softening agent (E) used in the step [I] will be described together with the step [II] described later.

  The dynamic heat treatment may be performed by further blending rubbers other than the olefin copolymer rubber (A) as long as the object of the present invention is not impaired. Examples of such rubbers include diene rubbers such as styrene-butadiene rubber (SBR), nitrile rubber (NBR), and natural rubber (NR), and silicon rubber. Further, as this rubber, polyisobutylene, butyl rubber, propylene / ethylene copolymer rubber having a propylene content of 70 mol% or more, propylene / 1-butene copolymer rubber, or the like may be used. This rubber may be used alone or in combination of two or more. Of these, propylene / ethylene copolymer rubber, polyisobutylene, butyl rubber, and silicon rubber are preferable in terms of performance and handling. From the viewpoint of improving the fluidity of the composition, the Mooney viscosity [ML (1 + 4) 100 ° C.] is preferably 60 or less. This rubber is preferably used so as to be contained in the above-mentioned amount in the finally obtained thermoplastic elastomer composition. For example, it is preferable to blend in an amount of more than 0 parts by weight and 50 parts by weight or less with respect to 100 parts by weight of the olefin copolymer rubber (Ax).

  Furthermore, the above-mentioned dynamic heat treatment includes known fillers, heat stabilizers, anti-aging agents, weathering stabilizers, antistatic agents, lubricants such as metal soaps, waxes, pigments, dyes, crystal nucleating agents, flame retardants, You may further mix | blend additives, such as an antiblocking agent and antioxidant, in the range which does not impair the objective of this invention.

  As the filler, fillers usually used for rubber are suitable. Specifically, carbon black, calcium carbonate, calcium silicate, clay, kaolin, talc, silica, diatomaceous earth, mica powder, asbestos, Examples thereof include barium sulfate, aluminum sulfate, calcium sulfate, magnesium carbonate, molybdenum disulfide, glass fiber, glass sphere, shirasu balloon, graphite, and alumina. A filler may be used independently or may use 2 or more types together. Among these, carbon black is preferably used when it is desired to produce a black foam from a thermoplastic elastomer composition.

  The amount of the filler used in the step [I] will be described together with the step [II] described later.

  Examples of the heat resistance stabilizer, anti-aging agent, weather resistance stabilizer, and antioxidant include phenol-based, sulfite-based, phenylalkane-based, phosphite-based, and amine-based stabilizers.

  The amount of the antioxidant used in the step [I] will be described together with the step [II] described later.

  By the dynamic heat treatment in the step [I], the olefin rubber (Ax) becomes an olefin rubber (A) that is at least partially crosslinked. And the dynamic heat processing thing which has a sea-island structure containing the olefin rubber (A) and the non-crosslinked polyolefin resin (B) at least partially crosslinked are manufactured. The olefinic rubber (A) that is at least partially crosslinked is a structure in which at least a part of the olefinic rubber molecules are crosslinked with other olefinic rubber molecules by dynamic heat treatment, It means cross-linking within the molecule. There may be non-crosslinked molecules in the olefin rubber molecules.

It can be confirmed that the olefin rubber (A) is at least partially crosslinked by measuring the gel content as follows.
[Measurement of Gel Content] About 100 mg of a sample of the thermoplastic elastomer composition is weighed and cut into 0.5 mm × 0.5 mm × 0.5 mm strips, and then the obtained strips are placed in a sealed container. Soak in 30 ml cyclohexane at 23 ° C. for 48 hours.

  Next, the sample is taken out on a filter paper and dried at room temperature for 72 hours or more until a constant weight is obtained. A value obtained by subtracting the weight of the cyclohexane insoluble component (fibrous filler, filler, pigment, etc.) other than the polymer component from the weight of the dry residue is defined as “corrected final weight (Y)”.

  On the other hand, a value obtained by subtracting the weight of a cyclohexane-soluble component other than the polymer component (for example, a softener) and the weight of a cyclohexane-insoluble component other than the polymer component (fibrous filler, filler, pigment, etc.) from the weight of the sample, The corrected initial weight (X) ”. The gel content (cyclohexane insoluble matter) is determined by the following formula.

Gel content [wt%] = [corrected final weight (Y) / corrected initial weight (X)] × 100
In the present invention, when at least a part of the olefinic rubber (A) is crosslinked, the gel content obtained as described above is usually 70 to 100%, depending on the degree of crosslinking. Thus, the olefin rubber (A) is considered to be crosslinked at a ratio of 70 to 100%.

  The dynamically heat-treated product has a sea-island structure composed of an island phase and a sea phase, and the island phase containing the olefin rubber (A) is dispersed in the sea phase containing the non-crosslinked polyolefin resin (B). . Specifically, the portion of the olefin rubber (A) that has been crosslinked into crosslinked particles is mainly present in the island phase, and the non-crosslinked polyolefin resin (B) is mainly dispersed in the sea phase. Conceivable. The sea-island structure can be observed with an electron microscope such as a transmission electron microscope after a slice of a pellet obtained from a dynamic heat-treated product is dyed with a heavy metal such as ruthenium.

  Note that the dynamic heat-treated product obtained in the step [I] may be taken out of the kneading apparatus and formed into a molded body such as a pellet.

[Step [II]]
Process [II] is a process performed as needed, and knead | mixes similarly the dynamic heat processing material which has the sea-island structure obtained by process [I], and an additional component as needed. In some cases, the olefin rubber (Cx) is not all crosslinked olefin rubber (C) even by this kneading, and the kneaded product includes the crosslinked olefin rubber (C), It is considered that the olefin rubber (Cx) may be included as it is.

  As the additional non-crosslinked polyolefin resin (B), the same one as in step [I] is used, and the preferred range is also the same. The non-crosslinked polyolefin resin (B) blended in the step [I] may contain molecules decomposed by dynamic heat treatment. When molecules decomposed as described above are included, the melt tension of the composition usually decreases, but when the non-crosslinked polyolefin resin (B) is blended also in the step [II], the melt tension of the composition is reduced. It can be adjusted to a preferred range.

  The non-crosslinked polyolefin resin (B) may be used only in the step [I] as described above, or may be used in both the steps [I] and [II]. In any case, the blending amount of the non-crosslinked polyolefin resin (B) may be used so as to be included in the amount described above in the finally obtained thermoplastic elastomer composition. For example, when the non-crosslinked polyolefin resin (B) is used only in the step [I], 1 to 100 with respect to 100 parts by mass of the olefin rubbers (Ax) and (Cx) used in the step [I]. It is preferable to mix | blend in the quantity of a mass part. Alternatively, when used in both steps [I] and [II], in steps [I] and [II] with respect to 100 parts by mass of the olefin rubber (Ax) and (Cx) used in step [I]. It is preferable to mix | blend so that the total amount of may become 1-100 mass parts.

  In the step [II], the dynamically heat-treated product obtained in the step [I] and the non-crosslinked polyolefin resin (B) are kneaded, preferably melt-kneaded as necessary.

  The kneading is performed using a kneading apparatus such as an open type mixing roll, a non-release type Banbury mixer, a kneader, a single or twin screw extruder, a continuous mixer, etc., but is preferably performed in a non-open type kneading apparatus. .

  When a twin screw extruder is used, the kneading temperature is usually 50 to 300 ° C., and the kneading time is usually 1 to 20 minutes.

  The kneading process may be performed by further blending the softening agent (E). The softening agent (E) weakens the intermolecular force of the rubber when rolling the rubber, facilitates the processing and helps disperse the carbon black and the like. As the softening agent (E), the same one as in step [I] is used, and the preferred range is also the same.

  The softening agent (E) may be used only in the step [I] or [II] as described above, or may be used in both the steps [I] and [II]. In any case, the blending amount of the softening agent (E) may be used so as to be included in the above-described amount in the thermoplastic elastomer composition finally obtained. For example, when the softener (E) is used only in the step [I] or [II], the olefin rubber (Ax), the non-crosslinked polyolefin resin (B) used in the steps [I] and [II] and It is preferable to mix | blend so that the quantity in process [I] or [II] may become the quantity of 1-200 mass parts with respect to a total of 100 mass parts of olefinic rubber (Cx). Alternatively, when used in both steps [I] and [II], the olefin rubber (Ax), non-crosslinked polyolefin resin (B) and olefin rubber (Cx) used in steps [I] and [II]. It is preferable to mix | blend so that the total amount in process [I] and [II] may be 1-200 mass parts with respect to a total of 100 mass parts.

  The kneading process may be performed by further blending the fluororesin (F). When the fluororesin (F) is used, when the foam is produced from the thermoplastic elastomer composition, the melt tension of the composition can be increased and foam breakage of the foam cell can be suppressed. As the fluororesin (F), polytetrafluoroethylene is preferably used.

  What is necessary is just to use the compounding quantity of a fluororesin (F) so that it may be contained in the quantity mentioned above in the thermoplastic elastomer composition finally obtained. For example, the fluororesin (F) is used in a total of 100 parts by mass of the olefin rubber (Ax), non-crosslinked polyolefin resin (B) and olefin rubber (Cx) used in the steps [I] and [II]. Thus, it is preferably blended so as to be more than 0 parts by mass and 20 parts by mass or less.

  Furthermore, the above-mentioned kneading treatment is carried out using known fillers, heat stabilizers, anti-aging agents, weathering stabilizers, antistatic agents, lubricants such as metal soaps, waxes, pigments, dyes, crystal nucleating agents, flame retardants, and blocking prevention. You may mix | blend and add additives, such as an agent and antioxidant, in the range which does not impair the objective of this invention. As said additive, the thing similar to process [I] is used, and its preferable range is also the same. Carbon black as a filler is preferably used in step [II] rather than step [I].

  As described above, the filler may be used only in step [I] or [II], or may be used in both steps [I] and [II]. In either case, the blending amount of the filler may be used so as to be included in the amount described above in the finally obtained thermoplastic elastomer composition. For example, when the filler is used only in the step [I] or [II], the olefin rubber (Ax), the non-crosslinked polyolefin resin (B) and the olefin rubber used in the steps [I] and [II]. It is preferable to mix | blend so that the quantity in process [I] or [II] may exceed 0 mass part and is 120 mass parts or less with respect to a total of 100 mass parts of (Cx). Alternatively, when used in both steps [I] and [II], the olefin rubber (Ax), non-crosslinked polyolefin resin (B) and olefin rubber (Cx) used in steps [I] and [II]. ) Is preferably blended so that the total amount in steps [I] and [II] exceeds 0 parts by mass and 120 parts by mass or less.

  As described above, the antioxidant may be used only in the step [I] or [II], or may be used in both the steps [I] and [II]. In any case, the blending amount of the antioxidant may be used so as to be included in the above-mentioned amount in the finally obtained thermoplastic elastomer composition. For example, when the antioxidant is used only in the step [I] or [II], the olefin rubber (Ax), the non-crosslinked polyolefin resin (B) and the olefin type used in the steps [I] and [II]. It is preferable to blend so that the amount in the step [I] or [II] is 0.01 to 10 parts by mass with respect to 100 parts by mass in total of the rubber (Cx). Alternatively, when used in both steps [I] and [II], the olefin rubber (Ax), non-crosslinked polyolefin resin (B) and olefin rubber (Cx) used in steps [I] and [II]. It is preferable to mix | blend so that the total amount in process [I] and [II] may be 0.01-10 mass parts with respect to a total of 100 mass parts.

  In addition, it is considered that not all of the olefin rubber molecules are cross-linked by kneading. In other words, the olefin rubber (Cx) may not be all crosslinked olefin rubber (C) by the kneading, and the kneaded product may contain the crosslinked olefin rubber (C). It is considered that the olefin rubber (Cx) may be included as it is.

  The thermoplastic elastomer composition has a sea-island structure composed of an island phase and a sea phase, and the island phase containing the olefin rubbers (A) and (C) contains the non-crosslinked polyolefin resin (B). It is considered to be dispersed in the sea phase.

  By such steps [I] and [II], the thermoplastic elastomer composition as described above is obtained.

  The sea-island structure can be observed with an electron microscope such as a transmission electron microscope after a slice of a pellet obtained from the thermoplastic elastomer composition is dyed with a heavy metal such as ruthenium. It is considered that the olefin rubber (A) is mainly present in the island phase and the non-crosslinked polyolefin resin (B) is mainly dispersed in the sea phase.

  Further, at least a part of the olefin rubber (A) is crosslinked, and such crosslinking can be confirmed by measuring the gel content as described in the step [I]. The presence of the cross-linked olefin rubber (C) can be indirectly confirmed from an increase in melt tension.

  As described above, the non-crosslinked polyolefin resin (B) is blended in the step [II] as necessary in addition to the step [I]. The molecules of the non-crosslinked polyolefin resin (B) may be decomposed by kneading in the steps [I] and [II]. Therefore, in the finally obtained thermoplastic elastomer composition, molecules decomposed by kneading can be mixed as the non-crosslinked polyolefin resin (B).

  By the way, when the molecule | numerator decomposed | disassembled as mentioned above is also included, although the melt tension of a composition will fall normally, in the thermoplastic elastomer composition of this invention, since the crosslinked olefin resin (C) exists. It is considered that the melt tension of the composition is increased and the interface strength between the island phase and the sea phase is also increased. For this reason, when manufacturing a foam using a foaming agent from a thermoplastic elastomer composition, foam breakage of a foam cell is suppressed. That is, since fine foam cells are uniformly dispersed, the weight of the foam can be reduced, and the obtained foam is excellent in appearance. Moreover, this foam is excellent also in specific gravity and the balance of an external appearance and a mechanical characteristic.

  In the thermoplastic elastomer composition of the present invention, the crystallization time from foaming the composition to forming a foam is shortened. Thereby, the state by which the fine foam cell in the composition was disperse | distributed uniformly can be maintained also in a foam. Furthermore, it has excellent mechanical properties.

  The thermoplastic elastomer composition may be taken out from the kneading apparatus and formed as a molded body such as a pellet. Thus, the molded body according to the present invention is composed of the thermoplastic elastomer composition.

  The thermoplastic elastomer composition produced in this way has the advantages of high melt tension and fast crystallization rate.

<Thermoplastic elastomer composition for foaming and foam>
The foaming thermoplastic elastomer composition of the present invention comprises the above-described thermoplastic elastomer composition and a foaming agent (G). A foam can be obtained from this thermoplastic elastomer composition for foaming.

  Examples of the foaming agent (G) include inorganic or organic pyrolytic chemical foaming agents and physical foaming agents.

  Examples of the inorganic pyrolytic chemical foaming agent include inorganic carbonates such as sodium hydrogen carbonate, sodium carbonate, ammonium hydrogen carbonate, and ammonium carbonate, and nitrites such as ammonium nitrite. An inorganic thermal decomposition type chemical foaming agent may be used independently, or may use 2 or more types together.

  Organic pyrolytic chemical foaming agents include nitroso compounds such as N, N′-dimethyl-N, N′-dinitrosoterephthalamide and N, N′-dinitrosopentamethylenetetramine; azodicarbonamide, azobis Azo compounds such as isobutyronitrile, azocyclohexyl nitrile, azodiaminobenzene, barium azodicarboxylate; benzenesulfonyl hydrazide, toluenesulfonyl hydrazide, p, p'-oxybis (benzenesulfonyl hydrazide), diphenylsulfone-3, Examples thereof include sulfonyl hydrazide compounds such as 3′-disulfonylhydrazide; azide compounds such as calcium azide, 4,4′-diphenyldisulfonyl azide and p-toluenesulfonyl azide. The organic pyrolytic chemical foaming agent may be used alone or in combination of two or more.

  Examples of the physical foaming agent include inert gas mainly composed of carbon dioxide, nitrogen, or a mixture of carbon dioxide and nitrogen. A physical foaming agent may be used independently or may use 2 or more types together. When carbon dioxide or nitrogen is used, it is preferably mixed into the thermoplastic elastomer composition in a supercritical state from the viewpoint of rapid and uniform mixing and finer bubbles.

  The foaming agent (G) is preferably blended in an amount of 0.1 to 30 parts by mass with respect to 100 parts by mass of the thermoplastic elastomer composition.

  The foaming thermoplastic elastomer composition may further contain a foam-forming nucleating agent, a wetting agent, and the like.

  Foam-forming nucleating agents include metal compounds such as zinc, calcium, lead, iron and barium, higher fatty acids such as stearic acid, and metal salts thereof, talc, barium sulfate, silica, zeolite, boron nitride, aluminum oxide, zirconium oxide Fine inorganic particles such as ethylene tetrafluoride resin fine powder, silicone rubber powder; citric acid, oxalic acid, fumaric acid, phthalic acid, malic acid, tartaric acid, lactic acid, cyclohexane 1,2 dicarboxylic acid, camphoric acid, ethylenediamine tetra Mixtures of polyvalent carboxylic acids such as acetic acid, triethylenetetramine hexaacetic acid, nitrilolic acid and inorganic carbonate compounds such as sodium hydrogen carbonate, sodium aluminum hydrogen carbonate, potassium hydrogen carbonate, and intermediates produced by these reactions, such as citric acid Polycarboxylic acids such as sodium dihydrogen and potassium oxalate Salts; nitroso compounds such as N, N′-dimethyl-N, N′-dinitrosoterephthalamide, N, N′-dinitrosopentamethylenetetramine; azodicarbonamide, azobisisobutyronitrile, azocyclohexylnitrile, azo Azo compounds such as diaminobenzene and barium azodicarboxylate; sulfonyl hydrazides such as benzenesulfonyl hydrazide, toluenesulfonyl hydrazide, p, p'-oxybis (benzenesulfonyl hydrazide), diphenylsulfone-3,3'-disulfonyl hydrazide Compounds; azide compounds such as calcium azide, 4,4′-diphenyldisulfonyl azide, p-toluenesulfonyl azide and the like. Among these, calcium stearate and ethylene tetrafluoride resin fine powder are particularly preferable.

  The addition amount of the foam-forming nucleating agent and the wetting agent is preferably 0.01 to 10 parts by mass and more preferably 0.02 to 5 parts by mass with respect to 100 parts by mass of the thermoplastic elastomer composition, respectively. .

  When preparing a foam using a thermal decomposable chemical foaming agent, for example, a pellet-shaped thermoplastic elastomer composition, a thermal decomposable chemical foaming agent in the form of a pellet using powder or resin as a binder, and if necessary Once the foam-forming nucleating agent and wetting agent are mixed with a tumbler-type brabender, V-type brabender, ribbon blender, Henschel mixer, etc., if necessary, an open type mixing roll, a non-open type Banbury mixer, an extruder Then, the mixture is kneaded with a kneader, a continuous mixer or the like below the decomposition temperature of the foaming agent to obtain a thermoplastic elastomer composition for foaming.

  Next, the obtained thermoplastic elastomer composition for foaming is supplied to an extruder, heated in the barrel above the melting point of the composition and the decomposition temperature of the blowing agent, and the foaming agent decomposition product gas is added to the composition while being pressurized. Disperse uniformly.

  Next, the foaming thermoplastic elastomer composition in which the foaming agent decomposition product gas is uniformly dispersed and melted is transferred to a die attached to the tip of the extruder set to the optimum foaming temperature, and from the die to the atmosphere or water. The pressure is rapidly reduced by extrusion and foamed, and then cooled and solidified by a subsequent cooling device to produce the desired foam. In addition, the temperature of the thermoplastic elastomer composition for foaming at the time of extrusion has the preferable range of 120-280 degreeC.

  On the other hand, when preparing a foam using carbon dioxide or nitrogen, an olefin-based thermoplastic elastomer composition and, if necessary, a foam-forming nucleating agent or a wetting agent are once combined with a tumbler-type Brabender or a V-type Brabender. , After being kneaded with a ribbon blender, Henschel mixer, etc., melted at 130-300 ° C. in a resin plasticizing cylinder, and the thermoplastic elastomer composition is melted with carbon dioxide or nitrogen to be melted thermoplastic for foaming An elastomer composition is formed. From the viewpoint of compatibility and foamed cell uniformity, carbon dioxide and nitrogen are preferably dissolved in the thermoplastic elastomer composition in a resin plasticizing cylinder in a supercritical state.

  Next, the molten thermoplastic elastomer composition for foaming is transferred to a die attached to the tip of the extruder set to the optimum foaming temperature, extruded from the die into the atmosphere, and the pressure is rapidly reduced, so that carbon dioxide and Nitrogen is gasified and foamed, and then cooled and solidified by a subsequent cooling device to obtain a desired foam. The temperature of the thermoplastic elastomer composition during extrusion is preferably in the range of 120 to 280 ° C.

  As a method for preparing a foam from the foamable olefin-based thermoplastic elastomer composition obtained as described above, in addition to the above-mentioned extrusion molding, press molding and injection conventionally used for obtaining foam molded products A molding method such as molding or calendar molding may be employed.

  Thus, the molded article of the present invention, specifically, the foam is obtained from the above-mentioned foaming thermoplastic elastomer composition. Since the foam of this invention is obtained from the thermoplastic-elastomer composition for foaming mentioned above, weight reduction can be achieved and it is excellent also in an external appearance. Furthermore, it is excellent in specific gravity, balance between appearance and mechanical properties. In other words, compared to a foam obtained from a conventional thermoplastic elastomer composition for foaming, weight reduction can be achieved while maintaining the mechanical properties, and the appearance is also excellent.

<Application>
Applications of the foam of the present invention include automobile interior skin materials, weatherstrip sponges, body panels, steering wheels, side shields and other automotive parts; civil engineering and building materials such as ground improvement sheets, water plates, and noise prevention walls; Industrial parts; Footwear such as shoe soles and sandals; Electrical and electronic parts such as wire covers, connectors and cap plugs; Sports and leisure products such as golf club grips, baseball bat grips, swimming fins, underwater glasses; gaskets and waterproof cloths , Garden hoses, belts, draining sheets, cosmetic puffs and other miscellaneous goods.

  EXAMPLES Hereinafter, although an Example demonstrates this invention, this invention is not limited to these Examples. In the following description, “parts” of the blending amount means “parts by mass”. In addition, the molding of foams and the evaluation of basic physical properties in the examples were performed by the following methods.

(Test method)
(1) Extrusion Foam Molding Equipment / Extruder: 65mmφ Single Screw Extruder [Nagata Seisakusho OSE-65]
Maximum cylinder temperature: 150-190 ° C
Die temperature: 170-190 ° C
Rotation speed: 25rpm
Take-up machine speed: 7.1 m / min Water tank belt take-up speed: 6.4 m / min ・ Die: Maruichi The die has the shape shown in FIG. 1, that is, the die has a shape with one under the circle. This is a die for extruding a scale. In order to extrude from the slit shown in FIG. 1, a hollow long object was obtained. In the present specification, the round shaped foam molded body obtained in this way is also referred to as a round foam.
-Carbon dioxide / nitrogen supply device: manufactured by AKICO Co., Ltd. Used for foaming using carbon dioxide gas.

(2) Basic physical properties For evaluation of basic physical properties, a sheet having a thickness of 2 mm was prepared using a press molding apparatus.
Press forming apparatus: 100 ton electric heat automatic press heating: temperature 190 ° C., preheating time 6 minutes, heating time 4 minutes Cooling: temperature 23 ° C., cooling time 5 minutes.

[Measurement of melt flow rate MFR]
The melt flow rate (MFR) was measured by the method of ASTM-D-1238-65T at 230 ° C., 2.16 kg, 5 kg load or 10 kg load.

(Measurement of crystallization time)
The crystallization time was measured using a DSC apparatus (DSC7; manufactured by PERKIN ELMER).
Temperature increase rate: 320 ° C / min (from normal temperature to 200 ° C)
Hold: 200 ° C for 5 minutes Temperature drop rate: 320 ° C / min (200 ° C to 120 ° C)
Measurement temperature: 120 ° C.

(Measurement of melt tension)
The melt tension was measured using CAPIROGRAPH (manufactured by TOYOSEIKI).
Conditions: L = 8.00 mm, D = 2.095 mm, L / D = 3.82
Temperature: 180 ° C
Take-off speed: 500 mm / min.

[Measurement of strength at break and elongation at break]
The strength at break and the elongation at break were determined by punching 5 dumbbell-shaped No. 3 test pieces described in JIS K6251 (possible if the parallel part reaches the specified dimensions) from a press-molded sheet, and described in JIS K6251. Measured by method.

[Measurement of compression set]
The compression set was measured by the method described in JIS K6262, with three samples punched out to an appropriate size from the press-molded sheet.

[Measurement of hardness]
The hardness was measured by the method described in JIS K6253 by stacking three samples punched out to an appropriate size from the press-molded sheet.

[Measurement of specific gravity of foam]
The specific gravity of the foam was obtained by cutting a round foam obtained by extrusion foaming into an appropriate size. Specifically, it can be determined by JIS K6268 A method or an automatic hydrometer sold by various manufacturers, for example, an electronic hydrometer MS-200S manufactured by Mirage Trading Co., Ltd. In the present example, it was obtained using an electronic hydrometer MS-200S manufactured by Mirage Trading.

(Measurement of foam water absorption)
The foam water supply rate was determined by cutting a round foam obtained by extrusion foaming into an appropriate size and measuring the sample weight with a precision balance. The sample was then immersed in a water tank equipped with a vacuum pump, depressurized to -635 mmHg, and allowed to stand for 3 minutes. Subsequently, the pressure was returned to 0, the weight of the sample that absorbed moisture was measured, and the water absorption was measured from the change in weight.
Water absorption rate = (sample weight after test−weight before test) / weight before test × 100 “%”
(Measurement of foam compressive stress)
The foam compression stress was obtained by cutting a round foam obtained by extrusion foaming into an appropriate size, holding the compression amount of 25% for 30 seconds, and calculating the stress per unit area at that time. As temperature conditions, it implemented at 23 degreeC and -30.

(Measurement of strength at break and elongation at break)
The strength at break and the elongation at break of the dumbbell-shaped No. 3 test piece described in JIS K6251 along the extrusion direction of the round one foam obtained by extrusion foaming (if the parallel part reaches the specified size) 5) were punched out and measured by the method described in JIS K6251.

(Measurement of foam compression set)
Foam compression set is obtained by cutting a round foam obtained by extrusion foaming into an appropriate size and compressing 25% or 50% from the head of the round part at a temperature of 70 ° C. for 22 hours. Then, it was measured by the method described in JIS K6262.

[Appearance of foam]
The appearance of the foam was determined by checking the appearance of the extruded round one foam and determining the following level.
“Level 5”: The surface of the molded article is smooth.
“Level 4”: The surface of the molded product is almost smooth.
"Level 3": There is a slight unevenness on the surface of the molded product.
"Level 2": There are many irregularities on the surface of the molded product.
"Level 1": The shape is unstable.

[Cell state of foam]
The cell state of the foam was confirmed at the following level by confirming the cell state of the extruded round one foam.
“Level 4”: The cells are fine and uniform, and the distribution is narrow.
"Level 3": The cells are almost uniform and the distribution is narrow.
“Level 2”: Cell shape is non-uniform and distributed.
"Level 1": The cell shape is non-uniform and there are many broken bubbles.

[Branching index]
The branching index can be calculated by measuring the frequency dependence of the viscoelasticity of the copolymer and applying it to the following equation.
Branch index = [Log (η0.01) −Log (0.116 × η8) ^1.2367 ] × 10
... (II)
(In the formula (II), η 0.01 represents a viscosity (Pa · sec) of 0.01 rad / sec at 190 ° C., and η 8 represents a viscosity (Pa · sec) of 8 rad / sec at 190 ° C.)
η0.01 and η8 were measured using a rheometric viscoelasticity tester (model RDS-2). Specifically, a sample formed into a disk shape having a diameter of 25 mm × 2 mm from a 2 mm thick sheet obtained by pressing the copolymer at 190 ° C. was measured under the following conditions. Note that RSI Orchestrator (Rheometric) was used as data processing software.
Geometry: parallel plate,
Measurement temperature: 190 ° C.
Frequency: 0.01-100 rad / sec,
Distortion rate: 1.0%.

  Under such conditions, the frequency dependence of the viscosity at a temperature of 190 ° C. was measured, and η * (viscosity) at 0.01 and 8 rad / sec was set to η0.01 and η8, respectively.

(Polymerization example of PET-1)
The dehydrated and purified n-hexane is supplied at a rate of 42 liters / hr to one supply port of a continuous polymerization vessel having a capacity of 300 liters, and bis (4-chlorophenyl) methylene (cyclopentadienyl) ( 1,2,3,4,7,8,9,10-octahydro-1,1,4,4,7,7,10,10-octamethyldibenzo (b, h) fluoren-12-yl) zirconium dichloride Hexane solution (0.24 mmol / liter) at a rate of 0.21 liter / hr, triisobutylaluminum hexane solution (10 mmol / liter) at 1.0 liter / hr, triphenylcarbenium tetrakis (pentafluorophenyl) Borate hexane slurry (0.1 mmol / liter) 2.0 liter / hr, vinyl norbornene It was continuously fed at a rate of 800 grams / hr (total hexane 45 liters / hr). At the same time, ethylene 1.2 kg / hr, propylene 13 kg / hr, and hydrogen 1.0 NL / h are continuously supplied to another supply port of the polymerization vessel, polymerization temperature 95 ° C., total pressure 1.6 MPaG, residence time Continuous solution polymerization was performed under conditions of 1.3 hours.

The hexane solution of ethylene-propylene-diene copolymer produced in the polymerization vessel was continuously discharged at a flow rate of 67 liter / hr through the discharge port provided in the side wall of the polymerization vessel, and the jacket portion was 8 kg / hr. It was led to a connecting pipe heated with cm ² steam. The hexane solution of the ethylene-propylene-diene copolymer heated to about 170 ° C. in the connection pipe with the steam jacket was provided at the end of the connection pipe so as to maintain the amount of solution in the polymerization tank of about 100 liters. By adjusting the opening of the liquid level control valve, the liquid was continuously fed to the flash tank through the inner pipe of a double pipe heated with 10 kg / cm ² steam. Immediately after the liquid level control valve, a supply port for injecting methanol, which is a catalyst deactivator, is attached and injected as a 1.0 vol% hexane diluted solution at a rate of 12 liters / hr. Merged. In the transfer into the flash tank, the solution temperature and the pressure adjustment valve opening were set so that the pressure in the flash tank was 0.05 MPaG and the temperature of the vapor part in the flash tank was maintained at 180 ° C. As a result, an ethylene-propylene-diene copolymer was obtained at a production speed of 8.0 kg / hr. The polymerization Mileage of the ethylene-propylene-diene copolymer was 159 kg / mmol-Zr, the [ethylene] of the obtained ethylene-propylene-diene copolymer was 1.36 dl / g, and the ethylene / propylene composition ratio was 17.0. /83.0mol%, iodine value was 7.6g / 100g.

(Polymerization example of PET-2 to PET-5)
In the same manner as in the above polymerization examples, except that the component composition ratios and polymerization conditions were changed, and copolymers having a composition and a branching index as shown in Table 1 were obtained.

[Example 1-1]
<Preparation of Kneading 1 Thermoplastic Elastomer Composition 1-1 (see Tables 1 and 2)>
Oil-extended EPT (4100E; ethylene 57.0 mol%, non-conjugated polyene: 5-ethylidene-2-norbornene, iodine value 20.0 (g / 100 g), oil-extended 48 parts) 51.3 parts; Melt flow rate (ASTM -D-1238-65T, 230 ° C., 2.16 kg load) is 2.0 g / 10 min. Polypropylene (F704NP; manufactured by Prime Polymer Co.) 10.3 parts; PET-1 shown in Table 1 (propylene 83.0 mol) %, Non-conjugated polyene: 5-vinyl-2-norbornene, iodine value 7.6 (g / 100 g)) 3.4 parts; oil-extended EPT (3072 EPM; ethylene 64.0 mol%, non-conjugated polyene: 5-ethylidene -2-norbornene, iodine value 11.5 (g / 100 g), oil exhibition 40 parts) 7.9 parts; butyl rubber (IIR065; manufactured by Exxon Chemical) 2.7 parts; 1.2 parts of pyrene (Prime Polypro E111G; manufactured by Prime Polymer); 2.0 parts of silicon oil (BY27-002; manufactured by Toray Dow Corning Silicone) and paraffinic oil (PW-100; Dynas Process manufactured by Idemitsu Kosan Co., Ltd.) Oil) (21.2 parts); for a total of 100 parts, the crosslinker 1,3-bis (tert-butylperoxyisopropyl) benzene (Perhexa 25B) 1.04 parts and the crosslinking aid divinylbenzene (DVB) -810) 2.08 parts of a mixed solution of 0.42 parts and 0.62 parts of paraffinic oil (PW-100); and the antioxidant tetrakis [methylene-3- (3 ', 5'-di-tert- Butyl-4′-hydroxyphenyl) propionate] 0.1 part of methane (Irganox 1010) was added to a 75 L Henschel mixer ( FM75-J; manufactured by Mitsui Mining Co., Ltd.) to obtain a thermoplastic elastomer composition.

  Next, this thermoplastic elastomer composition and 21 parts of paraffinic oil (PW-100) were mixed with a twin-screw mixing extruder (HyperKTX-46, manufactured by Kobe Steel Ltd.) at a cylinder temperature of 120 to 200 ° C., Melting and kneading, that is, dynamic thermal cross-linking treatment at a die temperature of 200 ° C., a rotational speed of 400 rpm, and an extrusion rate of 60 kg / hr, results in dynamic heat treatment 1 (dispersed particles of cross-linked EPT are uniformly dispersed in PP) A partially crosslinked thermoplastic elastomer composition 1-1) was obtained.

<Kneading 2-1> Preparation of thermoplastic elastomer composition 2-1 (see Table 3)
Subsequently, 93.6 parts of the obtained dynamic heat-treated product 1 (partially crosslinked thermoplastic elastomer composition) was mixed with polypropylene (propylene copolymer, B241; melt flow rate of 0.5 g / 10 min); (Prime Polymer Co., Ltd.) 0.7 parts, melt flow rate 3.0 g / 10 min polypropylene (propylene copolymer, VP103W; Prime Polymer Co., Ltd.) 2.4 parts, carbon black masterbatch (PE4993; CABOT Co., Ltd.) 3.3 parts), 1.15 parts fluorine resin (polytetrafluoroethylene, fluon G355; manufactured by Asahi Glass Co., Ltd.), 23.6 parts paraffinic oil (PW-100), oxidized The inhibitor tetrakis [methylene-3- (3 ′, 5′-di-tert-butyl-4′-hydroxyphenyl) propionate] methane ( Irganox 1010) 0.15 part was added, and the mixture was melt kneaded under the same conditions as kneading 1 using a kneading 1 shaft extruder to obtain a thermoplastic elastomer composition 2-1. The results of evaluating the physical properties are shown in Table 4.

[Examples 1-2 to 1-6, Comparative Examples 1-1 to 1-2]
A thermoplastic elastomer composition was obtained in the same manner as in Example 1-1 except that the compositions shown in Tables 1 to 3 were changed. The evaluation results are shown in Table 4.

[Example 2-1]
Per 100 parts of the thermoplastic elastomer composition obtained in the kneading 2-1, 3.5 parts of a foaming agent (soda-type EE385; manufactured by Eiwa Kasei Co., Ltd.) and calcium stearate (manufactured by Sansha Kikai Co., Ltd.) as a foam nucleating agent 0 .1 part was dry blended, using an extrusion foam molding apparatus (Nagata Corporation), cylinder temperature 150-220 ° C., die temperature 170 ° C., rotation speed 25 rpm, resin pressure 12.5 MPa, take-off speed 7.1 m / Minute, extrusion was carried out into a round shape at an Air flow rate of 0.8 L / min, to obtain a round-shaped foam molded body.

  Various physical properties were evaluated using the foamed molded product obtained here. The results are shown in Table 5.

[Examples 2-2 to 1-6, Comparative Examples 2-1 to 2-2]
Except having changed into the composition shown in Tables 1-3, the foaming molding was obtained like Example 2-1. The evaluation results are shown in Table 3.

  The amount of each component in the following tables is expressed in parts by mass.

  In each table, “EPT” represents ethylene / propylene / 5-ethylidene-2-norbornene copolymer rubber, “PP” represents polypropylene, and “PET” represents propylene / ethylene / diene copolymer.

Claims (18)

An olefin rubber (Ax) having an ethylene content of more than 50 mol%;
A non-crosslinked polyolefin resin (B);
A thermoplastic elastomer composition comprising: an olefin rubber (Cx) in which the content of each structural unit derived from an α-olefin having 2 to 20 carbon atoms (excluding propylene) is 50 mol% or less. An olefin rubber (A) in which at least a part of the olefin rubber (Ax) having an ethylene content of more than 50 mol% is crosslinked;
Non-crosslinked polyolefin resin (B);
Olefin rubber (Cx) in which the content of each structural unit derived from an α-olefin having 2 to 20 carbon atoms (excluding propylene) is 50 mol% or less, and at least part of the olefin rubber (Cx) is crosslinked. At least one selected from the olefin-based rubber (C),
A thermoplastic elastomer composition comprising: An olefin rubber (A) in which at least a part of the olefin rubber (Ax) having an ethylene content of more than 50 mol% is crosslinked;
Non-crosslinked polyolefin resin (B);
An olefin rubber (C) in which at least a part of the olefin rubber (Cx) is crosslinked;
The thermoplastic elastomer composition according to claim 2 comprising:   Dynamic heat-treated product obtained by the step [I] of dynamically heat-treating the olefin rubber (Ax), the non-crosslinked polyolefin resin (B), the olefin rubber (Cx), and the crosslinking agent (D). The thermoplastic elastomer composition according to claim 2 or 3.   Non-crosslinked polyolefin resin (B) is 10 to 200 parts by mass, olefin rubber (Cx) or olefin rubber (C) is 100 parts by mass of olefin rubber (Ax) or olefin rubber (A). The thermoplastic elastomer composition according to any one of claims 1 to 4, which is contained in an amount of 1 to 50 parts by mass. Ethylene / α-olefin / non-conjugated polyene copolymer obtained from olefin-based rubber (Ax) or olefin-based rubber (A) obtained from ethylene exceeding 50 mol%, α-olefin having 3 to 20 carbon atoms and non-conjugated polyene At least one olefin rubber selected from the combined rubber (A1) and an ethylene / α-olefin copolymer rubber (A2) obtained from ethylene exceeding 50 mol% and an α-olefin having 3 to 20 carbon atoms, or An olefin rubber in which at least a part of the olefin rubber is crosslinked,
The non-crosslinked polyolefin resin (B) is at least one non-crosslinked olefin resin selected from a propylene homopolymer, a propylene copolymer, and an ethylene copolymer,
Olefin rubber (Cx) or olefin rubber (C) is a propylene / ethylene / nonconjugated polyene copolymer rubber (C1) obtained from propylene, 50 mol% or less of ethylene and nonconjugated polyene, and propylene and 50 mol 2. At least one olefinic rubber selected from propylene / α-olefin copolymer rubber (C2) obtained from less than or equal to% ethylene, or an olefinic rubber in which at least a part of the olefinic rubber is crosslinked. The thermoplastic elastomer composition as described in any one of -5.   The thermoplastic elastomer composition according to any one of claims 1 to 6, wherein the intrinsic viscosity of the olefin rubber (Cx) measured in decalin at 135 ° C is 0.1 to 3.0 dl / g.   The non-conjugated polyene contained in the copolymer rubbers (A1) and (C1) is at least one of 5-ethylidene-2-norbornene and 5-vinyl-2-norbornene. Thermoplastic elastomer composition. The thermoplastic elastomer composition according to any one of claims 1 to 8, wherein a branching index represented by the following formula (1) of the olefin rubber (C1) or the olefin rubber (Cx) is 2 to 20. object.
Branch index = [Log (η0.01) −Log (0.116 × η8) ^1.2367 ] × 10 (1)
[In the formula, η0.01 indicates a viscosity (Pa · sec) of 0.01 rad / sec at 190 ° C., and η8 indicates a viscosity (Pa · sec) of 8 rad / sec. ]   The softener (E) is further contained, and the content of the softener (E) is 1 to 200 parts by mass with respect to 100 parts by mass of the olefin rubber (Ax) or the olefin rubber (A). The thermoplastic elastomer composition according to any one of the above.   A fluorine resin (F) is further included, and the content of the fluorine resin (F) is 0.05 to 20 parts by mass with respect to 100 parts by mass of the olefin rubber (Ax) or the olefin rubber (A). Item 11. The thermoplastic elastomer composition according to any one of Items 1 to 10.   The molded object which consists of a thermoplastic elastomer composition as described in any one of Claims 1-11.   The thermoplastic elastomer composition for foaming formed by mix | blending the thermoplastic elastomer composition as described in any one of Claims 1-11, and a foaming agent (G).   The thermoplastic elastomer composition for foaming according to claim 13, wherein the blending amount of the foaming agent (G) is 0.1 to 30 parts by mass with respect to 100 parts by mass of the thermoplastic elastomer composition.   The foaming thermoplastic elastomer composition according to claim 13 or 14, wherein the foaming agent (G) is an inorganic or organic thermal decomposition type chemical foaming agent or physical foaming agent.   The foam obtained from the thermoplastic-elastomer composition for foaming as described in any one of Claims 13-15.   An automobile part comprising the foam according to claim 16.   A civil engineering / building material, an industrial part, an electric / electronic part, a sports / leisure article or a miscellaneous product comprising the foam according to claim 16.

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